Influence of growth time and annealing on rutile TiO2 single-crystal nanorod arrays synthesized by hydrothermal method in dye-sensitized solar cells

Vertically aligned TiO₂ nanorod (NR) arrays have been grown on the fluorine doped tin oxide (FTO) substrates by hydrothermal methods and the structures were employed to fabricate the dye-sensitized solar cells (DSSCs). The charge transport properties were investigated by the current to voltage curves and the electrochemical impedance spectroscopy. It was found that DSSCs containing the as-prepared and 500 °C annealed TiO₂ NRs exhibit different trends with the growth time (t). The DSSCs assembled with the un-sintered NR arrays showed the highest power conversion efficiency (η) of 1.87%. When DSSCs were assembled with the sintered NR arrays, nearly 400% enhanced efficiency were obtained, and the values (η) showed a positive correlation with t. This behavior may be attributed to the improved adhesion and electric contact between TiO₂ and FTO, as well as the reduced number of recombination sites.     

Photocatalytic degradation of selected dyes by titania thin films with various nanostructures

Titania thin films with various nanostructures of quasi-aligned nanorods, well-aligned nanotubes and nanoparticle aggregates were fabricated and utilized to assist photodegradation of three typical dye derivatives in water, i. e., rhodamine B (RB), methylene blue (MB) and methyl orange (MO). The thin films were characterized by X-ray diffraction, scanning electron microscope and UV-Vis diffuse reflectance spectra. It is found that the bandgap of most lab-fabricated thin films can be estimated more appropriately assuming a direct transition between the valance band and the conduction band of titania. The so-called natural ageing phenomenon was evidence for all the films to assist photodegradation of RB and MB in water; but not discernible for MO, which was much reluctant to photodegradation. MB decomposed much quickly than RB when assisted by titania with predominantly anatase; on the other hand, rutile favored the photodegradation of RB than that of MB. Titania thin films with top morphologies of quasi-aligned nanorods or nanotubes were found to possess advantageous turnover frequency and photonic efficiency over commercial P25 titania and sol-gel derived titania to assist photodegradation of RB and MB in water.     

Femtosecond laser deposition of TiO2 by laser induced forward transfer

Femtosecond lasers have been used for laser induced forward transfer (LIFT) of TiO₂, a wide-band semiconductor with many industrial and research applications. TiO₂ polycrystalline thin films on quartz (obtained by pulsed laser deposition) were used as donors and both quartz and fluorine-doped tin dioxide coated glass substrates as acceptors. LIFT was performed at the laser wavelengths of 248 and 800 nm with pulses of 450 and 300 fs respectively. The transferred material was characterized by energy-dispersive X-ray spectroscopy, X-ray diffraction and micro-Raman spectroscopy to determine the composition and crystalline quality, and by scanning electron microscopy and atomic force microscopy to assess the surface morphology. The relation between these properties and the laser transfer conditions, including wavelength, pulse energy and acceptor substrate, are presented.     

Structural and morphological transformations of TiO2 nanotube arrays induced by excimer laser treatment

The structural and morphological transformations of TiO₂ nanotube arrays (TNAs) treated by excimer laser annealing (ELA) were investigated as a function of the laser fluence using parallel and tilted modes. Results showed that the crystallinity of the ELA-treated TNAs reached only about 50% relative to that of TNAs treated by furnace anneal at 400 °C for 1 h. The phase transformation starts from the top surface of the TNAs with surface damage resulting from short penetration depth and limited one-dimensional heat transport from the surface to the bottom under extremely short pulse duration (25 ns) of the excimer laser. When a tilted mode was used, the crystallinity of TNAs treated by ELA at 85° was increased to 90% relative to that by the furnace anneal. This can be attributed to the increased area of the laser energy interaction zone and better heat conduction to both ends of the TNAs.     

Multi-orientation patterned deposition of BaTiO3 thin films using an Au buffer layer

The control of crystallographic orientation for ferroelectric oxide thin films grown on single crystal substrates has been investigated. We find that perovskite BaTiO₃ has unusual orientation distributions when deposited on (100)- and (110)-oriented SrTiO₃ single crystal substrates that have predeposited patterned Au regions. BTO areas deposited on gold islands were found to have a (111) orientation, whereas those deposited directly on STO had the same orientation as the substrate. Based on this method, we can select, locate, and pattern an oxide film to have different orientation distributions, and thereby engineer films with the complete property anisotropy in-plane.     

