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.     

Sputter-induced cross-contamination in analytical AES and XPS instrumentation: utilization of the effect for the in situ deposition of ultrathin functional layers

Cross-contamination is observed on sample surfaces by Auger electron spectroscopy and X-ray photoelectron spectroscopy if multiple samples are mounted on one sample holder and a neighbouring sample was sputter depth profiling. During sputter depth profiling, sputtered material is deposited on inner surfaces of the instrument. In a secondary sputter process, which is due to species leaving the primary sputter target with higher kinetic energy, the previously deposited material is transported from the inner surfaces to the other samples mounted on the sample holder. This reflective sputtering is utilized to deposit ultrathin layers on sample surfaces for X-ray photoelectron spectroscopy binding energy referencing purposes and to build up ultrathin conductive layers to make possible Auger electron spectroscopy measurements on insulating samples.     

Chemical Composition and Microstructure of Plasma-Nitrided Aluminium

 Detailed examinations were made by AES depth profiling, SEM, TEM and electron diffraction to get information about the relation between treatment conditions and the state of plasma-nitrided aluminium. The chemical composition and the elemental depth distribution were proofed to be depending on gas phase mixture, pressure and temperature during plasma treatment. The admixture of hydrogen during presputtering for surface cleaning and during nitriding results both in an improved nitriding behaviour and in a reduction of the formation of conical-shaped particles at the surface. The microstructure of the nitride layer isn’t depending on tested process conditions significantly. Surface and interface between layer and substrate are roughly in a scale of a few ten nanometers owing to sputtering effects. The main phase inside the layer is nanocrystalline AlN of the known hexagonal modification. In addition, some crystallites of remaining aluminium are present as a second phase. In contrast to nitrogen-implanted aluminium no preferred lattice orientation of the AlN phase was evident.     

Investigation on anodized aluminium

Results of examinations with TEM, SEM, EDX, ISS, SIMS and AES on sulphuric acid anodized films on aluminium are reported. Important technical information about the 20-μm thick coatings were obtained by monolayer and depth analysis. The fine structure of the oxide film and its modifications during a sealing process are discussed. Possibilities to prevent sealing smut on the surface are shown. The metal distribution inside the films which are coloured electrolytically with metal salts, is investigated.     

Oxide and nitride protective layers on stainless steel studied by AES,WDS and XPS

Protective surface layers on AISI 321 stainless steel were prepared by thermal treatments at two different temperatures in air and two controlled atmospheres. Different oxide and/or nitride layers were formed. Surface morphology of the layers was investigated by scanning electron microscopy (SEM). Auger electron spectroscopy (AES) depth profiling of the samples was performed. Since depth profiling suggested layer thicknesses of the order of hundreds of nanometres, an attempt was made to obtain some fast, averaged information about the layer compositions using wavelength dispersive spectroscopy (WDS) at two different beam energies to obtain probing depths best suited to the layer thickness. X‐ray photoelectron spectroscopy (XPS) profiling of one layer was also performed to obtain information about the chemical states of the elements inside the layer. The analysed samples showed considerable differences with respect to their surface morphology, oxide/nitride layer thicknesses, compositions and layer–metal interface thickness. Copyright © 2007 John Wiley & Sons, Ltd.     

X-ray and electron induced Auger processes for I2 adsorption on uranium

The accurate determination of the kinetic energy of X-ray induced Auger electrons, which is necessary in XPS experiments, e.g. for calculating the Auger parameter, is sometimes hampered by peak interferences or by the high secondary electron background. The latter is of special importance for low kinetic energy electrons like e.g. the U(OPV) and U(OVV) Auger electrons. These problems can be circumvented by using electron induced Auger transitions (AES). However, since XPS and AES use different reference points for the energy scales, both scales have to be matched. This can be done by measuring the kinetic energy of an appropriate Auger transition in XPS and relating this value to the maximum of the second derivative of the same peak in AES.     

Simultaneous SIMS/AES Measurements for the Characterization of Multilayer Systems

The interface region of silicon dioxide layers deposited on indium phosphide was investigated by simultaneous secondary ion mass spectroscopy (SIMS) and Auger electron spectroscopy (AES) depth profile measurements. The results of such measurements depend strongly on the ion species used for sputtering. With Ar⁺ primary ions an enhancement of the P- and In-SIMS signals occurs in the mixing zone at the interface. This effect can be explained by an increase of the ionization yield of In and P in the presence of oxygen from the SiO₂. The use of O₂ ⁺ as sputter ions enlarges the phosphorus peak at the interface while the enhancement of the In-signal diminishes. The simultaneously measured AES spectra give clear evidence of oxygen bonded In and P at the interface. Additionally, preferential sputtering of phosphorus occurs. The understanding of these effects which complicate the interpretation of SIMS and AES depth profile measurements of the system SiO₂/InP allows us to investigate the silicon dioxide layers and the interface region in order to optimize the SiO₂ deposition process, e.g. for surface passivation or MIS structures.     

