Synthesis of Cr-based mixed oxides by reactive ion beam mixing of Cr/X interfaces (X=Al or Si)

The 3 keV O₂⁺\mathrm{O}_{2}^{+} reactive ion beam mixing of Cr/X interfaces (X=Al or Si) has been used to synthesize Cr-based mixed oxide thin films. The kinetics of growth, composition, and electronic structure of those films has been studied using X-ray photoelectron spectroscopy, Auger electron spectroscopy, ultraviolet photoelectron spectroscopy, and factor analysis. Initially, for low ion doses, Cr₂O₃ species are formed. Later, with increasing the ion dose, Cr₂O₃ species are first transformed into Cr³⁺–O–X species, and subsequently, those Cr³⁺–O–X species are transformed into Cr⁶⁺–O–X species. This sequential transformation, Cr₂O₃→Cr³⁺–O–X→Cr⁶⁺–O–X, is accompanied by a slight increase of the oxygen concentration and a decrease of the Cr/X ratio in the films formed leading to the synthesis of custom designed Cr-based mixed oxides. The changes observed in the valence band and Auger parameters further support the formation of Cr–X mixed oxide species. Angle resolved X-ray photoelectron spectroscopy shows that for low ion doses, when only Cr₂O₃ and Cr³⁺–O–X species coexist, Cr³⁺–O–X species are located nearer the surface than Cr₂O₃ species, whereas for higher ion doses, when only Cr³⁺–O–X and Cr⁶⁺–O–X species coexist, the Cr⁶⁺–O–X species are those located nearer the surface.     

The formation of V–Al–N thin films by reactive ion beam mixing of V/Al interfaces

The reactive ion beam mixing (IBM) of V/Al interfaces by low-energy N₂⁺ ions at room temperature leads to the formation of V–Al–N ternary nitride thin films. The kinetics, growth mechanisms, composition and electronic structure of those films have been studied using X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, Factor Analysis and Monte Carlo TRIDYN simulations. The comparison of experimental results with those obtained from TRIDYN simulations suggests that the chemical reaction with the nitrogen partial pressure and processes driven by residual defects are the rate-controlling mechanisms during the reactive IBM of V/Al interfaces. The kinetics of mixing is characterized by two stages. During the first stage (≤4×10¹⁶ ions/cm²), the formation of vanadium nitride is observed. In the second stage, vanadium nitride is transformed into a V–Al–N ternary nitride due to Al incorporation in the near surface region. Moreover, the V/Al ratio can be varied in a broad range, whereas the nitrogen concentration slightly decreases with increasing the aluminium content of the film.     

Time-resolved photoelectron spectroscopy of $\mathrm{Al}_{3}\mathrm{O}_{3}^{-}$: photoisomerization versus photofragmentation

In general, clusters are unstable and in many cases several metastable isomers exist even at low temperature. Therefore, a cluster may react with a dramatic geometry change to a small disturbance such as a weak field or to the absorption of a low-energy photon. Here, we study the response of Al₃O₃^-\mathrm{Al}_{3}\mathrm{O}_{3}^{-} to photoexcitation using time-resolved photoelectron spectroscopy. Earlier experimental and theoretical studies suggested that this cluster anion undergoes a geometry change after photoexcitation. In contrast, our time-resolved spectra indicate that photoexcitation triggers ultra-fast fragmentation. This example demonstrates that ultra-fast processes in clusters are not well understood and that it is still difficult to gain reliable experimental data about such processes.     

Structural, morphological and optical properties of \hbox {In}_{2}\hbox {S}_{3} thin films obtained by SILAR method

$\hbox {In}_{2}\hbox {S}_{3}$ thin films have been elaborated onto glass substrate by SILAR method at room temperature using different immersion time in the solution of cation and anion and fixing the rinsing time. The film composition, morphology and structure were investigated using energy dispersive X-ray analysis (EDAX), scanning electron microscopy (SEM) and X-ray diffraction techniques. Optical properties, such transmission and band gap have been also analyzed. The effects of annealing on the morphological structure thin films are also described. The x-rays diffraction spectra indicated that the formed compounds are $\upbeta $ - $\hbox {In}_{2}\hbox {S}_{3}$ polycrystalline thin films with $\hbox {In}_{6}\hbox {S}_{7 }$ as second phase in sample S1 and sample S2 and no another phase in sample 3. SEM revealed homogeneous and relatively uniform films and EDAX shows sample 3 with S/In=1.44. For sample 1 and sample 2, we noted an increase of band gap when rinsing time increases.     

