An investigation into ultra-thin pseudobinary oxide (TiO<Subscript>2</Subscript>)<Subscript>x</Subscript>(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>1-x</Subscript> films as high-<Emphasis Type="Italic">k</Emphasis> gate dielectrics

As potential gate dielectric materials, pseudobinary oxide (TiO₂)_x(Al₂O₃)_1-x (0.1≤x≤0.6) films (TAO) were deposited on Si (100) substrates by pulsed-laser deposition method and studied systematically via various measurements. By a special deposition process, including two separate steps, the TAO films were deposited in the form of two layers. The first layer was deposited at room temperature and the second layer was completed at the substrate temperature of 400 °C. Detailed data show that the properties of the TAO films are closely related to the ratio between TiO₂ and Al₂O₃. The existence of the first layer deposited at room temperature can effectively restrain the formation of the interfacial layer. And according to the results of X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy performed on the films, no other information belonging to the silicon oxide could be observed. For the (TiO₂)_0.4(Al₂O₃)_0.6 film, the best result has been achieved among all samples and its dielectric constant is evaluated to be about 38. It is valuable for the amorphous TAO film as one of the promising dielectric materials for high-k gate dielectric applications. PACS 77.55.+f; 73.40.Qv; 81.15.Fg     

Fowler-nordheim tunnelling in Au−TiO<Subscript>2</Subscript>−Ag film structures

I-V-characteristics have been measured for Au−TiO₂−Ag structures with TiO₂ layers of 30 and 180 nm thickness. The TiO₂ films were grown by atomic layer deposition (ALD) technique. In the case of negative bias on the Au electrode, the conduction currents through TiO₂ layers follow the Fowler-Nordheim formula for field emission over several orders of magnitude. The bulk of the currents may be attributed to tunnelling, seemingly through a Schottky barrier at the Au−TiO₂ junction. In the case of reversed polarity the currents are also observed, but cannot be interpreted as tunnelling.     

Structural, magnetic and electronic structure studies of Mn doped TiO2 thin films

We report structural, magnetic and electronic structure study of Mn doped TiO₂ thin films grown using pulsed laser deposition method. The films were characterized using X-ray diffraction (XRD), dc magnetization, X-ray magnetic circular dichroism (XMCD) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements. XRD results indicate that films exhibit single phase nature with rutile structure and exclude the secondary phase related to Mn metal cluster or any oxide phase of Mn. Magnetization studies reveal that both the films (3% and 5% Mn doped TiO₂) exhibit room temperature ferromagnetism and saturation magnetization increases with increase in concentration of Mn doping. The spectral features of XMCD at Mn L_3,2 edge show that Mn²⁺ ions contribute to the ferromagnetism. NEXAFS spectra measured at O K edge show a strong hybridization between Mn, Ti 3d and O 2p orbitals. NEXAFS spectra measured at Mn and Ti L_3,2 edge show that Mn exist in +2 valence state, whereas, Ti is in +4 state in Mn doped TiO₂ films.     

Nanostructured TiO<Subscript>2</Subscript> Films with a Mixed Phase for Perovskite Solar Cells

A series of thin films made with TiO₂ nanoparticles with a varied anatase/rutile phase ratio is prepared on conducting glass substrates using a spin-coating method. The structure, morphology, and optical properties of TiO₂ nanopowders and thin films fabricated are studied using powder X-ray diffraction, scanning electron microscopy, and optical spectroscopy. The TiO₂ nanostructured films created are used as photoelectrodes for the fabrication of perovskite solar cells (PSCs). The photovoltaic characteristics of PSCs under AM1.5 light illumination (1000 W/m²) under ambient conditions are studied. It is shown that the best efficiency of solar-to-electrical energy conversion, namely, 9.3%, is obtained for the PSC with a photoelectrode based on a TiO₂ film with an anatase/rutile mixed phase ratio of 86/14%.     

