Identification of iron oxide phases in thin films grown on Al2O3(0 0 0 1) by Raman spectroscopy and X-ray diffraction

We report on the identification of Fe₃O₄ (magnetite) and α-Fe₂O₃ (hematite) in iron oxide thin films grown on α-Al₂O₃(0 0 0 1) by evaporation of Fe in an O₂-atmosphere with a thickness of a few unit cells. The phases were observed by Raman spectroscopy and confirmed by X-ray diffraction (XRD). Magnetite appeared independently from the substrate temperature and could not be completely removed by post-annealing in an oxygen atmosphere as observed by X-ray diffraction. In the temperature range between 400 °C and 500 °C the X-ray diffraction shows that predominantly hematite is formed, the Raman spectrum shows a mixture of magnetite and hematite. At both lower and higher substrate temperatures (300 °C and 600 °C) only magnetite was observed. After post-annealing in an O₂-atmosphere of 5 × 10^?5 mbar only hematite was detectable in the Raman spectrum.     

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.     

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.     

Structural and magnetic properties of thin epitaxial Fe films on (1 1 0) GaAs prepared by metalorganic chemical vapor deposition

Iron films have been grown on (1 1 0) GaAs substrates by atmospheric pressure metalorganic chemical vapor deposition at substrate temperatures (T_s) between 135°C and 400°C. X-ray diffraction (XRD) analysis showed that the Fe films grown at T_s between 200°C and 330°C were single crystals. Amorphous films were observed at T_s below 200°C and it was not possible to deposit films at T_s above 330°C. The full-width at half-maximum of the rocking curves showed that crystalline qualities were improved at T_s above 270°C. Single crystalline Fe films grown at different substrate temperature showed different structural behaviors in XRD measurements. Iron films grown at T_s between 200°C and 300°C showed bulk α-Fe like behavior regardless of film thickness (100–6400 Å). Meanwhile, Fe films grown at 330°C (144 and 300 Å) showed a biaxially compressed strain between substrate and epilayer, resulting in an expanded inter-planar spacing along the growth direction. Magnetization measurements showed that Fe films (>200 Å) grown at 280°C and 330°C were ferromagnetic with the in-plane easy axis along the [1 1 0] direction. For the thinner Fe films (⩽200 Å) regardless of growth temperature, square loops along the [1 0 0] easy axis were very weak and broad.     

Synthesis and characterization of layered Li1−x(Ni0.5Co0.5)1−yFeyO2(0 ≤ (1 − x) ≤ 1 and 0 ≤ y ≤ 0.2) cathodes

Layered Li(Ni_0.5Co_0.5)_1−yFe_yO₂ cathodes with 0 ≤ y ≤ 0.2 have been synthesized by firing the coprecipitated hydroxides of the transition metals and lithium hydroxide at 700 °C and characterized as cathode materials for lithium ion batteries to various cutoff charge voltages (up to 4.5 V). While the y = 0.05 sample shows an improvement in capacity, cyclability, and rate capability, those with y = 0.1 and 0.2 exhibit a decline in electrochemical performance compared to the y = 0 sample. Structural characterization of the chemically delithiated Li_1−x(Ni_0.5Co_0.5)_1−yFe_yO₂ samples indicates that the initial O3 structure is maintained down to a lithium content (1 − x) ≈ 0.3. For (1 − x) < 0.3, while a P3 type phase is formed for the y = 0 sample, an O1 type phase is formed for the y = 0.05, 0.1 and 0.2 samples. Monitoring the average oxidation state of the transition metal ions with lithium contents (1 − x) reveals that the system is chemically more stable down to a lower lithium content (1 − x) ≈ 0.3 compared to the Li_1−xCoO₂ system. The improved structural and chemical stabilities appear to lead to better cyclability to higher cutoff charge voltages compared to that found before with the LiCoO₂ system.     

Oxygen assisted deposition of Sr2FeMoO6 thin films on SrTiO3(1 0 0)

Epitaxial thin films of Sr₂FeMoO₆ (SFMO) were prepared by pulsed laser deposition on SrTiO₃(1 0 0) substrate. Thin films have been grown under different gas environments and they were structurally characterised by XRD. In contrast to previous reports, deposition carried out in the presence of a small amount of O₂ with Ar yields high-quality SFMO films with a saturation magnetic moment of 3.8 μ_B. These SFMO films were strained in such a way that they were elongated along the c-axis and compressed in the ab-axes directions. The large low-field magnetoresistance seen in these films has been attributed to the tunneling across the antisite boundaries.     

