Single-calcination synthesis of pyrochlore-free Pb(Ni1/3Nb2/3)O3-PbTiO3 using a coating method

Pyrochlore-free 0.64Pb(Ni_1/3Nb_2/3)O₃-0.36PbTiO₃ (0.64PNN-0.36PT) powder has been successfully synthesized by only one calcination step using a coating method. The formation of pyrochlore phase is prevented by coating NiCO₃·2Ni(OH)₂·2H₂O on Nb₂O₅ particles. NiCO₃·2Ni(OH)₂·2H₂O-coated Nb₂O₅ powder is prepared by heterogeneous precipitation method. The coating structure is confirmed by transmission electron microscope (TEM) with energy dispersive spectroscope (EDS). Single calcination treatment of the coating powder mixed with appropriate amounts of Pb₃O₄ and TiO₂ powders at 900 °C for 2 h produces the pure-perovskite 0.64PNN-0.36PT powder. The elimination of the pyrochlore phase can be explained in terms of the separating of Pb₃O₄ and Nb₂O₅ by the NiCO₃·2Ni(OH)₂·2H₂O coating layer.     

Formation of GaAs1−xNx nanofilm on GaAs by low energy N2 implantation

Nitridation of GaAs (1 0 0) by N₂⁺ ions with energy E_i = 2500 eV has been studied by Auger- and Electron Energy Loss Spectroscopy under experimental conditions, when electrons ejected only by nitrated layer, without contribution of GaAs substrate, were collected. Diagnostics for quantitative chemical analysis of the nitrated layers has been developed using the values of NKVV Auger energies in GaN and GaAsN chemical phases measured in one experiment, with the accuracy being sufficient for separating their contributions into the experimental spectrum. The conducted analysis has shown that nanofilm with the thickness of about 4 nm was fabricated, consisting mainly of dilute alloy GaAs_1−xN_x with high concentration of nitrogen x ∼ 0.09, although the major part of the implanted nitrogen atoms are contained in GaN inclusions. It was assumed that secondary ion cascades generated by implanted ions play an important role in forming nitrogen-rich alloy.     

XPS depth profiling studies of L-CVD SnO2 thin films

In this paper we present the results of the XPS atomic depth profile analysis, using ion beam sputtering, of L-CVD SnO₂ thin films grown on an atomically clean SiO₂ substrate after annealing at 400 °C in dry atmospheric air. From the evolution of the Sn 3d_5/2, O 1s, Si 2p and C 1s core level peaks our experiments allowed the determination of the in depth atomic concentration of the main components of the SnO₂/SiO₂ interface. Thin (few nm) nearly stoichiometric SnO₂ films are present at the topmost layer of the thin films, and progressive intermixing with SnO and silicon oxide is observed at deeper layer. The interface between the Sn and the Si oxide layers (i.e. the effective Sn oxide thickness) is measured at 13 nm.     

XPS and AES investigations of hard magnetic Nd-Fe-B films

Nd-Fe-B is a promising material system for the preparation of thin films with good hard magnetic properties. One problem of this material class is the sensitivity against oxidation, resulting in a degradation of the magnetic properties. Using XPS depth profiling in combination with peak-shape analysis it is shown that already after several hours oxygen can diffuse deep into the thin laser-deposited films and that Nd is mainly responsible for the oxidation. Local element analysis with AES revealed boron inhomogeneities from droplet formation during laser deposition. These problems can be solved by using a capping Cr layer and an FeB target for thin film preparation, respectively.     

