Adsorption kinetics of alkanes on TiO2 nanotubesarray - structure-activity relationship

Presented are thermal desorption spectroscopy (TDS) measurements of iso-/n-butane adsorption on a variety of TiO₂ nanotubes (TiNTs) samples which are characterized by different crystal structures. The results are compared with a prior study on anatase(0 0 1) thin films grown on SrTiO₃(0 0 1). A distinct kinetic structure-activity relationship was present, i.e., the binding energies of the alkanes depend on the polymorph (anatase vs. mixed anatase/rutile) of TiO₂. A direct-fitting procedure of the TDS data has been applied to extract the kinetics parameters. The binding energies in the limit of zero coverage decrease as anatase thin film > amorphous-TiNTs ∼ polycrystalline anatase TiNTs > polycrystalline mixed anatase/rutile TiNTs.     

Si epitaxial growth on LaAlO3(0 0 1)

We report on the growth of Si on c(2 × 2) reconstructed LaAlO₃(0 0 1) surfaces at high substrate temperature (700 °C) by molecular beam epitaxy. An initial Volmer-Weber mode is evidenced using reflection high energy electron diffraction (RHEED), X-ray photoelectron diffraction (XPD) and atomic force microscopy. After the deposition of a few monolayers, the islands coalesce. Using X-ray photoelectron spectroscopy, we demonstrate that Si islands exhibit an abrupt interface with the LaAlO₃ substrate without formation of silicate or silica. Finally, combined RHEED and XPD measurements show the epitaxial growth of Si with a unique Si(0 0 1)//LaAlO₃(0 0 1) and Si<1 0 0>//LAO<1 1 0> relationship.     

Structural and electrical transport properties of Nb-doped TiO2 films deposited on LaAlO3 by rf sputtering

We have investigated the structural and electrical transport properties of Nb-doped TiO₂ films deposited on (1 0 0) LaAlO₃ substrates by rf magnetron sputtering at temperatures ranging from 873 K to 1073 K. Films deposited below 998 K are anatase, and mixed phases between anatase and rutile exist in the film grown at higher temperatures. We find that films deposited at low temperatures exhibit semiconductor behavior, while metallic conductivity is observed in the most conducting film deposited at 998 K. For this sample, compared to electron-phonon scattering mechanism, electron-phonon-impurity interference effect plays an important role in its electron transport process. Moreover, the temperature coefficient of the resistivity for the film deposited at 1073 K is negative from 2 K to 300 K. The temperature dependence of resistivity for the film is described by ∼exp(b/T)^1/2 at temperatures from 80 K down to 30 K, and by the fluctuation induced tunneling model from 80 K to 300 K.     

Band offsets at the epitaxial anatase TiO2/n-SrTiO3(0 0 1) interface

We have used high-energy resolution X-ray photoelectron spectroscopy to measure valence band offsets at the epitaxial anatase TiO₂(0 0 1)/n-SrTiO₃(0 0 1) heterojunction prepared by molecular beam epitaxy. The valence band offsets range between −0.06 ± 0.05 and +0.16 ± 0.05 eV for anatase thicknesses between 1 and 8 monolayers and three different methods of substrate surface preparation, with no systematic dependence on film thickness. The conduction band offset (CBO) varies over a comparable range by virtue of the fact that anatase and SrTiO₃ exhibit the same bandgap (∼3.2 eV). In contrast, density functional theory predicts the VBO to be +0.55 eV. The lack of agreement between theory and experiment suggests that either some unknown factor in the interface structure or composition excluded from the modeling is influencing the band offset, or that density functional theory cannot accurately calculate band offsets in these oxide materials. The small experimental band offsets have important implications for the use of this interface for fundamental investigations of surface photocatalysis. Neither electrons nor holes are likely to become trapped in the substrate and thus be unable to participate in surface photocatalytic processes.     