Synthesis of Ti-Cr-N thin films by reactive ion-beam mixing of Ti/Cr interfaces

Titanium/chromium interfaces produced by titanium thin film deposition on chromium substrates have been reactively mixed using ion-beams of 2 and 3 keV at room temperature (RT). The ion-beam mixing (IBM) has been analysed using X-ray photoelectron spectroscopy (XPS), angle-resolved X-ray photoelectron spectroscopy (ARXPS) and Monte Carlo TRIDYN simulations. Below ∼2 × 10¹⁶ ions/cm², the IBM kinetic is characterised by a strong decrease of the Ti concentration along with a fast nitrogen incorporation, that can be explained mainly by Ti sputtering and nitrogen implantation. Above that ion dose, the Ti/Cr ratio can be varied in a broad range maintaining nearly constant the nitrogen concentration (∼50%), as a consequence of sputtering, nitruration and mixing effects taking place simultaneously. ARXPS results show that the composition of the ternary films formed by reactive IBM is rather uniform in the near surface region. The comparison of experimental results with those obtained from TRIDYN, that uses pure ballistic mechanisms, suggests that the chemical reaction with the nitrogen partial pressure and processes driven by residual defects are the rate-controlling mechanisms during the reactive IBM of Ti/Cr interfaces.     

Mag netic properties of $$\hbox{Ni}_{13- n}\hbox{Al}_ n$$ clusters with n = 0–13

We report the magnetic properties of small Ni_13-nAl_n\hbox{Ni}_{13-n}\hbox{Al}_n clusters with n = 0–13 calculated in the framework of density functional theory. The cluster magnetic moment decreases with the sequential substitution of Ni by Al atoms, which can be attributed to a greater degree of hybridization that forces the pairing of the electrons in the molecular orbitals of Ni and Al. For Ni₇Al₆, the complete quenching of the cluster magnetic moment appears to be due to the antiferromagnetic alignment of atomic spins as revealed by the spin density plots.     

A novel Sr_{3}Pb_{6}Ce_{2}Ti_{12}O_{36} ferroelectric thin film grown by pulsed laser ablation

Complex perovskite oxide ferroelectric thin films are of great technological interest because of their high dielectric constant and large tunability. In this paper, we report the structural and electrical properties of Sr \(_{3}\) Pb \(_{6}\) Ce \(_{2}\) Ti \(_{12}\) O \(_{36}\) (SPCTO) thin films grown by pulsed laser deposition. The role of oxygen pressure and substrate temperature on the microstructure, dielectric properties and leakage current mechanism of SPCTO thin films was investigated. Strong oxygen partial pressure dependence on the microcrystalline properties and leakage current conduction mechanism was observed. Both Raman spectra and C-V characteristics show a ferroelectric phase rather than paraelectric phase for the deposited thin films. Investigations on the leakage current showed that SPCTO thin films deposited at different oxygen pressure have different dominant conduction mechanism at various electric fields. The low field conduction mechanism is governed by Ohmic and space charge limited conduction mechanisms, whereas at high fields, the conduction process is dominated by Schottky emission mechanism. The dielectric constant as well as the tunability is found to increase with increase in the crystallite size.     

NiTi合金薄膜厚度对相变温度影响的X射线光电子能谱分析

采用X射线衍射和X射线光电子能谱实验手段对不同厚度的NiTi薄膜相变温度的变化进行了分析.结果表明在相同衬底温度和退火条件下,3?μm厚度的薄膜晶化温度高于18?μm厚度的薄膜.衬底温度越高,薄膜越易晶化,退火后薄膜奥氏体相转变温度As越低.薄膜的表面有TiO₂氧化层形成,氧化层阻止了Ni原子渗出;膜与基片的界面存在Ti₂O₃和NiO.由于表面和界面氧化层的存在,不同厚度的薄膜内层的厚度也不同,因而薄膜越薄,Ni原子的含量就越高.Ni原子的含量的不同会影响薄膜的相变温度. 关键词： NiTi合金薄膜 X射线衍射 相变 X射线光电子能谱     

Compositional and structural evolution of the titanium dioxide formation by thermal oxidation

Titanium oxide films were prepared by annealing DC magnetron sputtered titanium films in an oxygen ambient. X-ray diffraction （XRD）, Auger electron spectroscopy （AES） sputter profiling, MCs^＋-mode secondary ion mass spectrometry （MCs^＋-SIMS） and atomic force microscopy （AFM） were employed, respectively, for the structural, com- positional and morphological characterization of the obtained films. For temperatures below 875 K, titanium films could not be fully oxidized within one hour. Above that temperature, the completely oxidized films were found to be rutile in structure. Detailed studies on the oxidation process at 925K were carried out for the understanding of the underlying mechanism of titanium dioxide （TiO2） formation by thermal oxidation. It was demonstrated that the formation of crystalline TiO2 could be divided into a short oxidation stage, followed by crystal forming stage. Relevance of this recognition was further discussed.     

