Scanning tunnelling microscopy studies of growth morphology in highly epitaxial c-axis oriented Pt thin film on (0 0 1) SrTiO3

A noble metal Pt thin film was successfully grown on (0 0 1) SrTiO₃ substrate by using a DC-sputtering technique. The surface morphology and growth features of the as-grown Pt films were investigated by scanning tunnelling microscopy. Growth conditions, such as pre-sputtering, deposition ambience, and oxygen ratio are found to greatly affect the orientation, the crystallinity, and the epitaxial behavior of Pt films on (0 0 1) SrTiO₃. Single-crystalline Pt films have been achieved by introducing a few percentage oxygen into the sputtering ambient. The in-plane-relationship of the c-axis oriented Pt thin films on (0 0 1) SrTiO₃ was determined to be (0 0 1)_Pt∥(0 0 1)_SrTiO3 and [0 0 1]_Pt∥[0 0 1]_SrTiO3. Oxygen in the sputtering ambient was found to be a key factor to achieve the epitaxial Pt films.     

DFT study of Pt adsorption on low index SrTiO3 surfaces: SrTiO3(1 0 0), SrTiO3(1 1 1) and SrTiO3(1 1 0)

Density Functional Theory has been used to determine the energetically preferred structures of submonolayer, monolayer, and multilayer Pt films on both ideal terminations of SrTiO₃(1 0 0), SrTiO₃(1 1 1), and SrTiO₃(1 1 0). The strength of the resulting metal/metal oxide interfaces was characterized by the adsorption energy of the film and the film’s work of separation. The two polar surfaces, SrTiO₃(1 1 1) and SrTiO₃(1 1 0), form significantly stronger interfaces than the non-polar SrTiO₃(1 0 0) surface. Approximate criteria were applied to predict the growth mode of Pt on each surface.     

Hierarchical nanoparticle morphology for platinum supported on SrTiO3 (0 0 1): A combined microscopy and X-ray scattering study

The morphology of metal nanoparticles supported on oxide substrates plays an important role in heterogeneous catalysis and in the nucleation of thin films. For platinum evaporated onto SrTiO₃ (0 0 1) and vacuum annealed we find an unexpected growth formation of Pt nanoparticles that aggregate into clusters without coalescence. This hierarchical nanoparticle morphology with an enhanced surface-to-volume ratio for Pt is analyzed by grazing incidence small-angle X-ray scattering (GISAXS), X-ray fluorescence (XRF), atomic force microscopy (AFM) and high-resolution scanning electron microscopy (SEM). The nanoparticle constituents of the clusters measure 2-4 nm in size and are nearly contiguously spaced where the average edge-to-edge spacing is less than 1 nm. These particles make up the clusters, which are 10-50 nm in diameter and are spaced on the order of 100 nm apart.     

Epitaxial growth of Co(0 0 0 1)hcp/Fe(1 1 0)bcc magnetic bi-layer films on SrTiO3(1 1 1) substrates

Co(0 0 0 1)_hcp/Fe(1 1 0)_bcc epitaxial magnetic bi-layer films were successfully prepared on SrTiO₃(1 1 1) substrates. The crystallographic properties of Co/Fe epitaxial magnetic bi-layer films were investigated. Fe(1 1 0)_bcc soft magnetic layer grew epitaxially on SrTiO₃(1 1 1) substrate with two type variants, Nishiyama–Wasserman and Kurdjumov–Sachs relationships. An hcp-Co single-crystal layer is obtained on Ru(0 0 0 1)_hcp interlayer, while hcp-Co layer formed on Au(1 1 1)_fcc or Ag(1 1 1)_fcc interlayer is strained and may involve fcc-Co phase. It has been shown possible to prepare Co/Fe epitaxial magnetic bi-layer films which can be usable for patterned media application.     

Texture of molybdenum thin films on SrTiO3(1 0 0): A RHEED study

The structure of ultrathin Mo films on SrTiO₃(1 0 0) was studied by in situ reflection high-energy electron diffraction (RHEED). A different structure was observed for films less than 20 Å thick than for thicker films. These films were epitaxial and had a metastable structure. Thicker films had the dimensions of equilibrium bcc Mo(1 1 0). Relaxation processes transformed the metastable Mo into bcc Mo, resulting in the following orientation relationships between Mo and SrTiO₃: (1 1 0)[0 0 1]_bcc Mo ∥ (1 0 0)[0 0 1]_SrTiO3 and (1 1 0)[1 1 1]_bcc Mo ∥ (1 0 0)[0 1 1]_SrTiO3. The formation of such specific orientations is related to transformations via the Bain and Needle Path, respectively.     