Magnetic anisotropy of epitaxial Fe layers grown on Si(0 0 1)

The magnetic properties of epitaxial iron films up to 80 monolayers (ML) thickness grown on Si(0 0 1) by using a template technique were investigated by means of superconducting quantum interference device and magneto-optic Kerr effect techniques. The thinnest films investigated (∼3 ML) exhibit a composition close to Fe₃Si with a Curie temperature below room temperature (RT) and strong out-of-plane remanent magnetization that reflects the presence of a dominant second order surface anisotropy term. Thicker films (⩾4 ML) are ferromagnetic at RT with remanent magnetization in film-plane and a composition closer to pure Fe with typically 8–10% silicon content. When deposited at normal incidence such films show simple in-plane fourfold anisotropy without uniaxial contribution. The relevant fourth-order effective anisotropy constant K₄^eff was measured versus film thickness and found to change its sign near 18 ML. The origin of this remarkable behavior is investigated by means of a Néel model and mainly traced back to fourth-order surface anisotropy and magneto-elastic effects related to the large biaxial in-plane compressive strain up to 3.5% in the thinnest (⩽25 ML) films.     

Ab initio study of structural and magnetic properties of cubic Fe4N(0 0 1) surface

First-principles calculations are employed to study the structural and magnetic properties of fully-relaxed cubic Fe₄N(0 0 1) surfaces with both Fe₂- and Fe₂N-termination. The results of surface stability calculations show that the (0 0 1) surface of Fe₄N is most possibly existing with Fe₂N-termination. Slab structures have more localized features in the density of states especially for the Fe₂N-terminated surface due to structure relaxation. The average magnetic moments of Fe atoms increase with increasing thickness of slabs. The calculated interlayer distances indicate that the decreases of d₁₂ and d₂₃ result in stronger hybridization and shorter bond distances between Fe2 atom in the second layer and other atoms in surface or the third layers, which lead to variation of magnetic moments with different slab thicknesses.     

Use of film thickness and Cu additive to improve (0 0 1) texture in MgO/FePtCu(C) bilayers

A multilayer structure has been proposed that demonstrates improved (0 0 1) texture for FePt-based L1₀ perpendicular media. Achieving a strong perpendicular magnetic anisotropy requires aligning the L1₀ crystallographic c-axis along the film normal. The ordered L1₀ FePt structure is tetragonal with a c/a ratio close to 0.965. This makes discriminating between the three crystallographic variants ([1 0 0], [0 1 0], and the desired [0 0 1]) difficult. Alloying FePt with Cu to reduce the c/a ratio and using a multilayer approach to keep the magnetic layers thin results in a structure with an adjustable M_rt and a strong (0 0 1) texture (rocking curve widths around 2°). This is a remarkable improvement in texture from pure FePt multilayered films or monolithic FePt(X) films. The proposed [MgO(2 nm)/Fe_50−xPt₅₀Cu_x(5 nm)]_×n structure limits grain size in the vertical (perpendicular) direction albeit not in the plane of the film. Carbon can be added to the FePtCu layer to reduce the grain size with minimal degradation of the (0 0 1) orientation.     

Optical properties of Cr/Fe(t)/MgO (0 0 1) thin films

In this work we report on the optical properties of single-crystalline iron thin films. For this, Cr-capped Fe films with thickness, t, in the range 30–300 Å were prepared on MgO (0 0 1) by DC magnetron sputtering, and then studied by optical absorption technique within the range from 1.0 to 3.6 eV. All measurements were carried out at room temperature using a fiber optics spectrophotometer. The intensity of the transmitted light decreases with increasing film thickness. The optical constants of the films are deduced from a model that considers the transmission of light by two absorbing films on an absorbing substrate. The absorption coefficient of the Fe films is also calculated from the transmission data. The absorption spectra show the following characteristics: (i) two large absorption peaks centered at about 1.20 and 2.65 eV; and (ii) a sharp step near 1.40 eV. These structures are associated with conventional interband transitions of the iron film.     

A high (0 0 1)-oriented CoPt/Ag film deposited on glass substrate

The magnetic properties and structures of CoPt_15 nm/Ag_0−100 nm films deposited by DC magnetron sputtering on glass substrates have been studied. The (0 0 1) texturing was improved by introducing an Ag underlayer. As the Ag underlayer thickness was 100 nm, a nearly perfect (0 0 1)-textured CoPt film was obtained.     

A competition between (0 0 1) and (0 1 1) alignments in yttria stabilized zirconia thin films fabricated by ion beam assisted deposition

Biaxially textured yttria stabilized zirconia (YSZ) thin films, were deposited on glass substrates by ion beam assisted deposition method with different deposition time. As contrasts, films were also fabricated without assisting ion beam. The orientation properties of the films were characterized by X-ray diffraction. A comparative study shows that there is a competition between (0 0 1) and (0 1 1) alignments during the growth process. Assisting ions make the films (0 0 1)-advantaged and biaxially textured. The competitive growth and the orientation development are explained by selective resputtering and anisotropic damage on growing films induced by assisting ions.     

Magnetic behaviour of nanocrystalline Ni–Cu ferrite and the effect of irradiation by 100 MeV Ni ions

The effects of 100 MeV Ni ion irradiation on magnetic properties of nanoparticles of Ni_0.8Cu_0.2Fe₂O₄ with average particle sizes of 40 Å and 60 Å, synthesized by chemical co-precipitation method have been studied. The spinel cubic structures were confirmed by XRD. The average particle size estimated by XRD and by Langevin function fitting are in good agreement for both the pristine and irradiated samples. The blocking temperature increases with particle size and does not change after irradiation. On irradiation by 100 MeV Ni ions, significant changes in the hysteresis loop features are observed, which may be attributed to formation of cluster of defects in the nanocrystalline samples due to swift heavy ion (SHI) irradiation. It is also found that SHI irradiation produces more dominant changes in the hysteresis loop of smaller particle size of 40 Å as compared to that of 60 Å.     