Effect of substrate temperature on the surface and interface oxidation of NiTi thin films

NiTi shape memory alloy thin films are deposited on pure Cu substrate at substrate ambient temperatures of 300 °C and 450 °C. The surface and interface oxidation of NiTi thin films are characterized by X-ray photoelectron spectroscopy (XPS). After a subsequent annealing treatment the crystallization behavior of the films deposited on substrate at different temperatures is studied by X-ray diffraction (XRD). The effects of substrate temperature on the surface and interface oxidation of NiTi thin films are investigated. In the film surface this is an oxide layer composed of TiO₂. The Ni atom has not been detected on surface. In the film/substrate interface there is an oxide layer with a mixture Ti₂O₃ and NiO in the films deposited at substrate temperatures 300 °C and 450 °C. In the films deposited at ambient temperature, the interface layer contains Ti suboxides (TiO) and metallic Ni.     

Investigation by X-ray photoelectron spectroscopy of the transient oxidation of NiAl

X-ray photoelectron spectroscopy (XPS) has been used to study the oxidation of NiAl in oxygen at atmospheric pressure. Prior to oxidation, the native oxide scale on the specimen was removed by ion sputtering and the specimens were (pre-)heated in vacuum before exposure to oxygen. At low oxidation temperatures (<750 K) scales consisted of Al₂O₃ and NiAl₂O₄, with a thin surface layer of NiO, but at higher temperatures were of Al₂O₃, apart from about 0.5 at % Ni. The Ni content in the latter case was constant throughout the scale and did not increase dramatically near the alloy/oxide interface. In the experimental conditions used in this study, initial formation of NiO and NiAl₂O₄ seems to be avoided at the higher oxidation temperatures ( > 750 K).     

The adsorption and stability of sulfur containing amino acids on Cu{5 3 1}

The adsorption of l-cysteine and l-methionine amino acids on a chiral Cu{5 3 1} surface was investigated with high resolution X-ray photoelectron spectroscopy (XPS) and carbon K-edge near edge X-ray absorption fine structure (NEXAFS) Spectroscopy using synchrotron radiation. XPS shows that at 300 K l-cysteine adsorbs through two oxygen, a nitrogen and a sulfur atom, in a four point ‘quadrangular footprint’, whereas l-methionine adsorbs through only two oxygen and a nitrogen atom in a ‘triangular footprint’. NEXAFS was used to clarify the adsorption geometry of both molecules, which suggests a binding orientation to the top layer and second layer atoms in two different orientations associated with adsorption sites on {1 1 0} and {3 1 1} microfacets of the Cu{5 3 1} surface.     

The atomic structure of alloy surfaces: Ni3Al{001}

The atomic structure of the {001} surface of Ni₃Al has been determined by LEED (low-energy electron diffraction) intensity analysis to correspond to simple truncation of the bulk structure with the Ni-Al mixed layer on top rather than the pure Ni layer. The first interlayer spacing is essentially equal to the bulk interlayer spacing between {001} planes. First-principles calculations of the cohesive energies of slabs terminating in the two types of layers also indicate that the mixed layer termination is more stable.     

Deposition of zinc oxide thin films by reactive pulsed laser ablation

Thin films of zinc oxide have been deposited by reactive pulsed laser ablation of Zn and ZnO targets in presence of a radio frequency (RF) generated oxygen plasma. The gaseous species have been deposited at several substrate temperatures, using the on-axis configuration, on Si (1 0 0). Thin films have been characterized by scanning electron microscopy, atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and infrared spectroscopy. A comparison among conventional PLD and reactive RF plasma-assisted PLD has been performed.     

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.     

Characterization of the current-induced resistive spots in superconducting \hbox {YBa}_{2} \hbox {Cu}_{3} \hbox {O}_{7} strips

For over a decade, ultrathin superconducting films have been developed for the detection of single photons at optical or near infrared frequencies, with competitive performances in terms of quantum efficiency, speed, and low dark count rate. In order to avoid the requirement of helium refrigeration, we consider here the use of high temperature materials, known to achieve very fast responsiveness to laser irradiation. We excite thin filaments of the cuprate \(\hbox {YBa}_{2} \hbox {Cu}_{3} \hbox {O}_{7}\) by rectangular pulses of supercritical current so as to produce either a phase-slip centre (PSC) or a normal hot spot (HS), according to the temperature and the current amplitude selected. That procedure provides information about the maximum bias current to be used in a particle detector, about the return current back to the quiescent state after excitation, and about the rate of growth and decay of a HS. We also measure the time of PSC nucleation. A unique feature of that approach is to provide the rate of heat transfer between the film and its substrate at whatever temperature, in the superconducting state, in the practical conditions of operation.     