Effects of experimental parameters on composition of boron carbon nitride thin films deposited by magnetron sputtering

We have synthesized boron carbon nitride thin films by radio frequency magnetron sputtering. The films structure and composition were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The results indicate that the three elements of B, C, N are chemically bonded with each other and atomic-level hybrids have been formed in the films. The boron carbon nitride films prepared in the present experiment possess a disordered structure. The influence of PN₂/PN₂+Ar, total pressure and substrate bias voltage on the composition of boron carbon nitride films is investigated. The atomic fraction of C atoms increases and the fractions of B, N decrease with the decrease of PN₂/PN₂+Ar from 75% to 0%. There is an optimum total pressure. That is to say, the atomic fractions of B, N reach a maximum and the fraction of C atoms reaches a minimum at the total pressure of 1.3 Pa. The boron carbon nitride films exhibit lower C content and higher B, N contents at lower bias voltages. And the boron carbon nitride films show higher C content and lower B, N contents at higher bias voltages.     

Growth of thin, crystalline oxide, nitride, and oxynitride films on NiAl and CoGa surfaces

At 300 K, an amorphous Al-oxide film is formed on NiAl(001) upon oxygen adsorption. Annealing of the oxygen-saturated NiAl(001) surface to 1200 K leads to the formation of thin well-ordered θ-Al₂O₃ films. At 300 K, and low-exposure oxygen atoms are chemisorbed on CoGa(001) on defects and on step edges of the terraces. For higher exposure up to saturation, the adsorption of oxygen leads to the formation of an amorphous Ga-oxide film. The EEL spectrum of the amorphous film exhibits two losses at ≈400 and 690 cm^-1. After annealing the amorphous Ga-oxide films to 550 K thin, well-ordered β-Ga₂O₃ films are formed on top of the CoGa(001) surface. The EEL spectrum of the β-Ga₂O₃ films show strong Fuchs-Kliewer (FK) modes at 305, 455, 645, and 785 cm^-1. The β-Ga₂O₃ films are well ordered and show (2×1) LEED pattern with two domains, oriented perpendicular to each other. The STM study confirms the two domains structure and allows the determination of the two-dimensional lattice parameters of β-Ga₂O₃. The vibrational properties and the structure of β-Ga₂O₃ on CoGa(001) and θ-Al₂O₃ on NiAl(001) are very similar. Ammonia adsorption at 80 K on NiAl(111) and NiAl(001) and subsequent thermal decomposition at elevated temperatures leads to the formation of AlN. Well-ordered and homogeneous AlN thin films can be prepared by several cycles of ammonia adsorption and annealing to 1250 K. The films render a distinct LEED pattern with hexagonal [AlN/NiAl(111)] or pseudo-twelve-fold [AlN/NiAl(001)] symmetry. The lattice constant of the grown AlN film is determined to be a_AlN= 3.11 Å. EEL spectra of AlN films show a FK phonon at 865 cm^-1. The electronic gap is determined to be E_g= 6.1±0.2 eV. GaN films are prepared by using the same procedure on the (001) and (111) surfaces of CoGa. The films are characterized by a FK phonon at 695 cm^-1 and an electronic band gap E_g= 3.5±0.2 eV. NO adsorption at 75 K on NiAl(001) and subsequent annealing to 1200 K leads to the formation of aluminium oxynitride (AlON). An oxygen to nitrogen atomic ratio of ≈2:1 was estimated from the analysis of AES spectra. The AlON films shows a distinct (2×1) LEED pattern and the EEL spectrum exhibits characteristic Fuchs-Kliewer modes. The energy gap is determined to be E_g= 6.6±0.2 eV. The structure of the AlON film is derived from that of θ-Al₂O₃ formed on NiAl(001). Received: 21 March 1997/Accepted: 12 August 1997     

Characterization of thin Ta-Si-Nx layers of different nitrogen content using XPS, UPS and STM

Reactively sputtered Ta-Si-N_x barrier systems of different nitrogen content on copper were investigated by photoelectron spectroscopy (XPS, UPS) and scanning tunnelling microscopy (STM). The measured photoelectron spectra (excitation He-I) showed a clear dependence of the electron state density near the Fermi edge on the content of nitrogen. These results correlate with the I(U) characteristics of the STM measurements and the electrical conductivity of these layers.     