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.     

Crystal growth and structural properties of the spinel-type Li1 + xMn2 − xO4 (x = 0.10, 0.14)

Single crystals of the lithium-rich lithium manganese oxide spinels Li_1 + xMn_2 − xO₄ with x = 0.10 and 0.14 have been successfully synthesized in high-temperature molten chlorides at 1023 K. The single-crystal X-ray diffraction study confirmed the cubic Fd3¯m space group and the lattice parameters of a = 8.2401(9) Å for x = 0.10 and a = 8.2273(10) Å for x = 0.14 at 300 K, respectively. The crystal structures have been refined to the conventional values R = 3.7% for x = 0.10 and R = 3.1% for x = 0.14, respectively. Low-temperature single-crystal X-ray diffraction experiments revealed that these single crystal samples showed no phase transition between 100 and 300 K. The electron-density distribution images in these compounds by the single-crystal MEM analysis clearly showed strong covalent bonding features between the Mn and O atoms due to the Mn–3d and O–2p interaction.     

Potential-induced structure transitions in self-assembled monolayers: II. Propanethiol on Au(1 0 0)

The structure of propanethiol self-assembled monolayers (SAMs) on Au(1 0 0) in 0.1 M H₂SO₄ has been investigated as a function of electrode potential by in situ scanning tunnelling microscopy (STM). These studies reveal a potential-induced, reversible transition between an in essence quadratic and a distorted hexagonal structure. We suggest that a thiolate-driven surface reconstruction, similar to Au(1 0 0)-(hex), is responsible for the hexagonal SAM structure, whereas the quadratic one refers to the unreconstructed substrate.     

First-principles study of small palladium clusters on NiAl(1 1 0) alloy surface

Theoretical calculations focused on the geometry, stability, electronic and magnetic properties of small palladium clusters Pd_n (n=1–5) adsorbed on the NiAl(1 1 0) alloy surface were carried out within the framework of density functional theory (DFT). In agreement with the experimental observations, both Ni-bridge and Al-bridge sites are preferential for the adsorption of single palladium atom, with an adsorption energy difference of 0.04 eV. Among the possible structures considered for Pd_n (n=1–5) clusters adsorbed on NiAl(1 1 0) surface, Pd atoms tend to form one-dimensional (1D) chain structure at low coverage (from Pd₁ to Pd₃) and two-dimensional (2D) structures are more stable than three-dimensional (3D) structures for Pd₄ and Pd₅. Furthermore, metal-substrate bonding prevails over metal–metal bonding for Pd cluster adsorbed on NiAl(1 1 0) surface. The density of states for Pd atoms of Pd/NiAl(1 1 0) system are strongly affected by their chemical environment. The magnetic feature emerged upon the adsorption of Pd clusters on NiAl(1 1 0) surface was due to the charge transfer between Pd atoms and the substrate. These findings may shade light on the understanding of the growth of Pd metal clusters on alloy surface and the construction of nanoscale devices.     

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.     

Structural and magnetic properties of BCC Fe/Co (0 0 1) superlattices

In thin layered Fe/Co (0 0 1), grown on MgO (0 0 1), both Fe and Co crystallize in the body-centered cubic (BCC) structure, as seen in a series of superlattices where the layer thickness of the components is varied from two to twelve atomic monolayers. These superlattices have novel magnetic properties as observed by magnetization and polarized neutron reflectivity measurements. There is a significant enhancement of the magnetic moments of both Fe and Co at the interfaces. Furthermore, the easy axis of the system changes from [1 0 0] for films of low cobalt content to [1 1 0] for a Co content exceeding 33%. No indication of a uniaxial anisotropy component is found in any of the samples. The first anisotropy constant (K₁) of BCC Co is found to be negative with an estimated magnitude of 110 kJ/m³ at 10 K. In all cases, the magnetic moments of Fe and Co have parallel alignment.     

Surface structure and morphology of InAs(1 1 1)B with/without gold nanoparticles annealed under arsenic or atomic hydrogen flux

We have investigated the structure and morphology of the InAs(1 1 1)B surface using Low Energy Electron Diffraction (LEED), Scanning Tunneling Microscopy (STM) and Scanning Electron Microscopy (SEM). The surface was prepared by annealing in the presence of an arsenic or atomic hydrogen pressure. A (2 × 2) reconstruction that changes into a (1 × 1) unreconstructed surface after prolonged annealing was observed irrespective of preparation method, while the surface morphology was distinctly different in the two cases. Detailed atomic scale models are proposed to explain the behavior. Deposition of Au aerosol nanoparticles on the sample prior to annealing was found to have no effect on the surface reconstruction. The Au particles were found to sink into the surface.