Spray-pyrolysis deposition of LaMnO3 and La1−xCaxMnO3 thin films

Ethylene glycol solutions of La-Mn(II) and La-Ca-Mn(II) citric complexes has been used as a starting material for spray-pyrolysis deposition of LaMnO₃ and La_1−xCa_xMnO₃ thin films on β-quartz, fused quartz, Si(0 0 1) and SrTiO₃(1 0 0) substrates heated during the deposition at 380 °C. At suitable post-deposition heating conditions highly uniform films, 0.1-1 μm in thickness, with good crystal structure were obtained. Highly textured LaMnO₃ films are obtained on SrTiO₃(1 0 0) substrate. Interaction between the layer and Si-containing substrates is observed during the post-deposition heating in static air.     

First principle study of SrTiO3 (0 0 1) surface and adsorption of NO on SrTiO3 (0 0 1)

The results of first-principles calculations about the two possible terminations of (0 0 1) surface of SrTiO₃ perovskite and adsorption of NO on SrTiO₃ (0 0 1) surface were presented. Both surface parameters (atomic structures and electronic configurations) and adsorption parameters (bond, energy and charge) of NO on SrTiO₃ (0 0 1) surface, which have never been investigated before as far as we know were investigated using density functional theory calculations with the local-density approximation (DFT-LDA). It was found that the two possible terminations of SrTiO₃ (0 0 1) surface have large surface relaxation, which leads to surface polarization and exhibits different reactivity toward the dissociative adsorption of NO. The electronic states of TiO₂-terminated surface have larger difference than that of bulk, so it is more favorable for adsorption of NO than SrO-terminated surface.     

Effects of magnesium film thickness and annealing temperature on formation of Mg2Si films on silicon (1 1 1) substrate deposited by magnetron sputtering

Magnesium films of various thicknesses were first deposited on silicon (1 1 1) substrates by magnetron sputtering method and then annealed in annealing furnace filled with argon gas. The effects of the magnesium film thickness and the annealing temperature on the formation of Mg₂Si films were investigated by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The Mg₂Si thin films thus obtained were found to be polycrystalline and the Mg₂Si (2 2 0) orientation is preferred regardless of the magnesium film thickness and annealing temperature. XRD results indicate that high quality magnesium silicide films are produced if the magnesium/silicon samples are annealed at 400 °C for 5 h. Otherwise, the synthesized films annealed at annealing temperatures lower than 350 °C or higher than 450 °C contain magnesium crystallites or magnesium oxide. SEM images have revealed that microstructure grains in the polycrystalline films are about 1-5 μm in dimensions, and the texture of the Mg₂Si films becomes denser and more homogeneous as the thickness of the magnesium film increases.     

Synthesis and characterization of GaN nanowires by ammoniating Ga2O3/Cr thin films deposited on Si(1 1 1) substrates

GaN nanowires have been successfully synthesized on Si(1 1 1) substrates by magnetron sputtering through ammoniating Ga₂O₃/Cr thin films at 950 °C. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), FT-IR spectrophotometer, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM), and photoluminescence (PL) spectrum were carried out to characterize the microstructure, morphology, and optical properties of GaN samples. The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure and high-quality crystalline, have the size of 30-80 nm in diameter and several tens of microns in length with good emission properties. The growth direction of GaN nanowires is perpendicular to the fringe of (1 0 1) plane. The growth mechanism of GaN nanowires is also discussed in detail.     

Granular L10 FePt (0 0 1) thin films for Heat Assisted Magnetic Recording

Granular L1₀ FePt (0 0 1) thin films were deposited on a Si substrate with Ta/MgO underlayers by rf sputtering. The effects of in-situ heating temperatures (350-575 °C), pressures (2-40 mTorr), and sputtering powers (15-75 W) on texture and microstructure were investigated for the FePt films. We obtained films with grain densities approaching 50 teragrains per in.², grains sizes down to 2.2 nm with center-to-center spacing of 4.2 nm and coercivity of 24 kOe. The order parameters for the L1₀ FePt thin films were derived and calculated to be as high as 0.91. Although the grain size is small, the spacing between grains is too large for practical heat assisted magnetic recording media. To reach the desired results, we propose that layer-by-layer growth should be promoted in the FePt layer by inserting another underlayer that provides a better lattice match to L1₀ FePt.     

Role of crystal orientation on the magnetic properties of CoFe2O4 thin films grown on Si (1 0 0) and Al2O3 (0 0 0 1) substrates using pulsed laser deposition

We report the influence of crystal orientation on the magnetic properties of CoFe₂O₄ (CFO) thin films grown on single crystal Si (1 0 0) and c-cut sapphire (Al₂O₃) (0 0 0 1) substrates using pulsed laser deposition technique. The thickness was varied from 200 to 50 nm for CFO films grown on Si substrates, while it was fixed at 200 nm for CFO films grown on Al₂O₃ substrates. We observed that the 200 and 100 nm thick CFO-Si films grew in both (1 1 1) and (3 1 1) directions and displayed out-of-plane anisotropy, whereas the 50 nm thick CFO-Si film showed only an (1 1 1) orientation and an in-plane anisotropy. The 200 nm thick CFO film grown on an Al₂O₃ substrate was also found to show a complete (1 1 1) orientation and a strong in-plane anisotropy. These observations pointed to a definite relation between the crystalline orientation and the observed magnetic anisotropy in the CFO thin films.     

