Ultrathin Y2O3(111) films on Pt(111) substrates

The growth of ultrathin films of Y₂O₃(111) on Pt(111) has been studied using scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS), and low energy electron diffraction (LEED). The films were grown by physical vapor deposition of yttrium in a 10^? 6 Torr oxygen atmosphere. Continuous Y₂O₃(111) films were obtained by post-growth annealing at 700 °C. LEED and STM indicate an ordered film with a bulk-truncated Y₂O₃(111)–1 × 1 structure exposed. Furthermore, despite the lattices of the substrate and the oxide film being incommensurate, the two lattices exhibit a strict in-plane orientation relationship with the [11?0] directions of the two cubic lattices aligning parallel to each other. XPS measurements suggest hydroxyls to be easily formed at the Y₂O₃ surface at room temperature even under ultra high vacuum conditions. The hydrogen desorbs from the yttria surface above ~ 200 °C.     

Preparation and characterization of iron–molybdate thin films

Mixed Fe–Mo oxides are used in industrial catalytic processes of selective oxidation of methanol to formaldehyde. For better understanding of the structure-reactivity relationships of these catalysts we aim to prepare well-ordered iron–molybdate thin films as model catalysts. Here we have studied Mo deposition onto Fe₃O₄ (111) thin films produced on Pt(111) as a function of Mo coverage and annealing temperature using LEED, AES, STM and IRAS. At low temperatures, the iron oxide film is covered by Mo = O terminated molybdena nanoparticles. Upon oxidation at elevated temperatures (T > 900 K), Mo species migrate into the film and form new bonds with oxygen in the film. The resulting films maintain the crystal structure of Fe₃O₄, and the surface undergoes a (√3 × √3)R30° reconstruction. The structure is rationalized in terms of Fe substitution by Mo in the surface layers.     

CO adsorption on clean and oxidized Pt3Ti(111)

CO adsorption on clean and oxidized Pt₃Ti(111) surfaces has been investigated by means of Auger Electron Spectroscopy (AES), Thermal Desorption Spectroscopy (TDS), Low Energy Electron Diffraction (LEED) and High Resolution Electron Energy Loss Spectroscopy (HREELS). On clean Pt₃Ti(111) the LEED patterns after CO adsorption exhibit either a diffuse or a sharp c(4 × 2) structure (stable up to 300 K) depending on the adsorption temperature. Remarkably, the adsorption/desorption behavior of CO on clean Pt₃Ti(111) is similar to that on Pt(111) except that partial CO decomposition on Ti sites and partial CO oxidation have also been evidenced. Therefore, the clean surface cannot be terminated by a pure Pt plane. Partially oxidized Pt₃Ti(111) surfaces (< 135 L O₂ exposure at 1000 K) exhibit a CO adsorption/desorption behavior rather similar to that of the clean surface, showing again a c(4 × 2) structure (stable up to 250 K). Only the oxidation of CO is not detectable any more. These results indicate that some areas of the substrate remain non-oxidized upon low oxygen exposures. Heavily oxidized Pt₃Ti(111) surfaces (> 220 L O₂ exposure at 1000 K) allow no CO adsorption indicating that the titanium oxide film prepared under these conditions is completely closed.     

Growth and characterization of CoSi2 films on Si (1 0 0) substrates

In the present work, a special solid phase epitaxy method has been adapted for the preparation of CoSi₂ film. This method includes an epitaxial growth of Co films on Si (1 0 0) substrate, and in situ annealing of the Co/Si films in vacuum. It has been found that at the substrate temperature of 360°C, fcc cobalt film grows epitaxially on the Si (1 0 0) surface. The crystallographic orientation relations between fcc Co film and Si substrate determined from the electron diffraction result are: (0 0 1) Co//(0 0 1) Si, [1 0 0] Co//[1 1 0]Si. Upon annealing at temperatures range from 500 to 600°C, Co film reacts with Si substrate and transforms into CoSi₂. The CoSi₂ films prepared by this way are characterized by XTEM, XPS and AFM.     