Monte Carlo simulation of full energy spectrum of electrons emitted from silicon in Auger electron spectroscopy

A Monte Carlo simulation including surface excitation, Auger electron‐ and secondary electron production has been performed to calculate the energy spectrum of electrons emitted from silicon in Auger electron spectroscopy (AES), covering the full energy range from the elastic peak down to the true‐secondary‐electron peak. The work aims to provide a more comprehensive understanding of the experimental AES spectrum by integrating the up‐to‐date knowledge of electron scattering and electronic excitation near the solid surface region. The Monte Carlo simulation model of beam–sample interaction includes the atomic ionization and relaxation for Auger electron production with Casnati's ionization cross section, surface plasmon excitation and bulk plasmon excitation as well as other bulk electronic excitation for inelastic scattering of electrons (including primary electrons, Auger electrons and secondary electrons) through a dielectric functional approach, cascade secondary electron production in electron inelastic scattering events, and electron elastic scattering with use of Mott's cross section. The simulated energy spectrum for Si sample describes very well the experimental AES EN(E) spectrum measured with a cylindrical mirror analyzer for primary energies ranging from 500 eV to 3000 eV. Surface excitation is found to affect strongly the loss peak shape and the intensities of the elastic peak and Auger peak, and weakly the low energy backscattering background, but it has less effect to high energy backscattering background and the Auger electron peak shape. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface analytical examinations of welded nickel alloys by XPS, SNMS and SEM/EDX

Tarnish layers are formed in the heat affected zone during the welding of steels and nickel based alloys. They commonly consist of oxides of the alloying elements. The corrosion behaviour of welded components is generally influenced by the thickness and composition of the oxide films. In the following the corrosion behaviour of annealed samples cut from NiMo28 and NiMo16Cr16Ti is investigated, correlating XPS, SNMS and SEM/EDX data to their pitting corrosion potentials.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Preferential sputtering observed in Auger electron spectroscopy sputter depth profiling of AlAs/GaAs superlattice using low‐energy ions

Auger electron spectroscopy (AES) sputter depth profiling of an ISO reference material of the GaAs/AlAs superlattice was investigated using low‐energy Ar⁺ ions. Although a high depth resolution of ～1.0 nm was obtained at the GaAs/AlAs interface under 100 eV Ar⁺ ion irradiation, deterioration of the depth resolution was observed at the AlAs/GaAs interface. The Auger peak profile revealed that the enrichment of Al due to preferential sputtering occurred during sputter etching of the AlAs layer only under 100 eV Ar⁺ ion irradiation. In addition, a significant difference in the etching rates between the AlAs and GaAs layers was observed for low‐energy ion irradiation. Deterioration of the depth resolution under 100 eV Ar⁺ ion irradiation is attributed to the preferential sputtering and the difference in the etching rate. The present results suggest that the effects induced by the preferential sputtering and the significant difference in the etching rate should be taken into account to optimize ion etching conditions using the GaAs/AlAs reference material under low‐energy ion irradiation. Copyright © 2005 John Wiley & Sons, Ltd.     

Quantitative Auger depth profiling of LPCVD and PECVD silicon nitride films

Summary Thin silicon nitride films (100–210 nm) with refractive indices varying from 1.90 to 2.10 were deposited on silicon substrates by low pressure chemical vapour deposition (LPCVD) and plasma enhanced chemical vapour deposition (PECVD). Rutherford backscattering spectrometry (RBS), ellipsometry, surface profiling measurements and Auger electron spectroscopy (AES) in combination with Ar⁺ sputtering were used to characterize these films. We have found that the use of (p-p)heights of the Si LVV and N KLL Auger transitions in the first derivative of the energy distribution (dN(E)/dE) leads to an accurate determination of the silicon nitride composition in Auger depth profiles over a wide range of atomic Si/N ratios. Moreover, we have shown that the Si KLL Auger transition, generally considered to be a better probe than the low energy Si LVV Auger transition in determining the chemical composition of silicon nitride layers, leads to deviating results.