Correlation between density and structure. in boron nitride thin films by X-ray diffraction

* _ion=100 eV. Above E^* _ion the average density (deduced from X-ray reflectivity) shows a strong increase, indicating the sudden appearance of the cubic boron nitride phase consistent with the sp³ concentration deduced from IR absorption spectroscopy. The in-plane X-ray diffraction shows that this cubic phase consists of small nanocrystals of 70 Å linear size. Received: 26 November 1996/Accepted: 27 January 1997     

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 ?.     

Prerequisites for high-quality magnetic tunnel junctions: XPS and NMR study of Co/Al bilayers

Aluminum films with thicknesses ranging from 1 nm to 12 nm have been sputtered on 20 nm thick Co layers. The properties of the Co/Al bilayers were studied by X-ray photoemission spectroscopy (XPS) and spin-echo nuclear magnetic resonance (NMR). Both methods show independently that a 1 nm Al film covers the Co surface completely. XPS and NMR also showed that layers thicker than 1 nm Al are not oxidized completely in ambient air. Similarities to and deviations from niobium with Al overlayers (Nb/Al) are described. Prerequisites for the fabrication of tunneling magnetoresistance devices based on Co or NiFe ferromagnets and an aluminum oxide barrier are discussed. Received: 7 July 1999 / Accepted: 11 November 1999 / Published online: 8 March 2000     

A comparative study of the microstructures and optical properties of Cu- and Ag-doped ZnO thin films

Cu- and Ag-doped ZnO films were deposited by direct current co-reactive magnetron sputtering technique. The microstructure, the chemical states of the oxygen, zinc, copper and silver and the optical properties in doped ZnO films were investigated by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS) and UV-Visible spectroscopy. XRD analysis revealed that both of Cu- and Ag-doped ZnO films consist of single phase ZnO with zincite structure while the doping elements had an evident effect on the (0 0 2) preferential orientation. The XPS spectra showed that the chemical states of oxygen were different in Cu- and Ag-doped ZnO thin films, which may lead to the shift of the band gap as can be observed in the transmittance and absorption spectra. Meanwhile, the widths of band tails of ZnO films became larger after Cu and Ag doping.     

Atomic layer deposition of PbZrO3 thin films

In this paper, we report on the preparation of lead zirconate films for the first time using atomic layer deposition in an attempt to investigate some of the film properties and also to evaluate possible use of the precursor combination to prepare more complex lead titanate zirconate. In the depositions tetraphenyl lead (Ph₄Pb) was used as the lead and zirconium 2,2,6,6-tetramethyl-3,5-heptadionato (Zr(thd)₄) as the zirconium precursor, while ozone was used as the oxygen source. Film growth, stoichiometry and quality were studied using different pulsing ratios at deposition temperatures of 275 and 300 °C. According to X-ray diffraction, the crystalline perovskite phase was observed when films deposited on SrTiO₃(1 0 0) were annealed at 600 °C. Surface roughness was reduced for lead deficient films as well as in annealed samples.     

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.     

Growth and characterization of Y2O3 thin films

Y₂O₃ thin films were grown on silicon (1 0 0) substrates by pulsed-laser deposition at different substrate temperatures and O₂ pressures. The structure and composition of films are studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Y₂O₃ thin films deposited in vacuum strongly oriented their [1 1 1] axis of the cubic structure and the film quality depended on the substrate temperature. The magnitude of O₂ pressure obviously influences the film structure and quality. Due to the silicon diffusion and interface reaction during the deposition, yttrium silicate and SiO₂ were formed. The strong relationship between composition and growth condition was discussed.     