Nucleation and growth of Si on Pb monolayer covered Si(111) surfaces

With a scanning tunneling microscope (STM), we study the initial stage of nucleation and growth of Si on Pb monolayer covered Si(111) surfaces. The Pb monolayer can work as a good surfactant for growth of smooth Si thin films on the Si(111) substrate. We have found that nucleation of two-dimensional (2D) Pb-covered Si islands occurs only when the substrate temperature is high enough and the Si deposition coverage is above a certain coverage. At low deposition coverages or low substrate temperatures, deposited Si atoms tend to self-assemble into a certain type of Si atomic wires, which are immobile and stable against annealing to ~ 200 °C. The Si atomic wires always appear as a double bright-line structure with a separation of ~ 9 Å between the two lines. After annealing to ~ 200 °C for a period of time, some sections of Si atomic wires may decompose, meanwhile the existing 2D Pb-covered Si islands grow laterally in size. The self-assembly of Si atomic wires indicate that single Si adatoms are mobile at the Pb-covered Si(111) surface even at room temperature. Further study of this system may reveal the detailed atomic mechanism in surfactant-mediated epitaxy.     

The growth of Ag films on a TiO2(110)-(1×1) surface

We report here the growth of Ag film and its thermal stability on the TiO₂(1 1 0)-(1×1) surface using combination techniques of low-energy ion scattering (LEIS), X-ray photoelectron spectroscopy (XPS), and low-energy electron diffraction (LEED). At a surface temperature as low as 125 K, a 2D growth of Ag films seems to occur for submonolayer coverages up to ∼0.8 ML. Annealing of low temperature grown Ag films to 500 K for coverage of 1–2.4 ML would result in the formation of metastable Ag layers with rest of Ag forming 3D needle-like islands on top of this Ag film.     

Silver sulphide growth on Ag(111): A medium energy ion scattering study

The interaction of S₂ with Ag(111) under ultra-high vacuum conditions has been investigated by medium energy ion scattering (MEIS). 100 keV He⁺ MEIS measurements provide a direct confirmation of a previous report, based on thermal desorption, that the growth of multilayer films of Ag₂S occurs through a continuous corrosion process. These films show a commensurate (√7 × √7)R19° unit mesh in low energy electron diffraction, consistent with the epitaxial growth of (111) layers of the high-temperature F-cubic phase of Ag₂S. The substantial range of co-existing film thicknesses found indicates that the growth must be in the form of variable-thickness islands. The use of 100 keV H⁺ incident ions leads to a very rapid decrease in the sulphide film thickness with increasing exposure that we attribute to an unusual chemical leaching, with implanted H atoms interacting with S atoms and desorption of H₂S from the surface.     

Oscillation of surface in-plane lattice spacing during epitaxial growth of BaTiO3 and SrTiO3 on SrTiO3(1 0 0)

In-plane lattice spacing oscillation was observed as functions of surface coverage and growing film thickness by reflection high-energy electron diffraction during the growth of strained BaTiO₃ and unstrained SrTiO₃ epitaxial layers on SrTiO₃(1 0 0). For BaTiO₃/SrTiO₃, the oscillation continued until the critical thickness is reached, whereas for SrTiO₃/SrTiO₃, oscillation was observed only at the initial few monolayer growth. The origin of oscillations is discussed in relation to the non-tetragonal elastic distortion occurring at the free edges of 2D single monolayer islands. The amplitude of the oscillation strongly depended on the island size and density.     

Enhanced superconducting properties in epitaxial FeSe thin films with self-assembled Fe3O4 nanoparticles

In this paper we report epitaxial tetragonal iron selenide thin films grown on single crystal SrTiO₃ (STO) (0 0 1) and MgO (0 0 1) substrates by a pulsed laser deposition (PLD) technique. Deposition temperature and annealing process are found to be critical for achieving the tetragonal phase and the optimum superconducting properties of the films. The critical transition temperature of the thin films ranges from 2 K to 11.5 K depending on the deposition temperature and annealing condition. The samples with higher critical transition temperatures show better film crystallinity along with self-assembled Fe₃O₄ nanoparticles (～15 nm in average particle size) in the films according to both X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis. Besides the better crystallinity achieved in the films, the formation of Fe₃O₄ nanoparticles could assist the formation of the tetragonal FeSe phase and thus lead to the enhanced superconducting properties.     

