X-ray photoelectron spectroscopy study of magnetic films

Ta/NiO_x/Ni₈₁Fe₁₉/Ta films were prepared by rf reactive and dc magnetron sputtering. The exchange coupling field H_ex and the coercivity H_c of NiO_x/Ni₈₁Fe₁₉ as a function of the ratio of Ar to O₂ during the deposition process were studied. The composition and the chemical states in the interface region of NiO_x/NiFe were also investigated using X-ray photoelectron spectroscopy (XPS) and the peak decomposition technique. The results show that the ratio of Ar to O₂ has a great effect on the chemical states of nickel in NiO_x films. The exchange coupling field H_ex and the coercivity H_c of Ta/NiO_x/Ni₈₁Fe₁₉/Ta are thus seriously affected. XPS is shown to be a powerful tool for characterizing magnetic films. Received: 18 July 2001 / Accepted: 21 December 2001 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-010/6232-7283, E-mail: guanghua_yu@263.net     

X-ray photoelectron spectroscopy study of NiSi formation on shallow junctions

The influence of boron (B)/arsenic (As) on X-ray photoelectron spectroscopy (XPS) study of NiSi formation on shallow junctions is investigated in this paper. The Ni-silicide film was formed after 30 s soak anneal at 450 °C on ultra shallow p+/n or n+/p junctions. The atomic ratio of Ni/Si profile in depth was probed by XPS and the results show that a uniform NiSi layer forms on B-doped p+/n junction while a non-uniform, Ni-rich silicide layer forms on As-doped n+/p junction. It does not agree with the results of other independent phase identification methods such as X-ray diffraction, Rutherford backscattering spectroscopy, and Raman scattering spectroscopy, which all demonstrate the formation of NiSi on both n+/p and p+/n junctions. Comparing the raw binding energy spectra of Ni and Si for each silicide film, the similar spectra for Ni signals are revealed. But the Si signals with an obviously smaller intensity is found to be responsible for the apparent Ni rich silicide formation on As-doped n+/p junction. It indicates that As atoms in the silicide film can affect the sputtering yield of Ni and Si, while no noticeable effect is observed for B atoms. More As atoms than B atoms segregation into the silicide layer is indeed verified by secondary ion mass spectroscopy. And micro-Raman scattering spectroscopy further confirms that the degree of crystallinity for NiSi on n+/p junction is inferior to that on p+/n junction.     

Thickness determination of molecularly thin lubricant films by angle-dependent X-ray photoelectron spectroscopy

An angle-dependent X-ray photoelectron spectroscopy (XPS) method used to measure the thickness of molecularly thin lubricants was developed. The method was built based on an island model of patched overlayer on a flat substrate by using the photoemission signal solely from the lubricant film. Typical molecularly thin Zdol films on the CHx overcoat of unused commercial magnetic disks were measured to verify the metrology. The lubricant thickness determined by the metrology was equal to the recent result by thermostatic high vacuum atomic force microscopy. The measured deduction in the thickness of the molecularly thin lubricant films, successively irradiated by the monochromatic source operated at 14 kV/250 W, was as low as 1 ? during the first irradiation hour. XPS spectra showed that no hydrocarbons, water or oxygen were adsorbed over the Zdol outer surfaces in the tested XPS conditions. The inelastic mean free path (IMFP) of C 1s in Zdol or in CHx was found to be independent of take off angle (TOA) when TOA < 40°. The IMFP of C 1s in Zdol was ∼63.5 ? and the lubricant island thickness was ∼35 ?.     