Growth and structure of vanadium oxide on anatase (1 0 1) terraces

The interaction of vanadium oxide with epitaxial anatase films exposing (1 0 1) terraces was characterized. The TiO₂ films were grown on vicinal LaAlO₃ (1 1 0) substrates by oxygen plasma-assisted molecular beam epitaxy (OPA-MBE); reflection high energy and low energy electron diffraction (RHEED and LEED) indicated that the films exposed (1 0 1) terraces of the anatase TiO₂ polymorph. When a vanadium oxide monolayer was deposited onto the anatase surface by OPA-MBE at 725 K, only (1 × 1) RHEED and LEED patterns were observed. The V X-ray photoelectron spectroscopy (XPS) peak intensities indicated that the monolayer wetted the anatase surface and so the diffraction patterns were attributed to an epitaxial vanadia layer. Analysis of the vanadium oxide monolayer by X-ray and ultraviolet photoelectron spectroscopies revealed that the V was predominantly 5+. When the vanadia coverage was increased at 725 K, Auger electron spectra showed only very slow attenuation of the anatase Ti peaks while spots began to develop in RHEED patterns recorded along the LaAlO₃ direction; both indicative of 3-D cluster formation. In the orthogonal direction, the RHEED patterns showed unusual diagonal streaks. Meanwhile, the (1 × 1) LEED pattern persisted even after 30 nm of vanadia was deposited. This was attributed to gaps between the 3-D clusters exposing the epitaxial monolayer. Core level XPS spectra of the 3-D clusters revealed a broad V 2p_3/2 peak that was centered at the position expected for V⁴⁺ but could be deconvoluted into three peaks corresponding to V³⁺, V⁴⁺, and V⁵⁺. It is shown that crystallographic shear that accommodates such variations in the oxygen content of V oxides can lead to the diagonal streaks in RHEED patterns recorded along the LaAlO₃ [0 0 1] direction even as the pattern in the orthogonal direction shows sharp transmission spots. The results show that vanadia growth on anatase (1 0 1) proceeds through the Stranski-Krastanov mode with a strong vanadia-titania interaction stabilizing a dispersed vanadia monolayer. The results are compared with previous data for vanadia growth on anatase (0 0 1) where smooth, epitaxial VO₂ films grow ad infinitum.     

Epitaxial growth La0.67Ca0.33MnO3 thin film by radio frequency sputtering method

Perfect epitaxial growth of La_0.67Ca_0.33MnO₃ (LCMO) thin film has been achieved on (1 0 0) LaAlO₃ (LAO) single crystal substrate by radio frequency sputtering method. X-ray diffraction (XRD) and electron diffraction analysis indicates that La_0.67Ca_0.33MnO₃ film grows epitaxially on LaAlO₃ along [1 0 0] direction of the substrate. The resistivity variation with temperature of the film shows a sharp metal to semiconductor transition peak around 253 K, which is close to that of the target. The magnetoresistance (MR) also reveals high quality epitaxy film characteristic at low temperatures and near the metal to semiconductor transition temperature.     

Dynamic nucleation and growth of Ni nanoparticles on high-surface area titania

Nucleation and growth mechanisms of Ni nanoparticles synthesized via an incipient wetness technique on a high-surface area titania support (i.e., a mixture of anatase and rutile) are studied using environmental transmission electron microscope (ETEM). Most Ni nanoparticles are found to nucleate from the Ni precursor coated on the surface of the titania support. Even though both anatase and rutile supports are the nucleation sites for Ni nanoparticles, it was observed that the particles have different morphologies on the supports, i.e., a non-wetting morphology on the anatase support versus a wetting morphology on the rutile {1 0 1}. This is because the interfacial energy of Ni/rutile is lower than that of Ni/anatase. Titania clusters are found to nucleate on the surface of the Ni particles during in situ ETEM reduction, indicating that the presence of partial titania overlayers is directly related to the synthesis of the Ni/TiO₂ catalysts. The growth mode of the Ni nanoparticles on the titania support is three-dimensional, while that of the rutile cluster on the surface of the Ni is two-dimensional layer-by-layer.     