Fabrication of Gd0.5Sr0.5CoO3 film for SOFC cathode by pulsed laser deposition

Gd_0.5Sr_0.5CoO₃ (GSCO) film has been fabricated by pulsed laser deposition (PLD) to be used as the cathode of the solid oxide fuel cell (SOFC). The GSCO thin film obtained has a columnar crystalline structure so that it will have a high permeation property. The PLD technique has been found suitable for growing a film of complex composition because of its good control of stoichiometry and thus for fabricating a GSCO film used as the cathode of the SOFC. The GSCO film has been studied for porosity electrical conductivity and power density. The GSCO film grown at a substrate temperature of 1100 K and oxygen gas pressure of 100 Pa has high electrical conductivity which is 820 S cm^− 1 at 973 K with post annealing at a rather low temperature (1000 K). This value is higher than that of the GSCO film prepared by RF-sputtering with post annealing at a higher temperature (1273 K).     

Structural and magnetic properties of HCP-CoCrPt–SiO2 granular media

Granular HCP-(CoCrPt)_100−x(SiO₂)_x thin films with Cr underlayers have been fabricated by sputtering multilayers followed by post-deposition annealing. Magnetic and structural properties of the films for potential applications in magnetic recording media have been investigated in detail. In as-deposited films coercivities exceeding 2.5 kOe have been obtained with SiO₂ varying from 8 to 16 vol%; high coercivity of 5.6 kOe and anisotropy of 4.6×10⁶ erg/cm³ have been achieved at low M_rt value (about 0.4 memu/cm²) in the post-annealed films. VSM measurements showed that the magnetic moment lies well in the film plane under proper preparation conditions. Grain isolation in the magnetic layer was improved by segregating SiO₂ into grain boundaries and further enhanced by post-deposition annealing. The rapid increase of the coercivity upon annealing is most likely due to the significant decrease in intergranular exchange coupling, as shown by the δM measurement in which the peak value of δM curves changed from a positive value to a negative value upon annealing. Magnetic reversal properties of the films have also been systematically studied. These results show that the HCP-CoCrPt–SiO₂ granular film is a promising candidate for ultra-high-density recording media up to 100 Gbit/in² or beyond because of its low Pt content and desirable properties.     

Morphology and thermal stability of AlF3 thin films grown on Cu(100)

The growth of ultrathin epitaxial layers of aluminum fluoride on Cu(100) has been studied by a combination of surface science techniques. Deposition at room temperature results in step decoration followed by the formation of dendritic two-dimensional islands that coalesce to form porous films. Ultrathin layers (up to 2 monolayers in thickness) are morphologically unstable upon annealing; de-wetting takes place around 430 K with the formation of three-dimensional islands and leaving a large fraction of the Cu surface uncovered. Films several nanometers thick, on the contrary, are stable up to ca. 730 K where desorption in molecular form sets on. The effect of electron irradiation on the AlF₃ has also been characterized by different spectroscopic techniques; we find that even small quantities of stray electrons from rear electron beam heating can provoke significant decomposition of the aluminum fluoride, resulting in the release of molecular fluorine and the formation of deposits of metallic aluminum. These features make AlF₃ an interesting material for spintronic applications.     