Chemical analysis of semiconducting and metallic SmS thin films by X-ray photoelectron spectroscopy

We studied the chemical state of semiconducting and metallic SmS thin films by X-ray photoelectron spectroscopy (XPS), which were fabricated using dual-target magnetron sputtering by controlling the power applied to both metal and chalcogenide targets. On the basis of the valence band spectra obtained, it was suggested that semiconducting SmS has the final state corresponding to the Sm²⁺(4f⁶) configuration below the Fermi level, and metallic SmS has mainly the Sm³⁺(4f⁵) final state and a virtual band state in the Sm 5d band, contributing to the delocalization of 4f electrons and the emergence of metallic conductivity (4f⁶d⁰-4f⁵d¹). Thus, the spectra of our fabricated SmS thin films correspond to the band structure obtained from the dielectric property. This is the first work performed on the intrinsically prepared metallic SmS while the former works done for the sample transformed from semiconductor to metal phase by hard polishing.     

Synthesis and thermal stability of Zn3N2 powder

This paper reports that Zn₃N₂ powder of high quality has been synthesized by a nitridation reaction of Zn powder with NH₃ gas (flow rate 500 ml/min) at the nitridation temperature of 600 °C for 120 min. X-ray diffraction indicates that Zn₃N₂ is cubic in structure with the lattice constant being a=9.788 Å. X-ray photoelectron spectroscopy shows the differences of chemical bonding states between Zn₃N₂ and ZnO, and confirms the formation of N-Zn bonds. Thermal gravimetric analysis and differential thermal analysis are employed to investigate the thermal decomposition behavior of Zn₃N₂ powder. It is found that Zn₃N₂ is unstable when exposed to open air above 500 °C.     

Investigation of the interaction of evaporated aluminum with vapor deposited Teflon AF films via X-ray photoelectron spectroscopy

The interfacial bonding and mixing between evaporated aluminum and a vapor deposited Teflon AF (abbreviated to AF) film have been investigated with X-ray photoelectron spectroscopy. Graphite carbon (C–C), and aluminum carbide (Al–C), oxide (Al–O–C) and fluoride (Al–F) are formed when aluminum atoms are deposited on to the AF film. With increasing deposition of aluminum, the concentrations of these newly formed components increase gradually. Moreover, in situ annealing results in remarkable increases in the C–C, Al–C, Al–O–C and Al–F configurations and a decrease in metallic aluminum. No significant diffusion of aluminum into the AF film was observed during the annealing. The Al compounds form a layer at the Al/AF interface that acts as an adhesion promoter and diffusion barrier. Received: 21 October 2002 / Accepted: 22 October 2002 / Published online: 15 January 2003 RID="*" ID="*"Corresponding author. Fax: +49-431/880-6229, E-mail: sjding@yahoo.com     

Method of observation of low density interface states by means of X-ray photoelectron spectroscopy under bias and passivation by cyanide ions

X-ray photoelectron spectroscopy (XPS) measurements under bias can observe low density interface states for metal-oxide-semiconductor (MOS) diodes with low densities. This method can give energy distribution of interface states for ultrathin insulating layers for which electrical measurements cannot be performed due to a high density leakage current. During the XPS measurements, a bias voltage is applied to the rear semiconductor surface with respect to the ∼3 nm-thick front platinum layer connected to the ground, and the bias voltage changes the occupation of interface states. Charges accumulated in the interface states shift semiconductor core levels at the interface, and thus the analysis of the bias-induced shifts of the semiconductor core levels measured as a function of the bias voltage gives energy distribution of interface states. In the case of Si-based MOS diodes, the energy distribution and density of interface states strongly depend on the atomic density of silicon dioxide (SiO₂) layers and the interfacial roughness, respectively. All the observed interface state spectra possess peaked-structures, indicating that they are due to defect states. An interface state peak near the Si midgap is attributable to isolated Si dangling bonds at the interface, while those above and below the midgap to Si dangling bonds interacting weakly with Si or oxygen atoms in the SiO₂ layers. A method of the elimination of interface states and defect states in Si using cyanide solutions has been developed. The cyanide method simply involves the immersion of Si in KCN solutions. Due to the high Si-CN bond energy of ∼4.5 eV, the bonds are not ruptured at 800 °C and upon irradiation. The cyanide treatment results in the improvement of the electrical characteristics of MOS diodes and solar cells.     