Ultra-thin film growth of titanium dioxide on W(1 0 0)

We have employed low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy to follow the epitaxial growth of thin films of TiO₂ on W(1 0 0). The films were grown both by metal vapour deposition of titanium onto the substrate in UHV with subsequent annealing in a low partial pressure of oxygen, and by metal vapour deposition in a low partial pressure of oxygen. LEED patterns showed the characteristic patterns of (1 1 0) oriented rutile. A systematic spot splitting was observed and attributed to a stepped surface. The calculated step height was found to be in good agreement with that expected for rutile TiO₂(1 1 0), 3.3 Å. Titanium core level shifts were used to identify oxidation states as a function of film thickness allowing the interpretation in terms of a slightly sub-stoichiometric interface layer in contact with the substrate. In combination with the LEED patterns, the film structure is therefore determined to be (1 1 0) oriented rutile with a comparable level of stoichiometry to UHV prepared bulk crystals. The ordered step structure indicates considerable structural complexity of the surface.     

Computational study of adsorption, diffusion, and dissociation of precursor species on the GaN (0 0 0 1) surface during GaN MOCVD

The adsorption, diffusion, and dissociation of precursor species, MMGa (monomethylgallium) and NH₃, on the GaN (0 0 0 1) surface have been investigated using the DFT (density functional theory) calculation combined with a GaN (0 0 0 1) surface cluster model. The energetics of NH₃(ad) dissociation on the surface proposed of NH₃(ad) via NH₂(ad) to NH(ad) was facile with small activation barriers. A combined analysis with surface diffusion of adatoms demonstrated Ga(ad) and NH(ad) become primary reactant species for 2D film growth, and N(ad) develops into a nucleation center. Our studies suggest the control of NH₃(ad) dissociation are essential to improve epitaxial film quality as well as Ga-rich condition. In addition, the adsorbability of H(ad)s resulted from NH₃(ad) dissociation were found to influence on the surface chemistry during film growth.     

Comparison of the reduction of metal oxide surfaces: TiO2-anatase, TiO2-rutile and SnO2-rutile

Reduction of stoichiometric metal oxide can be reached by two processes: oxygen vacancies or hydrogenation. We present DFT-GGA periodic calculations for the O vacancies in the bulk and selected slabs of TiO₂-rutile, TiO₂-anatase, and SnO₂-rutile as well as their hydrogenation. We focus on the comparison between these structures. Anatase is found more difficult to reduce than rutile. Contrary to the reduced rutile structure which has a high spin state, all the electrons of the reduced anatase are paired. SnO₂ is more easily reduced than TiO₂. Strongly reduced (1 1 0) surfaces undergo reconstructions. Hydrogenated structures of rutile and anatase show also different patterns. While on the rutile (1 1 0) face, all the H atoms are adsorbed on the bridging O atoms in rows and form bridging OH groups, in the most stable hydrogenated anatase (1 0 0) structure only half of them are located while the other half is bound to the fivefold coordinated Ti surface atoms.     

Influence of epitaxial growth on phase competition in Pr0.5Sr0.5MnO3 films

A series of Pr_0.5Sr_0.5MnO₃ (PSMO) films with various thickness were epitaxially grown on substrates of (0 0 1)-oriented (LaAlO₃)_0.3(SrAl_0.5Ta_0.5O₃)_0.7 (LSAT), LaAlO₃ (LAO) and SrTiO₃ (STO), and (0 1 1)-oriented STO using pulse laser deposition. Influence of epitaxial growth on phase competition was investigated. A ferromagnetic metal to antiferromagnetic insulator (FMM-AFI) transition upon cooling is present in both largely compressed situations deposited on LAO (0 0 1) and tensile cases deposited on STO (0 0 1) but absent in little strained films grown on LSAT (0 0 1), indicating that the antiferromagnetic insulating state is favored by strains. On the other hand, the 400 nm films deposited on (0 1 1)-oriented STO as well as LAO substrates show FMM-AFI transition. These results reveal that both the orientation of epitaxial growth and substrate-induced strain affect the FMM-AFI transition.     

Stabilization of the anatase phase in TiO2(Fe, PEG) nanostructured coatings

Multilayered TiO₂(Fe³⁺, PEG) films were deposited on glass and SiO₂/glass substrates by sol-gel dipping method. The influence of Fe³⁺ and PEG(polyethylene glycol) concentrations, the number of layers, the thermal treatment time and the temperature on the optical and microstructural properties of the TiO₂ films were studied.As-deposited TiO₂(Fe³⁺, PEG) films were very porous, but after the thermal treatment at 500 °C, the PEG decomposed and burned out to porosity decreasing. Homogeneous nanostructured films were obtained, where the amorphous and the anatase phases coexist. XRD analysis showed that no rutile phase is observed in the films deposited on SiO₂/glass as compared with those deposited directly on glass and that the presence of the anatase phase in the films without PEG is more evident in the three-layers film. The XRD intensity of the main peak of anatase from 25° decreases with the increase of PEG concentration.The optical gap of the TiO₂(Fe³⁺, PEG) films is found in 2.52-2.56 eV range and does not essentially depend on the PEG content.     