Initial stages of Bi/Ge(111) interface formation: A detailed STM study

We present a detailed scanning tunneling microscopy investigation of ultra-thin Bi films on Ge(111)-c(2 × 8) in the range up to 1.5 ML. During growth at 300 K, the second/third atomic layer of Bi already starts to nucleate before the completion of the first/second layer correspondingly. Laterally isolated first layer Bi atoms, clusters and islands posses no electronic states in the range ~ 0.5 eV above the Fermi level of the substrate. In contrast, metallic electronic properties are found for continuous films when Bi coverage nears 1 ML. Annealing the as-deposited Bi films at 450 K causes lateral redistribution of Bi due to surface diffusion: coarsening of two-dimensional Bi islands with no long range order in the adsorbate layer is observed up to 1 ML; long range ordered (√3 × √3)-Bi/Ge(111) interface plus three-dimensional Bi clusters are obtained for coverages in excess of 1 ML.     

Annealing temperature dependent on structural,optical and electrical properties of indium oxide thin films deposited by electron beam evaporation method

In the present work the influence of annealing temperature on the structural and optical properties of the In₂O₃ films deposited by electron beam evaporation technique in the presence of oxygen was studied. The deposited films were annealed from 350 to 550 °C in air. The chemical compositions of In₂O₃ films were carried out by X-ray photoelectron spectroscopy (XPS). The film structure and surface morphologies were investigated as a function of annealing temperature by X-ray diffraction (XRD) and atomic force microscopy (AFM). The structural studies by XRD reveal that films exhibit preferential orientation along (2 2 2) plane. The refractive index (n), packing density and porosity (%) of films were arrived from transmittance spectral data obtained in the range 250–1000 nm by UV–vis-spectrometer. The optical band gap of In₂O₃ film was observed and found to be varying from 3.67 to 3.85 eV with the annealing temperature.     

Infrared study of triruthenium dodecacarbonyl interactions with gold

We present here a study of the interaction of triruthenium dodecacarbonyl Ru₃(CO)₁₂ with gold surfaces using time-evolved and temperature-programmed infrared reflection absorption spectroscopy (IRAS) and STM. Ru₃(CO)₁₂ exhibits drastically different adsorption/desorption behavior on high-index surfaces of gold in comparison to the smooth Au(111) surface. On the smooth Au(111) surface, the adsorption of Ru₃(CO)₁₂ at 200 K is observed to be molecular and reversible with the molecule's Ru₃-plane oriented essentially perpendicular to the surface in the first and second layer. In the multilayer (> 3 ML), the molecule is oriented parallel (or moderately inclined) to the surface. On high-index gold surfaces, prepared by partial annealing of rough gold films, the molecules dissociate. Vibrational spectra reveal dissociation of carbonyl to Ru and CO at elevated temperature (> 250 K) with the formation of CO covered Ru-islands and the subsequent desorption of CO from Ru-islands. Increasing amounts of CO observed with increasing surface roughness demonstrate that the rate of Ru₃(CO)₁₂ dissociation is related directly to the surface roughness of the gold surface. STM images reveal at low coverage the formation of 2-D islands of carbonyl fragments with lateral sizes of 1 to 1.5 nm and at higher coverage the formation of larger 3-D islands of 1 to 3 layers and lateral sizes above 10 nm.     

Growth mode of Pt1−xNix films biased dc-sputter-deposited on MgO(0 0 1)

A study is made by TEM, XRD and by measuring electrical/magnetic properties, of growth mode and properties of Pt_1−xNi_x alloy films deposited on MgO(0 0 1) at 250°C by dc-sputtering at 2.5–2.7 kV in Ar. A bias voltage V_s≤−160 V was applied to the substrate during deposition. It was confirmed that the Pt film was polycrystalline with the texture of Pt(1 1 1)/MgO(0 0 1) while the films of Pt_0.14Ni_0.86 and Pt_0.19Ni_0.81 were epitaxially grown with Pt–Ni(0 0 1)[1 0 0]/MgO(0 0 1)[1 0 0] similarly to the case of Ni/MgO(0 0 1). Thus the growth mode transformation between Pt–Ni(1 1 1)/MgO(0 0 1) and Pt–Ni(0 0 1)/MgO(0 0 1) may be induced at x less than 0.81 for Pt_1−xNi_x alloy films. The temperature coefficient of resistance TCR from 100 to 300 K of Pt_0.14Ni_0.86 films was estimated to be 0.0044–0.0053 K⁻¹ and saturation magnetization at 300 K to be 1.7–3.2 kG, respectively, while TCR of Pt films was estimated to be 0.0035–0.0048 K⁻¹.     