Thermal sensors based on Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> and (Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>)<Subscript>70</Subscript>(Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>)<Subscript>30</Subscript> thin films

Thin films of Sb₂Te₃ and (Sb₂Te₃)₇₀(Bi₂Te₃)₃₀ alloy and have been deposited on precleaned glass substrate by thermal evaporation technique in a vacuum of 2?×?10^?6 Torr. The structural study was carried out by X-ray diffractometer, which shows that the films are polycrystalline in nature. The grain size, microstrain and dislocation density were determined. The Seebeck coefficient was determined as the ratio of the potential difference across the films to the temperature difference. The power factor for the (Sb₂Te₃)₇₀ (Bi₂Te₃)₃₀ and (Sb₂Te₃) is found to be 19.602 and 1.066 of the film of thickness 1,500 Å, respectively. The Van der-Pauw technique was used to measure the Hall coefficient at room temperature. The carrier concentration was calculated and the results were discussed.     

Manganese doping effects on interband electronic transitions,lattice vibrations,and dielectric functions of perovskite-type Ba<Subscript>0.4</Subscript>Sr<Subscript>0.6</Subscript>TiO<Subscript>3</Subscript> ferroelectric ceramics

The Ba_0.4Sr_0.6−x Mn _x TiO₃ (BSMT) ceramics with different Mn composition (from 1% to 10%) have been prepared via the conventional solid-state reaction sintering. The X-ray diffraction analysis shows that the ceramics are polycrystalline with the single perovskite phase. The lattice vibrations and optical properties have been investigated using Raman scattering, spectroscopic ellipsometry (SE), and infrared reflectance spectra. It was found that the optical bandgap for the BSMT ceramics is varied between 3.40 and 3.65 eV. The three first-order Raman-active phonon modes can be observed, and the frequency of the A ₁(LO₃)/E(LO) mode shows a blue shift of 8 cm⁻¹ with the Mn composition, which can be attributed to the distortion of the TiO₆ octahedron. With increasing Mn composition, the frequency of the infrared-active TO₄ mode decreases from 532 to 520 cm⁻¹, owing to the local variation of the lattice constant induced by the Mn incorporation. Moreover, the optical functions of the ceramics from the far-infrared to ultraviolet region are obtained based on the SE and reflectance spectra, which is useful for the potential applications in ferroelectric-based optoelectronic devices.     

Photoactivity passivation of TiO<Subscript>2</Subscript> nanoparticles using molecular layer deposited (MLD) polymer films

Pigment-grade anatase TiO₂ particles (160 nm) were passivated using ultra-thin insulating films deposited by molecular layer deposition (MLD). Trimethylaluminum (TMA) and ethylene glycol (E.G) were used as aluminum alkoxide (alucone) precursors in the temperature range of 100–160 °C. The growth rate varied from 0.5 nm/cycle at 100 °C to 0.35 nm/cycle at 160 °C. Methylene blue oxidation tests indicated that the photoactivity of pigment-grade TiO₂ particles was quenched after 20 cycles of alucone MLD film, which was comparable to 70 cycles of Al₂O₃ film deposited by atomic layer deposition (ALD). Alucone films would decompose in the presence of water at room temperature and would form a more stable composite containing aluminum, which decreased the passivation effect on the photoactivity of TiO₂ particles.     

Synthesis of nanocrystalline multiphase titanium oxycarbide (TiC<Subscript>x</Subscript>O<Subscript>y</Subscript>) thin films by UNU/ICTP and NX2 plasma focus devices

Nanocrystalline multiphase titanium oxycarbide (TiC_xO_y) thin films composed of TiC₂, TiO_0.325, Ti₂O₃ and graphitic carbon have been deposited on titanium substrates, using energetic carbon ions delivered by the UNU/ICTP and the NX2 plasma focus devices operated at different repetition rates. X-ray diffraction (XRD) patterns of the nanocomposite films reveal the relative transformation of various oxide and carbide phases accompanied by the suppression of the TiC₂ phase when the energy flux of the ion beam and the repetition rate are increased. A field emission scanning electron microscope (FESEM) with an energy dispersive X-ray spectroscopy (EDS) attachment reveals a non-porous microcrack-free nanocrystalline granular surface morphology of the composite films with uniform carbon distribution. X-ray photoelectron spectroscopy (XPS) confirms the formation of oxycarbides (TiC_xO_y) along with significant carbon adsorbate. Raman studies of the films also verify the relative phase transformation in the TiC_xO_y nanocomposite by tuning the deposition parameters. The Vickers microhardness of the sample surface is improved more than 400%. PACS 52.59.Hq; 52.77.Dq; 68.55.Jk; 81.15.-z; 81.65.Lp     