Magnetoresistance of magnetite thin films grown by pulsed laser deposition on GaAs(1 0 0) and Al2O3(0 0 0 1)

Magnetotransport properties of magnetite thin films deposited on gallium arsenide and sapphire substrates at growth temperatures between 473 and 673 K are presented. The films were grown by UV pulsed laser ablation in reactive atmospheres of O₂ and Ar, at working pressure of 8 × 10⁻² Pa. Film stoichiometry was determined in the range from Fe_2.95O₄ to Fe_2.97O₄. Randomly oriented polycrystalline thin films were grown on GaAs(1 0 0) while for the Al₂O₃(0 0 0 1) substrates the films developed a (1 1 1) preferred orientation. Interfacial Fe³⁺ diffusion was found for both substrates affecting the magnetic behaviour. The temperature dependence of the resistance and magnetoresistance of the films were measured for fields up to 6 T. Negative magnetoresistance values of ∼5% at room temperature and ∼10% at 90 K were obtained for the as-deposited magnetite films either on GaAs(1 0 0) or Al₂O₃(0 0 0 1).     

Structure, dielectric and ferroelectric properties of highly (1 0 0)-oriented BaTiO3 grown under low-temperature conditions

The highly (1 0 0)-oriented BaTiO₃ thin films were fabricated on LaNiO₃(1 0 0)/Pt/Ti/SiO₂/Si substrates under low-temperature conditions. Substrate temperatures throughout the fabrication process remained at or below 400 °C, which allows this process to be compatible with many materials commonly used in integrated circuit manufacturing. X-ray diffraction data provided the evidence for single BaTiO₃ phase. Field-emission scanning electron microscopy was used to study the columnar structure of the films. The dielectric properties as a function of frequency in the range of 1 kHz to 1 MHz was obtained. The room temperature remanent polarization (2P_r) and coercive field were found to be ∼5 μC/cm² and 50 kV/cm, respectively. The BTO film maintains an excellent fatigue-free character even after 10⁹ switching cycles.     

Probing of local ferroelectricity in BiFeO3 thin films and (BiFeO3)m(SrTiO3)m superlattices

Ferroelectric BiFeO₃ thin films and artificial superlattices of (BiFeO₃)_m(SrTiO₃)_m (m∼1-10 unit cells) were fabricated on (0 0 1)-oriented SrTiO₃ substrates by pulsed laser ablation. The variation of leakage current and macroscopic polarization with periodicity was studied. Piezo force microscopy studies revealed the presence of large ferroelectric domains in the case of BiFeO₃ thin films while a size reduction in ferroelectric domains was observed in the case of superlattice structures. The results show that the modification of ferroelectric domains through superlattice could provide an additional control on engineering the domain wall mediated functional properties.     

Nonlinear optical properties in SrTiO3 thin films by pulsed laser deposition

Well-crystallized 250 nm-thick SrTiO₃ thin films on fused-quartz substrate were prepared by pulsed laser deposition. The band-gap of SrTiO₃ thin film by transmittance spectra is equal to 3.50 eV, larger than 3.22 eV for the bulk crystal. The nonlinear optical properties of the films were examined with picosecond pulses at 1.064 μm excitation. A large two-photon absorption (TPA) with absorption coefficient of 87.7 cm/GW was obtained, larger than 51.7 cm/GW for BaTiO₃ thin films. The nonlinear refractive index n₂ is equal to 5.7×10⁻¹⁰ esu with a negative sign, larger than 0.267×10⁻¹¹ esu for bulk SrTiO₃. The large TPA is attributed to intermediate energy levels introduced by the grain boundaries, and the optical limiting behaviors stemming from both TPA and negative nonlinear refraction were also discussed.     

Electronic structure and topography of annealed SrTiO3(1 1 1) surfaces studied with MIES and STM

Perovskites of ABO₃ type like strontium titanate (SrTiO₃) are of great practical concern as materials for oxygen sensors operating at high temperatures. It is well known that the surface layer shows different properties compared to the bulk. Numerous studies exist for the SrTiO₃(1 0 0) and (1 1 0) surfaces which have investigated the changes in the electronic structure and topography as a function of the preparation conditions. They have indicated a rather complex behaviour of the surface and the near surface region of SrTiO₃ at elevated temperatures. Up to now, the behaviour of the SrTiO₃(1 1 1) surfaces under thermal treatment is not sufficiently known. This contribution is intended to work out the relation between alteration of the surface topography with respect to the preparation conditions and the simultaneous changes of the electronic structure. We applied scanning tunneling microscopy (STM) to investigate the surface topography and, additionally, metastable impact electron spectroscopy (MIES) to study the surface electronic structure of reconstructed SrTiO₃(1 1 1) surfaces. The crystals were heated up to 1000 °C under reducing and oxidizing conditions. Both preparation conditions cause strong changes of the surface topography and electronic structure. A microfaceting of the topmost layers is found.     