Surface composition and electronic structure of Ni2+xMn1−xGa studied by X-ray photoelectron spectroscopy

The surface of Ni_2+xMn_1−xGa have been studied using X-ray photoelectron spectroscopy under different conditions of surface preparation. We find that the surface becomes Ni rich by argon ion sputtering. However, the change in surface composition due to sputtering can be reverted by annealing at appropriate temperature so that the bulk composition is restored at the surface. The origin of a satellite feature observed both in the valence band and the Ni 2p core-level spectra is discussed. The magnetic microstructures at the surface have been observed by using magnetic force microscopy.     

Core level spectroscopy and RHEED analysis of KGd(WO4)2 surface

Structural and electronic characterisation of mechanically polished (010) KGd(WO₄)₂ (KGW) has been produced by reflection high-energy electron diffraction (RHEED) and X-ray photoelectron spectroscopy (XPS). With XPS analysis the original element binding energies, chemical composition and valence band structure of KGW have been determined.     

Characterization of Pd-CeOx interaction on α-Al2O3 support

The Pd-Ce interaction was studied over CeO₂ (0.3-2.5 wt.%)-Pd (1 wt.%)/α-Al₂O₃ catalysts used in the reforming reaction of CH₄ with CO₂. The samples were characterized by using high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). The activity and selectivity behavior was in good agreement with that of other supported metal catalysts (Ni and Pd) modified with different promoters. The preliminary results of HRTEM would indicate that the CeO_x forms small crystallites around the Pd particle. The XPS analysis for the regions of Ce 3d and Pd 3d, gives an account of Ce being present mostly as Ce³⁺ and a high binding energy for Pd 3d_5/2 (335.3 eV), an evidence of Pd-Ce chemical interaction. The Pd/Al XPS intensity ratios vs. the Pd average particle size, determined by TEM, show an excellent correlation for fresh and used catalyst. These results indicate that the diminution of the Pd/Al ratios was due to Pd sintering. Consequently, the small amounts of CeO_x species do not cover the Pd particle, in agreement with the HRTEM results. The overall results stand for the promoter action mechanism of the CeO_x for the reforming reaction with CO₂.     

Characterization of a thin CeO2-ZrO2-Y2O3 films electrochemical deposited on stainless steel

In this paper, we report for the first time formation of a thin CeO₂-ZrO₂-Y₂O₃ films electrodeposited on a stainless steel substrate. The samples have been characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The XRD and XPS data indicate formation of a solid solution and additional existence of Ce³⁺ states near the surface. After annealing, SEM examination has shown a microstructure formed by dispersed spherical agglomerates having a size between 20 and 60 nm.     

Auger electron spectroscopy of Au/NiOx contacts on p-GaN annealed in N2 and O2 + N2 ambients

We have designed a promising contact scheme to p-GaN. Au/NiO_x layers with a low concentration of O in NiO_x are deposited on p-GaN by reactive dc magnetron sputtering and annealed in N₂ and in a mixture of O₂ + N₂ to produce low resistivity ohmic contacts. Annealing has been studied of NiO_x layers with various contents of oxygen upon the electrical properties of Au/NiO_x/p-GaN. It has been found that the Au/NiO_x/p-GaN structure with a low content of oxygen in NiO_x layer provides a low resistivity ohmic contact even after subsequent annealing in N₂ or O₂ + N₂ ambient at 500 °C for 2 min.Auger depth profiles and transmission electron microscopy (TEM) micrographs reveal that while annealing in O₂ + N₂ ambient results in reconstruction of the initial deposited Au/NiO_x/p-GaN contact structure into a Au/p-NiO/p-GaN structure, annealing in N₂ brings about reconstruction into Au/p-NiO/p-GaN and Ni/p-NiO/p-GaN structures. Hence, in both cases, after annealing in N₂ as well as in O₂ + N₂ ambient, the ohmic properties of the contacts are determined by creation of a thin oxide layer (p-NiO) on the metal/p-GaN interface. Higher contact resistivities in the samples annealed in O₂ + N₂ ambient are most likely caused by a smaller effective area of the contact due to creation of voids.     