X-ray spectroscopic examination of thin HfO<Subscript>2</Subscript> films ALD- and MOCVD-grown on the Si(100) surface

HfO₂ films 5 nm thick grown on Si(100) substrates by the methods of MOCVD hydride epitaxy and atomic layer deposition (ALD) are studied using X-ray photoelectron spectroscopy combined with Ar⁺ ion etching and X-ray reflectometry. It is found that (i) the ALD-grown HfO₂ films are amorphous, while the MOCVD-grown films show signs of a crystal structure; (ii) the surface of the ALD-grown films is more prone to contamination and/or is more reactive; and (iii) the amount of interfacial silicon dioxide in the case of the MOCVD-grown film is greater than in the case of the films synthesized by ALD. It is also shown that the argon ion etching of the HfO₂ film results in the formation of a metallic hafnium layer at the interface. This indicates that HfO₂ can be used not only as a gate dielectric but also as a material suitable for fabricating nanodimensional conductors by direct decomposition.     

Photoconductivity studies on amorphous and crystalline TiO<Subscript>2</Subscript> films doped with gold nanoparticles

In this work, amorphous and crystalline TiO₂ films were synthesized by the sol–gel process at room temperature. The TiO₂ films were doped with gold nanoparticles. The films were spin-coated on glass wafers. The crystalline samples were annealed at 100°C for 30 minutes and sintered at 520°C for 2 h. All films were characterized using X-ray diffraction, transmission electronic microscopy and UV-Vis absorption spectroscopy. Two crystalline phases, anatase and rutile, were formed in the matrix TiO₂ and TiO₂/Au. An absorption peak was located at 570 nm (amorphous) and 645 nm (anatase). Photoconductivity studies were performed on these films. The experimental data were fitted with straight lines at darkness and under illumination at 515 nm and 645 nm. This indicates an ohmic behavior. Crystalline TiO₂/Au films are more photoconductive than the amorphous ones.     

Electric and magnetic properties of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Pb(Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>)O<Subscript>3</Subscript> bilayer thin films prepared by pulsed-laser deposition

CoFe₂O₄ (CFO) thin film with highly (111)-preferential orientation was first deposited on the silicon substrate by a pulsed-laser deposition, and then Pb(Zr_0.52Ti_0.48)O₃ (PZT) layers were deposited with different oxygen pressures to form the bilayer CFO/PZT nanocomposite thin films. X-ray diffraction showed that the PZT preferential orientation was strongly dependant on the oxygen pressure. The smooth film surface was obtained after depositing the CFO and PZT layers. The bilayer thin films exhibit good ferromagnetic and ferroelectric properties, and a low leakage current density of 0.004 μA/cm² at 50 kV/cm. The leakage current density curves show loops for the electric polarized field when the electric field reverses. PACS 77.84.Lf; 75.80+q; 81.05.Zx; 81.15.Fg     

Influence of nanocrystalline structure and composition on hardness of thin films based on TiO<Subscript>2</Subscript>

In this work, the influence of Tb-doping on structure, and especially hardness of nanocrystalline TiO₂ thin films, has been described. Thin films were formed by a high-energy reactive magnetron sputtering process in a pure oxygen atmosphere. Undoped TiO₂-matrix and TiO₂:Tb (2 at. % and 2.6 at. %) thin films, had rutile structure with crystallite sizes below 10 nm. The high-energy process produces nanocrystalline, homogenous films with a dense and close packed structure, that were confirmed by X-ray diffraction patterns and micrographs from a scanning electron microscope. Investigation of thin film hardness was performed with the aid of a nanoindentation technique. Results of measurements have shown that the hardness of all manufactured nanocrystalline films is above 10 GPa. In the case of undoped TiO₂ matrix, the highest hardness value was obtained (14.3 GPa), while doping with terbium results in hardness decreasing down to 12.7 GPa and 10.8 GPa for TiO₂:(2 at. % Tb) and TiO₂:(2.6 at. % Tb) thin films, respectively. Incorporation of terbium into TiO₂-matrix also allows modification of the elastic properties of the films.     