Point-defect properties of and sputtering events in the {001} surfaces of Ni3Al I. Surface and point-defect properties

Constant-area and fully relaxed molecular dynamics methods are employed to study the properties of the surface and point defects at and near {001} surfaces of bulk and thin-film Ni, Al and Ni₃Al respectively. The surface tension is larger than the surface energy for all {001} surfaces considered in the sequence: Al (1005?mJ?m^?2)<?Ni₃Al (mixed Ni–Al plane outermost, 1725?mJ?m^?2)<?Ni₃Al (all-Ni-atoms plane outermost, 1969?mJ?m^?2)<?Ni (1993?mJ?m^?2). For a surface of bulk Ni₃Al crystal with a Ni–Al mixed plane outermost, Al atoms stand out by 0.0679?Å compared with the surface Ni atoms and, for the all-Ni-atoms surface, Al atoms in the second layer stand out by 0.0205?Å compared with Ni atoms in the same layer. Vacancy formation energies are about half the bulk values in the first layer and reach a maximum in the second layer where the atomic energy is close to the bulk value but the change in embedding energy of neighbouring atoms before and after vacancy formation is greater than that in the bulk. Both the vacancy formation energy and the surface tension suggest that the fourth layer is in a bulk state for all the surfaces. The formation energy of adatoms, antisite defects and point-defect pairs at and near {001} surfaces of Ni₃Al are also given.     

Morphology and composition of nanoscale surface oxides on Fe–20Cr–18Ni{1 1 1} austenitic stainless steel

Surface oxidation ranging from initial stages to the onset of passive oxide layer formation have been investigated on Fe–20Cr–18Ni{1 1 1} single crystal surface by X-ray photoelectron spectroscopy (XPS). Surface segregation of the alloying elements and the morphology of the surface oxide nanostructure were characterized quantitatively by inelastic electron background analysis. Our results demonstrate that by increasing the oxidation temperature the relative concentrations of Fe²⁺ and Fe³⁺ cations increase due to their enhanced mobility. Higher temperature also improves the mobility of chromium, thus enhancing its segregation to the oxygen-rich surface and thereby reinforcing the passive layer on the alloy. This is in agreement with the results showing the sudden decrease in oxide film thickness at the oxidation temperatures exceeding 600 K. Additionally, a pronounced segregation of metallic nickel is found in the interface between the surface oxide layer and the bulk alloy.     

Preliminary studies of the Raman spectra of \hbox {Ag}_{2}\hbox {Te}\hbox { and }\hbox {Ag}_{5}\hbox {Te}_{3}

The theoretical calculations indicated that the monoclinic low-temperature phase of silver telluride $(\upbeta \hbox {-Ag}_{2}\hbox {Te})$ is a new binary topological insulator with highly anisotropic single Dirac cone surface. We obtained $\upbeta \hbox {-Ag}_{2}\hbox {Te}$ crystal ingots containing few grains by the Bridgman method. We also deposited thin films of tellurium, $\hbox {Ag}_{5}\hbox {Te}_{3}\hbox { and }(\hbox {Te+Ag}_{5}\hbox {Te}_{3})$ by thermal evaporation method. The Raman spectra of $\upbeta \hbox {-Ag}_{2}\hbox {Te}$ , tellurium and $\hbox {Ag}_{5}\hbox {Te}_{3}$ were measured at three excitation wave lengths: 633, 515 and 488 nm. The Raman active modes of $\upbeta \hbox {-Ag}_{2}\hbox {Te}$ , tellurium and $\hbox {Ag}_{5}\hbox {Te}_{3}$ are situated at frequencies below 300  $\hbox {cm}^{-1}$ while vibrations of other phases appear at higher frequencies.     

Initial growth of platinum on oxygen-covered Ni(1 1 0) surfaces

The initial growth of Pt on the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) surfaces has been studied by coaxial impact collision ion scattering spectroscopy (CAICISS), low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). Prior to Pt deposition, the atomic structure of the near-surface regions of the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) structures were studied using CAICISS, finding changes to the interlayer spacings due to the adsorption of oxygen. Deposition of Pt on the Ni(1 1 0)-(3 × 1)-O surface led to a random substitutional alloy in the near-surface region at Pt coverages both below and in excess of 1 ML. In contrast, when the surface was treated with 1800 L of atomic oxygen in order to form a NiO(1 1 0) surface, a thin Pt layer was formed upon room temperature Pt deposition. XPS and LEED data are presented throughout to support the CAICISS observations.