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Quantitative Auger-Tiefenprofilanalyse von LPCVD- und PECVD-Siliciumnitridfilmen

     

Depth profiling with SNMS and SIMS of Zn(O,S) buffer layers for Cu(In,Ga)Se2 thin‐film solar cells

Zn(O,S) is a promising candidate to replace the commonly used CdS buffer layer for Cu(In,Ga)Se₂ (CIGS) thin‐film solar cells due to its non‐toxicity and its potential to enhance the conversion efficiency of the CIGS solar cell. The composition of chemical bath deposited (CBD) and sputtered Zn(O,S) layers with thicknesses well below 100 nm was determined by sputtered neutral and secondary ion mass spectrometry (SNMS and SIMS). Despite numerous mass interferences of double‐charged atoms and dimers with single Zn, O and S isotopes, we developed an evaluation algorithm for quantification of SNMS depth profiles of Zn(O,S) layers. In particular, the superposition of double‐charged S and Zn atoms with O and S isotopes is accounted for numerically in the quantification procedure. For sputtered Zn(O,S) layers, the S/(S + O) atomic ratio and the vertical composition profile can be controlled by the O₂ content in the gas flow and the substrate temperature during sputtering whereas for CBD Zn(O,S) the S/(S + O) ratio is constant around 0.7–0.8. A Cu‐depleted layer of about 5 nm on the CIGS surface after buffer deposition was observed for both preparation methods. With negative SIMS, we found more hydroxides and carbon residues in CBD Zn(O,S) as compared to sputtered layers. Best cell performance with sputtered Zn(O,S) layers was achieved for S/(S + O) ratios of 0.25–0.40, yielding efficiencies up to 13%. Our solar cells with CBD Zn(O,S) buffers exhibit higher efficiencies due to an improved open‐circuit voltage. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface analytical investigation of the electrochemical and corrosion behaviour of nanocrystalline FeAl8

From the higher fraction of grain boundaries in nanocrystalline substances a different corrosion behaviour in comparison to the conventional polycrystalline material can be expected, which may be utilised for the development of new corrosion resistant alloys. Therefore, the oxidation behaviour of these two different crystallisation states of FeAl8 was compared by means of electrochemical and surface analytical experiments. The oxide films formed after electrochemical passivation were investigated by Auger Electron Spectroscopy. The application of inelastic peak shape analysis by the method of Tougaard showed, that for both materials the oxide layer may be described by a model of a (below the contamination) buried layer with a thickness of only a few nanometers depending on the preparation conditions. Factor Analysis was applied for the evaluation of the differentiated low energy Auger electron spectra (20–100 eV) as a function of depth profiling sputtering time. For both, the nanocrystalline and the polycrystalline material, the inner part of the oxide layer was enriched in Al, whereas the very outer part (surface region) was enriched in Fe. No differences concerning the sputtering time for removal of the oxide layers were found for the two alloys.     

Quantitative surface analysis by Auger and x-ray photoelectron spectroscopy

Recent developments in quantitative surface analysis by Auger (AES) and x-ray photoelectron (XPS) spectroscopies are reviewed and problems relating to a more accurate quantitative interpretation of AES/XPS experimental data are discussed. Special attention is paid to consideration of elementary physical processes involved and influence of multiple scattering effects on signal line intensities. In particular, the major features of core-shell ionization by electron impact, Auger transitions and photoionization are considered qualitatively and rigorous approaches used to calculate the respective transition probabilities are analysed. It is shown that, in amorphous and polycrystalline targets, incoherent scattering of primary and signal Auger and photoelectrons can be described by solving analytically a kinetic equation with appropriate boundary conditions. The analytical results for the angular and energy distribution, the mean escape depth, and the escape probability as a function of depth of origin of signal electrons as well as that for the backscattering factor in AES are in good agreement with the corresponding Mote Carlo simulation data. Methods for inelastic background subtraction, surface composition determination and depth-profile reconstructions by angle-resolved AES/XPS are discussed. Examples of novel techniques based on x-ray induced photoemission are considered.     

Microscopic study of ultra-thin gold layers on polyethyleneterephthalate

Continuous and discontinuous gold layers sputtered on polyethyleneterephthalate (PET) were characterized using atomic force microscopy (AFM), scanning electron microscopy (SEM) and by reflection of microwave radiation. The changes in the surface morphology of the continuous and discontinuous gold layers as a function of the sputtering time were clearly observed by AFM technique. SEM imaging of very thin gold layers was adversely affected by specimen charging. For medium sputtering times, when a continuous gold coverage is already formed, the SEM technique still show the presence of regions with very thin gold coverage which gradually disappear at longer sputtering times. Both, the AFM and SEM techniques confirmed that in the course of the gold deposition the initially small gold clusters grow and finally associate in a continuous layer. It was shown that the sub-microne metallic structures could be modeled by artificial, significantly larger structures prepared on PET by lithographic etching.     