Memory effect in Ba<Subscript>0.85</Subscript>Sr<Subscript>0.15</Subscript>TiO<Subscript>3</Subscript> ferroelectric films on silicon substrates

Ba_0.85Sr_0.15TiO₃ ferroelectric films on single-crystal silicon wafers were grown and studied. X-ray diffraction and electron microscopy studies showed that the films are characterized by a limited texture with a perovskite structure. It was shown that the grown films can be used as recording media for nonvolatile rerecorded data carriers in kinematic-type external memory devices. A possible mechanism of data recording and storage in the structures was considered.     

Optical and electrical properties of nanocrystalline TiO<Subscript>2</Subscript>:Pd semiconducting oxides

Electrical and optical properties of TiO₂:Pd thin films deposited from Ti-Pd mosaic targets sputtered in reactive oxygen plasma have been studied. The properties were investigated for thin films with the Pd amount of 5.5 at. %, 8.4 at. % and 23 at. %. Based on resistivity measurements a drop from 10³ down to almost 10⁻³Ωcm has been recorded when the Pd amount was varied from 5.5 at. % to 23 at. %, respectively. Moreover, it was shown that doping with different amounts of Pd results in the possibility of obtaining both types of electrical conduction: n-type for the TiO₂ with 5.5 at. % and 8.4 at. % of Pd and p-type for the TiO₂ with 23 at. % of Pd thin films. From optical measurements it has been found that as the Pd amount was increased the transmission through the thin films was reduced and position of the fundamental absorption edge was shifted toward a longer wavelength range of up to 600 nm. The optical band gap was calculated for direct and indirect transitions from optical absorption spectra. Structural properties were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). The XRD patterns displayed occurrence of the crystalline, TiO₂-rutile for lower Pd amounts (5.5 at. %, 8.4 at. %), while the TiO₂:Pd (23 at. %) thin films displayed XRD-amorphous behaviour. Images obtained from AFM displayed dense, nanocrystalline structure with homogenous distribution of crystallites. Additionally performed secondary ion mass spectroscopy investigation confirmed homogenous distribution of Pd in the whole thickness of the prepared thin films.     

Ion beam sputter deposition of TiO<Subscript>2</Subscript> films using oxygen ions

TiO₂ thin films were grown by ion beam sputter deposition (IBSD) using oxygen ions, with the ion energy and geometrical parameters (ion incidence angle, polar emission angle, and scattering angle) being varied systematically. Metallic Ti and ceramic TiO₂ served as target materials. The thin films were characterized concerning thickness, growth rate, surface topography, structural properties, mass density, and optical properties. It was found that the scattering geometry has the main impact on the film properties. Target material, ion energy, and ion incidence angle have only a marginal influence. Former studies on reactive IBSD of TiO₂ using Ar and Xe ions reported equivalent patterns. Nevertheless, the respective ion species distinctively affects the film properties. For instance, mass density and the refractive index of the TiO₂ thin films are remarkably lower for sputtering with oxygen ions than for sputtering with Ar or Xe ions. The variations in the thin film properties are tentatively attributed to the angular and the energy distribution of the film-forming particles, especially, to those of the backscattered primary particles.     

Controlling the orientation of ZnO nanorod arrays using TiO<Subscript>2</Subscript> thin film templates dip-coated by sol–gel

The oriented ZnO nanorod arrays have been synthesized on a silicon wafer that coated with TiO₂ films by aqueous chemical method. The morphologies, phase structure and the photoluminescence (PL) properties of the as-obtained product were investigated by field-emission scanning electron microscopy (FE-SEM), X-ray diffractometer (XRD), transmission electron microscope (TEM) and PL spectrum. The nanorods were about 100 nm in diameter and more than 1 μm in length, which possessed wurtzite structure with a c axis growth direction. The room-temperature PL measurement of the nanorod arrays showed strong ultraviolet emission. The effect of the crystal structure and the thickness of TiO₂ films on the morphologies of ZnO nanostructures were investigated. It was found that the rutile TiO₂ films were appropriate to the oriented growth of ZnO nanorod arrays in comparison with anatase TiO₂ films. Moreover, flakelike ZnO nanostructures were obtained with increasing the thickness of anatase TiO₂ films.     