Amorphous film thickness dependence for epitaxy of perovskite oxide films under excimer laser irradiation

We have studied the epitaxial growth of perovskite manganite LaMnO₃ (LMO) on SrTiO₃(1 0 0) in the excimer laser assisted metal organic deposition process. The LMO was preferentially grown from the substrate surface by the KrF laser irradiation. The study of amorphous LMO film thickness dependence on epitaxial growth under the excimer laser irradiation revealed that the photo-thermal heating effect strongly depended on the amorphous film thickness due to a low thermal conductivity of amorphous LMO: the ion-migration for chemical bond-forming at the reaction interface would be strongly enhanced in the amorphous LMO film with the large film thickness about 210 nm. On the other hand, the photo-chemical effect occurred efficiently for the amorphous film thickness in the range of 35-210 nm. These results indicate that the epitaxial growing rate was dominated by the photo-thermal heating after the photo-chemical activation at the growth interface.     

Effect of interface layer on growth behavior of atomic-layer-deposited Ir thin film as novel Cu diffusion barrier

Growth and nucleation behavior of Ir films grown by atomic layer deposition (ALD) on different interfacial layers such as SiO₂, surface-treated TaN, and 3-nm-thick TaN were investigated. To grow Ir thin film by ALD, (1,5-cyclooctadiene) (ethylcyclopentadienyl) iridium (Ir(EtCp)(COD)) and oxygen were employed as the metalorganic precursor and reactant, respectively. To obtain optimal deposition conditions, the deposition temperature was varied from 240 to 420 °C and the number of deposition cycles was changed from 150 to 300. The Ir film grown on the 3-nm-thick TaN surface showed the smoothest and most uniform layer for all the deposition cycles, whereas poor nucleation and three-dimensional island-type growth of the Ir layer were observed on Si, SiO₂, and surface-treated TaN after fewer number of deposition cycles. The uniformity of the Ir film layer was maintained for all the different substrates up to 300 deposition cycles. Therefore we suggest that the growth behavior of the Ir layer on different interface layer is related to the chemical bonding pattern of the substrate film or interface layer, resulting in better understand the growth mechanism of Ir layer as a copper diffusion barrier. The ALD-grown Ir films show the preferential direction of (1 1 1) for all the reflections, which indicates the absence of IrO₂ in metallic Ir.     

Maintaining particle size in the transformation of anatase to rutile titania nanostructures

We study the temperature-dependent transformation of two distinctly synthesized TiO₂ nanoparticles from the anatase to the rutile phase. These studies are carried out over the temperature range extending from room temperature to an excess of 800 °C where the anatase to rutile conversion is found to occur. Results obtained for both a sol-gel-generated nanocolloid (3-20 nm) and a sol-gel-generated micelle nanostructure (∼40 nm) are evaluated. While the TiO₂ nanocolloid structures aggregate to form larger crystallites as a function of increasing temperature with sizes comparable to the sol-gel-generated micelle structures, the resulting anatase crystallites, which are of a diameter 40-50 nm, appear to transform to comparable or slightly smaller rutile structures at 800 °C. This is in contrast to the transformation to larger rutile structures, observed for larger anatase particles. The importance of kinetic effects is considered as it enhances the rate of anatase to rutile conversion. These characteristics are established using a combination of Raman spectroscopic, X-ray diffraction, and scanning electron microscopy. The relative playoffs of the Raman and X-ray diffraction techniques are considered as they are used for the analysis of particles at the nanoscale, especially when phase transformations are evaluated.     