Effects of non-stoichiometric RuO x thin films on the dielectric properties of BaTiO3 thin films

The deconvolution process of X-ray photoemission spectra for O 1s and Ru 3d, X-ray diffraction and Rutherford backscattering spectrometry reveal that the RuO _x films (x = 2.0 – 2.2) deposited at a O₂ partial pressure less than 30% show (110)-oriented grains, whereas the RuO _x films (x = 2.3 – 2.4) deposited at a 40–50% O₂ partial pressure show amorphous and (101)-oriented grains due to the excess O interstitials and RuO₃ or RuO₄. These differences in the crystal phases of RuO _x influence the crystal structure of BaTiO₃ deposited on these RuO _x bottom electrodes, resulting in a higher dielectric constant and a lower dissipation factor for tetragonal BaTiO₃/RuO _x (x = 2.1) than amorphous BaTiO₃/RuO _x (x = 2.4).     

Structure and magnetic properties of Co nanoclusters fabricated by ion beam synthesis in SiO2 films

Co nanoparticles fabricated by ion beam synthesis in SiO₂ films were investigated with transmission electron microscopy and superconducting quantum interference device technique. Variation of the thermal treatment enables the formation of Co nanoclusters of different sizes ranging from 2 to 40 nm. Small nanoclusters of about 2–3 nm are amorphous, whereas clusters above 7 nm show the configuration of cubic Co nanocrystals. Measurements of magnetisation at temperatures between 2 K and 360 K reveal superparamagnetic behaviour for the small nanoclusters up to 3 nm and ferromagnetism for clusters above 7 nm. Received: 12 February 2001 / Accepted: 3 May 2001 / Published online: 27 June 2001     

Studies of interface structures of W films grown on patterned and bare Si(100) by TEM

+ Si(100) and bare Si(100) wafers by low pressure chemical vapour deposition (LPCVD) at 230–280 °C. The films were investigated by transmission electron microscopy (TEM). The cross-sectional TEM samples of W/Si(100) exhibited a fine scale interface roughness, which was attributed to the surface preparation. Irregular W plug structures were observed depending on the predeposition procedures. It was observed that an insufficient deposition of W films on the contact surface leads to the presence of aluminium around and underneath the plugs. This was observed by energy dispersive X-ray spectrometry (EDX). A study, using conventional electron diffraction, confirmed that no silicides formed at the interfaces of W-bare Si(l00) wafers. Received: 16 December 1996/Accepted: 6 May 1997     

Synthesis of molybdenum silicide by both ion implantation and ion beam assisted deposition

Two groups of Mo/Si films were deposited on surface of Si(1 0 0) crystal. The first group of the samples was prepared by both ion beam assisted deposition (IBAD) and metal vapor vacuum arc (MEVVA) ion implantation technologies under temperatures from 200 to 400 °C. The deposited species of IBAD were Mo and Si, and different sputtering Ar ion densities were selected. The mixed Mo/Si films were implanted by Mo ion with energy of 94 keV, and fluence of Mo ion was 5 × 10¹⁶ ions/cm². The second group of the samples was prepared only by IBAD under the same test temperature range. The Mo/Si samples were analyzed by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), sheet resistance, nanohardness, and modulus of the Mo/Si films were also measured. For the Mo/Si films implanted with Mo ion, XRD results indicate that phase of the Mo/Si films prepared at 400 and 300 °C was pure MoSi₂. Sheet resistance of the Mo/Si films implanted with Mo ion was less than that of the Mo/Si films prepared without ion implantation. Nanohardness and modulus of the Mo/Si films were obviously affected by test parameters.     

Multifractal analysis of ITO thin films prepared by electron beam deposition method

In this work, we developed the multifractality and its formalism to investigate the surface topographies of ITO thin films prepared by electron beam deposition method for various annealing temperatures from their atomic force microscopy (AFM) images. Multifractal analysis shows that the spectrum width, Δα (Δα = α_max − α_min), of the multifractal spectra, f(α), can be used to characterize the surface roughness of the ITO films quantitatively. Also, it is found that the f(α) shapes of the as-deposited and annealed films remained left hooked (that is Δf = f(α_min) − f(α_max) > 0), and falls within the range 0.149-0.677 depending upon the annealing temperatures.