Characterization of bicrystalline epitaxial LaNiO3 films fabricated on MgO (1 0 0) substrates by pulsed laser deposition

A series of metallic LaNiO₃ (LNO) thin films were deposited on MgO (1 0 0) substrates by pulsed laser deposition (PLD) under the oxygen pressure of 20 Pa at different substrate temperatures from 450 to 750 °C. X-ray diffraction (XRD) was used to characterize the crystal structure of LNO films. θ-2θ scans of XRD indicate that LNO film deposited at a substrate temperature of 700 °C has a high orientation of (l l 0). At other substrate temperatures, the LNO films have mixed phases of (l l 0) and (l 0 0). Furthermore, pole figure measurements show that LNO thin films, with the bicrystalline structure, were epitaxially deposited on MgO (1 0 0) substrates in the mode of LNO (1 1 0)//MgO (1 0 0) at 700 °C. Reflection high-energy electric diffraction (RHEED) and atomic force microscopy (AFM) were also performed to investigate the microstructure of LNO films with the high (l l 0) orientation. RHEED patterns clearly confirm this epitaxial relationship. An atomically smooth surface of LNO films at 700 °C was obtained. In addition, bicrystalline epitaxial LNO films, fabricated at 700 °C, present a excellent conductivity with a lower electrical resistivity of 300 μ Ω cm. Thus, the obtained results indicate that bicystalline epitaxial LNO films could serve as a promising candidate of electrode materials for the fabrication of ferroelectric or dielectric films.     

Epitaxial C60 thin films on Bi(0 0 0 1)

We have used the Bi(0 0 0 1)/Si(1 1 1) template to grow highly ordered C₆₀ epitaxial thin films and analyzed them using scanning tunneling microscopy and low-energy electron microscopy. The in situ low-energy electron microscope investigations show that the initial nucleation of the C₆₀ islands on the surface takes place at surface defects, such as domain boundaries and multiple steps. The in-plane lattice parameters of this C₆₀ film turns out to be the same as that of the bulk fcc(1 1 1) C₆₀. The line-on-line epitaxial structure is realized in spite of a weak interaction between the C₆₀ molecules and Bi(0 0 0 1) surface, while scanning tunneling spectroscopy indicates that there is a negligible charge transfer between the molecules and the surface.     

The crystalline orientation and ferroelectric properties of Bi3.25La0.75Ti3O12 thin films mediated by the intermediate layer of LaNiO3

c-Axis-oriented and (1 1 7)-oriented Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films are successfully controlled by the intermediate layer of LaNiO₃ (LNO) with chemical solution deposition (CSD), respectively. X-ray diffraction (XRD) demonstrates that the structure and orientation of LNO thin films have a strong effect on the orientation of BLT thin films. Scanning electron microscopy suggests that BLT thin films on LNO electrode exhibit crack-free, uniform size grains and dense microstructure. A crystalline orientation dependent remanent polarization is observed in BLT thin films, and it is found that the remanent polarization (2P_r) of (1 1 7)-oriented films is larger than that of c-axis-oriented films. Our research directly demonstrates that the vector of the main spontaneous polarization in these layered perovskite materials (BLT) is along a-axis.     

The ferroelectric and ferromagnetic characterization of CoFe2O4/Pb(Mg1/3Nb2/3)O3-PbTiO3 multilayered thin films

The multiferroic (PMN-PT/CFO)_n (n = 1,2) multilayered thin films have been prepared on SiO₂/Si(1 0 0) substrate with LNO as buffer layer via a rf magnetron sputtering method. The structure and surface morphology of multilayered thin films were determined by X-ray diffraction (XRD) and atom force microscopy (AFM), respectively. The smooth, dense and crack-free surface shows the excellent crystal quality with root-mean-square (RMS) roughness only 2.9 nm, and average grain size of CFO thin films on the surface is about 44 nm. The influence of the thin films thickness size, periodicity n and crystallite orientation on their properties including ferroelectric, ferromagnetic properties in the (PMN-PT/CFO)_n multilayered thin films were investigated. For multilayered thin films with n = 1 and n = 2, the remanent polarization Pr are 17.9 μC/cm² and 9.9 μC/cm²; the coercivity H_c are 1044 Oe and 660 Oe, respectively. In addition, the relative mechanism are also discussed.