Structural-optical study of high-dielectric-constant oxide films

High-k polycrystalline Pr₂O₃ and amorphous LaAlO₃ oxide thin films deposited on Si(0 0 1) are studied. The microstructure is investigated using X-ray diffraction and scanning electron microscopy. Optical properties are determined in the 0.75-6.5 eV photon energy range using spectroscopic ellipsometry. The polycrystalline Pr₂O₃ films have an optical gap of 3.86 eV and a dielectric constant of 16-26, which increases with film thickness. Similarly, very thin amorphous LaAlO₃ films have the optical gap of 5.8 eV, and a dielectric constant below 14 which also increases with film thickness. The lower dielectric constant compared to crystalline material is an intrinsic characteristic of amorphous films.     

Fabrication of FeSe1−x superconducting films with bulk properties

We have fabricated high-quality FeSe_1−x superconducting films with a bulk T_c of 11–12 K on different substrates, Al₂O₃(0 0 0 1), SrTiO₃(1 0 0), MgO(1 0 0), and LaAlO₃(1 0 0), by using a pulsed laser deposition technique. All the films were grown at a high substrate temperature of 610 °C, and were preferentially oriented along the (1 0 1) direction, the latter being to be a key to fabricating of FeSe_1−x superconducting thin films with high T_c. According to the energy dispersive spectroscopy data, the Fe:Se composition ratio was 1:0.90 ± 0.02. The FeSe_1−x film grown on a SrTiO₃ substrate showed the best quality with a high upper critical magnetic field [H_c2(0)] of 56 T.     

Structure and optical anisotropy of pulsed-laser deposited TiO2 films for optical applications

The evolution of the crystal, the microstructural and the optical properties of pulsed-laser deposited TiO₂ films, investigated by X-ray diffraction, atomic force microscopy, scanning electron microscopy, optical transmittance and m-line spectroscopy measurements are reported. The samples were grown on (0 0 1) SiO₂ substrates at temperatures from 250 to 600 °C and oxygen pressures from 1 to 15 Pa. Crystalline films consisting of single anatase or anatase and rutile phases, were obtained at temperatures higher than 400 °C. A tendency toward columnar-like growth morphology was observed in the samples. Strong dependence of the optical properties on the surface roughness and the microstructure was determined. All films revealed single-mode waveguiding and optically anisotropic properties.     

Thermochemical behavior of metallic citrate precursors for the production of pure LaAlO3

Pure LaAlO₃ nanoparticles were synthesized, using a citrate-precursor technique. La(NO₃)₃, Al(NO₃)₃, and C₃H₄(OH)(COOH)₃, in a molar ratio of 1:1:4.5, were dissolved in deionized water. The pH of the aqueous solution was adjusted using NH₄OH. After drying, the citrate precursors were charred at 350 °C, followed by calcination at different temperatures. The thermochemical behavior of the charred citrate precursor to form LaAlO₃ was investigated using X-ray diffractometry, infrared spectroscopy, thermogravimetric analysis, and differential thermal analysis. While the charred specimen obtained at pH=2 (without NH₄OH addition) was composed of LaAl(OOCH₂)₃, the charred specimens obtained at pH>2 were composed of LaAlO_3−x−y(CO₃)_x(OH)_2y. All these metallic salts were decomposed at temperatures between 600 and 780 °C to form crystalline LaAlO₃ but calcining the specimens in air at ?800 °C were required to remove all residual chars to produce pure LaAlO₃. At 900 °C, the citrate-derived particles obtained at pH>2 were composed of LaAlO₃ crystallites with an average size of ∼30 nm.     

Ferromagnetism at 300 K in spin-coated films of Co doped anatase and rutile-TiO2

Thin films of Ti_1−xCo_xO₂ (x=0 and 0.03) have been prepared on sapphire substrates by spin-on technique starting from metalorganic precursors. When heat treated in air at 550 and 700 °C, respectively, these films present pure anatase and rutile structures as shown both by X-ray diffraction and Raman spectroscopy. Optical absorption indicate a high degree of transparency in the visible region. Such films show a very small magnetic moment at 300 K. However, when the anatase and the rutile films are annealed in a vacuum of 1×10⁻⁵ Torr at 500 and 600 °C, respectively, the magnetic moment, at 300 K, is strongly enhanced reaching 0.36μ_B/Co for the anatase sample and 0.68μ_B/Co for the rutile one. The ferromagnetic Curie temperature of these samples is above 350 K.