Crystallographic and magnetic properties of (Nd,Dy)3Fe27.5(Ti,Mo)1.5 compounds

A systematic study of the formation, structure and magnetic properties of (Nd,Dy)₃Fe_27.5(Ti,Mo)_1.5 compounds has been performed. Rietveld analyses of the X-ray patterns of the samples indicate that the concentrations of Ti and Mo affect the formation and structural properties slightly, whereas different rare-earth (Nd and Dy) contents influence them significantly. It is found that high Dy contents make it difficult to form the 3:29-type structures. The Curie temperatures of Nd_2.1Dy_0.9Fe_27.5Ti_1.5−xMo_x decrease monotonically as more Ti was replaced by Mo but their saturation magnetizations remain almost unchanged; in contrast, for Nd_3−yDy_yFe_27.5TiMo_0.5, their saturation magnetizations decrease monotonically with increasing Dy contents while their Curie temperatures are constant.     

X-ray diffraction characterization of a spatially coherent crystalline nanocomposite obtained from a melt of KCl, KBr and KI salts

Crystalline bulks, obtained by the Bridgman technique from a melt that was previously prepared by mixing equal molar fractions of the salts KBr, KCl and KI were characterized by powder and single-plate X-ray diffraction. The crystalline bulks are formed by a composite material consisting of a highly textured aggregation of crystallites of two different face-centred-cubic solid solutions with corresponding unit-cell sizes of 7.020(2) and 6.456(3) Å. The relative molar fraction concentrations of these solid solutions in the composite are about 0.348 and 0.652, respectively. From these solutions, the first is identified as the binary KBr(9.7%):KI(90.3%) mixed phase and the second is discussed to be the ternary KBr (45.9%):KCl (51.1%):KI (3.0%) mixed phase. The lattices of most of the crystallites forming the composite, no matter the phase they belong to, are spatially coherent to each other within the crystalline bulk.     

A method for the experimental determination of the net atomic charge via X-ray photoemission spectroscopy

A method for the experimental determination of the net charge distribution over the atoms in a large class of compounds is described. The method is based on X-ray photoemission spectroscopy and requires the determination of two core-level energies per constituting atomic species. Two special cases of large conceptual and practical interest are discussed: the silicon charge in CoSi₂, Si_1-xGe_x (0≤x≤0.3), SiC, Si₃N₄ and SiO₂, and the aluminum charge in aluminum-doped zeolites. Received: 20 March 2000 / Accepted: 28 March 2000 / Published online: 21 March 2001     

An XPS study of CrOx on a thin alumina film and in alumina supported catalysts

We have investigated chromium layers evaporated onto a thin alumina film at room temperature. The oxidation and reduction behavior of this model catalyst was compared to atomic layer deposition (ALD) and impregnated alumina supported catalysts using X-ray photoelectron spectroscopy (XPS) with a detailed analysis method utilizing asymmetric peak shapes to represent both metallic and oxidic states. The ALD and impregnated catalysts were measured after calcination in air and after reduction with several gases at 850 K. Both catalysts show Cr³⁺ and Cr⁶⁺ species after calcination and mostly Cr³⁺ after reduction. The chromium layers deposited in vacuum show initially small partial oxidation due to the interaction with the oxygen terminated alumina film. These model catalysts can be oxidized in vacuum to Cr³⁺ species but not to higher oxidation states. The model catalysts were also subjected to calcination and reduction treatments after deposition in vacuum. Under these conditions the model systems exhibit similar oxidation/reduction behavior as the supported catalysts. Photoreduction of Cr⁶⁺ during the measurements was also studied and found to be very slow having a negligible effect on the results.     