Correlation of process parameters and properties of TiO<Subscript>2</Subscript> films grown by ion beam sputter deposition from a ceramic target

The correlation between process parameters and properties of TiO₂ films grown by ion beam sputter deposition from a ceramic target was investigated. TiO₂ films were grown under systematic variation of ion beam parameters (ion species, ion energy) and geometrical parameters (ion incidence angle, polar emission angle) and characterized with respect to film thickness, growth rate, structural properties, surface topography, composition, optical properties, and mass density. Systematic variations of film properties with the scattering geometry, namely the scattering angle, have been revealed. There are also considerable differences in film properties when changing the process gas from Ar to Xe. Similar systematics were reported for TiO₂ films grown by reactive ion beam sputter deposition from a metal target [C. Bundesmann et al., Appl. Surf. Sci. 421, 331 (2017)]. However, there are some deviations from the previously reported data, for instance, in growth rate, mass density and optical properties.     

Nonlinear dielectric response of epitaxial Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript> TiO<Subscript> 3</Subscript> thin films

Based on Landau-Devonshire (LD)-type phenomenological thermodynamic theory, the electric field dependence of the dielectric properties of tetragonal single-domain barium strontium titanate(Ba_1-xSr_xTiO₃) films on cubic substrates is theoretically investigated by taking into account the high order terms of the polarization. At room temperature, the nonlinear dielectric responses of epitaxial Ba_0.6Sr_0.4TiO₃ films are provided by adjusting the film thickness and growth temperature. The strong nonlinearity of relative dielectric constant and pyroelectric coefficient are attained around critical film thickness on MgO (69 nm) and LaAlO₃ (132 nm) substrates or critical growth temperature on MgO (337 °C) substrate with respect to epitaxy-induced lattice misfit and thermal stresses during deposition. This can be explained that small compressive stresses are effective to support high nonlinearity of dielectric constant and pyroelectric coefficient for Ba_0.6Sr_0.4TiO₃ films irrespective of whether they are on compressive substrate or tensile substrate. It is also predicted that a large tunability may be achieved by altering processing conditions, such as the film thickness and growth temperature for different substrates. Our theoretical results are in good agreement with the experimental data reported in literature.     

Characterization and electrical properties of high-<Emphasis Type="Italic">k</Emphasis> GdScO<Subscript>3</Subscript> thin films grown by atomic layer deposition

Gadolinium scandium oxide (Gd-scandate, GdScO₃) thin films were grown by atomic layer deposition (ALD) from β-diketonate precursors M(thd)₃ (M=Gd, Sc; thd=2,2,6,6-tetramethyl-3,5-heptanedionato) and ozone. The deposition parameters were optimized to produce films with the stoichiometric 1:1 metal ratio and a series of samples with nominal thicknesses of 5, 10, 15, and 20 nm were prepared. At 300 °C the metal precursor pulsing ratio Gd:Sc=5:6 yielded amorphous stoichiometric films and a growth rate of 0.21 Å/cycle. The films stayed amorphous up to 900 °C. The surface was probed with an AFM and the rms roughness was found to be 0.3 nm for the 5–20 nm thick films. The electrical properties of the as-deposited films proved to be very promising, with a dielectric constant of ～22 and leakage current density of 340 μA/cm², measured at -2 V.     

PLD and RF-PLD synthesis of Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> ferroelectric thin films for electrically controlled devices

Ba_0.6Sr_0.4TiO₃ (BST) bulk ceramic synthesized by solid state reaction was used as target for thin films grown by pulsed laser deposition (PLD) and radiofrequency beam assisted PLD (RF-PLD). The X-ray diffraction patterns indicate that the films exhibit a polycrystalline cubic structure with a distorted unit cell. Scanning Electron Microscopy investigations showed a columnar microstructure with size of spherical grains up to 150 nm. The capacitance–voltage (C–V) characteristics of the BST films were performed by applying a DC voltage up to 5 V. A value of 280 for dielectric constant and 12.5% electrical tunability of the BST capacitor have been measured at room temperature.