The effects of annealing and growth temperature on the morphologies of Bi nanostructures on HOPG

We report on the growth of ultra-thin bismuth (Bi) films on the basal plane of highly ordered pyrolitic graphite (HOPG) substrates; we investigate the morphologies of films grown at room temperature and then annealed at high temperature, and the morphologies of Bi structures grown at high temperature. Films grown at room temperature nucleate flat islands on the HOPG terraces, and 1D nanorods from HOPG step edges, the islands and rods both have heights in the range 1–3 nm. During annealing, the flat islands break up into groups of aligned, ～ 2.5 nm tall rods. For films grown at high temperature, terrace nucleation is almost nonexistent, and 1D structures grow from step edges, with heights up to 30 nm. Finally, we observe rods with distinctively different morphologies corresponding to (110) and (111) orientations, and infer a surface energy driven Bi(110) to Bi(111) orientation transition. We speculate that the dominant mechanism for the reorientation is coalescence.     

Effects of growth rate and buffer-layer on Bi2Sr2CaCu2Oy thin film fabrication

The effect of the growth rate on the Bi₂Sr₂CaCu₂O_y (Bi2212) thin film quality on MgO substrate is investigated at several growth rates from 0.175 to 3 nm/min. The maximal step height on the film surface is improved from about 100 to 6 nm by the reduction of growth rate to 0.5 nm/min and simultaneously the superconducting critical temperature attaining to a zero resistance T_c(R=0), is also improved from 50 to 63 K. The surface morphologies of the upmost Bi-superconducting thin films with the intermediate layers on MgO substrate is also studied in contrast to that deposited directly on the MgO substrate.     

Comparison of electrochromic amorphous and crystalline electron beam deposited WO3 thin films

Tungsten oxide (WO₃) thin films were prepared by an electron beam deposition technique. Films were deposited onto fluorine-doped tin oxide (FTO)-coated glass substrates maintained at 523 K. The as-deposited films were found to be amorphous and crystallized after annealing at 673 K. The electrochromic and optical properties, structure, and morphology are strongly dependent on the annealing conditions. Cyclic voltammetry (C-V) was carried out in the potential range −1 to +1 V. Before and after colouration, the films were characterized by measuring transmittance and reflectance. The colouration efficiencies at 630 nm are about 39.4 cm² C⁻¹ and 122.2 cm² C⁻¹ for amorphous and crystalline films, respectively. An investigation of self-bleaching for the coloured film revealed that the film fades gradually over time.     

Characterization of LSGM films obtained by electrophoretic deposition (EPD)

The application of the electrophoretic deposition (EPD) technique to the preparation of high quality electrolyte films for intermediate temperature solid oxide fuel cells (IT-SOFCs) was investigated. Films of La_0.83Sr_0.17Ga_0.83Mg_0.17O_2.83 (LSGM) were deposited on Pt and La_0.8Sr_0.2MnO₃ (LSM) substrates from suspensions in acetone/ethanol (3:1 by volume) mixture solvent and sintered at 1300 °C. Pt supported LSGM films, 10–20 μm thick, exhibited good adhesion to the Pt substrate, well-distributed microporosity and some surface roughness. LSM supported films exhibited cracking after sintering at 1300 °C for 3 h. Up to 900 °C the bulk conductivity of the Pt supported LSGM film showed the same behaviour of LSGM pellet (E_a = 0.93 eV and 0.99 eV, respectively). The LSGM film exhibited lower bulk electrical conductivity than the latter (4.1 × 10^− 3 and 4.4 × 10^− 2 Ω^− 1 cm^− 1, respectively, at 700 °C). This difference should be ascribed to the slight Ga depletion in the LSGM film. An important issue remains the selection of adequate electrode for LSGM electrolyte films.