Comprehensive comparison of various techniques for the analysis of elemental distributions in thin films

The present work shows results on elemental distribution analyses in Cu(In,Ga)Se2 thin films for solar cells performed by use of wavelength-dispersive and energy-dispersive X-ray spectrometry (EDX) in a scanning electron microscope, EDX in a transmission electron microscope, X-ray photoelectron, angle-dependent soft X-ray emission, secondary ion-mass (SIMS), time-of-flight SIMS, sputtered neutral mass, glow-discharge optical emission and glow-discharge mass, Auger electron, and Rutherford backscattering spectrometry, by use of scanning Auger electron microscopy, Raman depth profiling, and Raman mapping, as well as by use of elastic recoil detection analysis, grazing-incidence X-ray and electron backscatter diffraction, and grazing-incidence X-ray fluorescence analysis. The Cu(In,Ga)Se2 thin films used for the present comparison were produced during the same identical deposition run and exhibit thicknesses of about 2 μm. The analysis techniques were compared with respect to their spatial and depth resolutions, measuring speeds, availabilities, and detection limits.     

Application of positron annihilation induced Auger Electron Spectroscopy to the study of surface chemistry

Positron annihilation induced Auger Electron Spectroscopy (PAES), makes use a beam of low energy positrons to excite Auger transitions by annihilating core electrons. This novel mechanism provides PAES with a number of unique features which distinguishes it from other methods of surface analysis. In PAES the very large collisionally induced secondary electron background which is present under the low energy Auger peaks using conventional tecniques can be eliminated by using a positron beam whose energy is below the range of Auger electron energies. In addition, PAES is more surface selective than conventional Auger Spectroscopy because the PAES signal originates almost exclusively from the topmost atomic layer due to the fact that the positrons annihilating with the core electrons are trapped in an image correlation well just outside the surface. In this paper, recent applications of Positron Annihilation Induced Auger Electron Spectroscopy (PAES) to the study of surface structure and surface chemistry will be discussed including studies of the growth, alloying and inter-diffusion of ultrathin layers of metals, metals on semiconductors, and semiconductors on semiconductors. In addition, the possibilities for future application of PAES to the study of catalysis and surface chemistry will be outlined.     

Determination of the relative sputtering yield of carbon to tantalum by means of Auger electron spectroscopy depth profiling

The relative sputtering yield of carbon with respect to tantalum was determined for 1 keV Ar⁺ ion bombardment in the angular range of 70°–82° (measured from surface normal) by means of Auger electron spectroscopy depth profiling of C/Ta and Ta/C bilayers. The ion bombardment‐induced interface broadening was strongly different for the C/Ta and Ta/C, whereas the C/Ta interface was found to be rather sharp, the Ta/C interface was unusually broad. Still the relative sputtering yields (Y_C/Y_Ta) derived from the Auger electron spectroscopy depth profiles of the two specimens agreed well. The relative sputtering yields obtained were different from those determined earlier on thick layers, calculated by simulation of SRIM2006 and by the fitting equation of Eckstein. The difference increases with increase of angle of incidence. Copyright © 2009 John Wiley & Sons, Ltd.     

Depth profile analysis of thin film solar cells using SNMS and SIMS

SNMS (sputtered neutrals mass spectrometry) and SIMS (secondary ion mass spectrometry) are used for the depth profile analysis of thin film solar cells based on amorphous silicon. In order to enhance depth resolution, model systems are analyzed only representing parts of the layered system. Results concerning the TCO (transparent conducting oxide)/p interface and the n/i interface are presented. To minimize matrix effects, SNMS is used when the sample consists of layers with different matrices. Examples are the TCO/p interface (where the transition lengths of the depth profiles are found to be sharper when ZnO is used as TCO compared to SnO₂) and SnO₂/ZnO interfaces in coated TCO layers (where a Sn contamination inside the ZnO layer is found depending on the plasma pressure during the ZnO deposition). SIMS is used when the limits of detection reached by SNMS are not sufficient. Examples are H depth profiles in ZnO layers or P depth profiles near the n/i-interface.