XPS and ToF-SIMS analysis of natural rubies and sapphires heated in an inert (N2) atmosphere

Advanced surface analysis techniques: X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry, have been employed in the study of heat treatment of natural corundum as ruby and sapphire. The stones were heat treated in an inert (N₂) atmosphere. The setting temperatures were: 1000, 1100, 1200, 1300, 1400, 1500 and 1600 °C. The XPS studies and the parallel ToF-SIMS experiments revealed diffusion behavior of Fe and Ti in the as-mined stones as evidenced by surface observations. Both metals exhibited broad maxima in surface concentration near 1300 °C. Owing to its superlative detection limit, ToF-SIMS spectra are able to provide the temperature-dependent concentration profiles of trace transition metals such as Cr, Cu and V at a level not detectable by XPS. Visible appearance of the stones is clearly affected by heat treatment. Interestingly, the ruby stones did not exhibit cloudy inclusion (“silk”) on heating, contrary to previous experiments under atmospheric conditions.     

Effect of alkali leaching on the surface structure of Ni3Al catalyst

The surface structure of the alkali-leached single-phase Ni₃Al powder was investigated by X-ray diffraction, BET (Brunauer-Emmett-Teller) surface area analysis, electron microscopy, X-ray photoelectron spectroscopy, and temperature-programmed reduction. It was found that fine Ni particles of several nm in diameter were formed on the outer surface layer of the Ni₃Al powder after the alkali leaching process. The surface of the Ni particles was covered with a thin layer of Ni oxides and hydroxide, Ni₂O₃, NiO and Ni(OH)₂, and these Ni oxides and hydroxide can be easily reduced by hydrogen to the metallic nickel that is catalytically active. The inside of the Ni₃Al powder remained as the original Ni₃Al ordered structure after alkali leaching. Having heat resistant properties, the Ni₃Al phase can serve as a support of the fine Ni particles and provide the structural and thermal stabilities to the fine Ni particles.     

Order-disorder transformation in the binary MPt3 and ternary CuMPt6 (M=3d metals) alloys

The order-disorder(O-D) transformation in the binary MPt₃ and the ternary CuMPt₆ (M=3d transition metals) alloys were studied. The O-D transformation temperatures (T_c) were calculated by combining the method of pseudopotentials with the static concentration waves. The method originally proposed by Khachaturyan [Progress in Materials Science, vol. 22, Pergamon Press Ltd., Oxford, 1978, pp. 47-49; Phys. Met. Metallography 13 (1962) 493; Sov. Phys. Solid State 5 (1963) 16; Sov. Phys. Solid State 5 (1963) 548] was applied to the case of ternary CuMPt₆ alloys by using the concept of a pseudoatom. It is found that this model predicts results that are consistent with the experimental data.     

Crystal structure and the magnetic properties of CeTiGe3

The crystal structure of the RTiGe₃ compounds (R=La, Ce and Pr) has been studied by X-ray powder diffraction methods; Rietveld refinement has been carried out on the La homologue. These compounds crystallise in the BaNiO₃ prototype structure, hP10-P6₃/mmc, also called the hexagonal perovskite (a=6.300(1), c=5.915(1) Å for LaTiGe₃). This seems to be the first example in which an intermetallic phase adopts such a structure type which can be considered as derived from the Ni₃Sn type (anti) by a distortion of the lattice and the occupation of the quasi-octahedral 2a site at the origin of the cell (0, 0, 0) by Ti. The composition, also confirmed by microprobe analyses, was found to be strictly 1:1:3 indicating that these are line compounds, forming very likely by a peritectoid reaction. The existence of homologous compounds has been established for the lighter rare earths La, Ce and Pr. Heat capacity and magnetisation data show that CeTiGe₃ orders ferromagnetically with a Curie temperature of nearly 14 K. On the other hand a−ln T variation of the magnetic part of the resistivity below 300 K is consistent with that expected for single impurity Kondo behaviour. CeTiGe₃ is thus an uncommon example of a ferromagnetic dense Kondo lattice.