Study on TiO2 thin films grown by advanced pulsed laser deposition on ITO

TiO₂ films were grown by an advanced pulsed laser deposition method (PLD) on ITO substrates to be used as functional electrodes in the manufacturing of solar cells. A pure titanium target (99.99%) was irradiated by a Nd:YAG laser (355 and 532 nm, 5 ns, 35 mJ, 3 J/cm²) in an oxygen atmosphere at different pressures (20-160 mTorr) and at room temperature. After deposition, the films were subjected to an annealing process at 350 °C. The film structure, surface morphology, thickness, roughness, and optical transmission were investigated. Regardless of the wavelength used, the films deposited at room temperature presented only Ti₂O and TiO peaks. After thermal treatment, the TiO₂ films became strongly crystalline, with a tetragonal structure and in the anatase phase; the threshold temperature value was 250 °C. The deposition rate was in the range of 0.035-0.250 nm/pulse, and the roughness was 135-305 nm. Optical transmission of the films in the visible range was between 40% and 60%.     

Pulsed laser deposition of silicon-substituted hydroxyapatite coatings

Thin films of Si-substituted hydroxyapatite (Si-HA) were deposited on Si and Ti substrates by pulsed laser deposition (PLD), in the presence of a water vapour atmosphere. The PLD ablation targets were made with different mixtures of commercial carbonated HA and Si powder, in order to produce the Si-HA thin films. The physicochemical properties of the coatings and the incorporation of the Si into the HA structure was studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Si atoms were successfully incorporated into the HA structure, and were found to be in the form of SiO₄⁴⁻ groups, principally displacing carbonate groups off the HA structure.     

A parametric study of AlN thin films grown by pulsed laser deposition

High quality AlN thin films were grown at 200–450°C on sapphire substrates by laser ablation of Al targets in nitrogen reactive atmosphere. The nitrogen pressure was varied between 10⁻³ and 10⁻¹ mbar. The reactive gas pressure during irradiation and the temperature of the substrate were found to essentially influence the quality of the layers. X-ray diffraction analysis evidenced the formation of highly orientated layers for a very restrictive set of parameters. Other analysis techniques, like X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, optical transmission spectroscopy have been used to evidence the good stoichiometry and purity of the films. The characteristics of these films were compared with those of AlN thin films deposited in similar experimental conditions, on Si (100) and Si (111) substrates.     

Nanostructured tungsten and tungsten trioxide films prepared by glancing angle deposition

Nanostructured tungsten (W) and tungsten trioxide (WO₃) films were prepared by glancing angle deposition using pulsed direct current magnetron sputtering at room temperature with continuous substrate rotation. The chemical compositions of the nanostructured films were characterized by X-ray photoelectron spectroscopy, and the film structures and morphologies were investigated using X-ray diffraction and high resolution scanning electron microscopy. Both as-deposited and air annealed tungsten trioxide films exhibit nanostructured morphologies with an extremely high surface area, which may potentially increase the sensitivity of chemiresistive WO₃ gas sensors. Metallic W nanorods formed by sputtering in a pure Ar plasma at room temperature crystallized into a predominantly simple cubic β-phase with <100> texture although evidence was found for other random grain orientations near the film/substrate interface. Subsequent annealing at 500 °C in air transformed the nanorods into polycrystalline triclinic/monoclinic WO₃ structure and the nanorod morphology was retained. Substoichiometric WO₃ films grown in an Ar/O₂ plasma at room temperature had an amorphous structure and also exhibited nanorod morphology. Post-deposition annealing at 500 °C in air induced crystallization to a polycrystalline triclinic/monoclinic WO₃ phase and also caused a morphological change from nanorods into a nanoporous network.     

Improved dielectric and ferroelectric properties in Ti-doped BiFeO3-PbTiO3 thin films prepared by pulsed laser deposition

Ti-modified thin films of multiferroic 0.72Bi(Fe_1 − xTi_x)O₃-0.28PbTiO₃ (BFPT, x = 0 and 0.02) solid solution were prepared by pulsed laser deposition. The BFPT (x = 0 and 0.02) films possess a tetragonal structure with highly preferential (001) orientation. The effects of the ionic substitution on the properties of BFPT (x = 0 and 0.02) films have been investigated. The leakage current of the BFPT (x = 0.02) thin film is significantly reduced, and the dielectric and ferroelectric properties greatly improved by the aliovalent ionic substitution of Ti⁴⁺ for Fe³⁺. The BFPT (x = 0.02) thin film exhibits a reasonably high remnant polarization P_r with 2P_r up to 90 μC/cm² at 312 kV/cm and a switchable polarization up to 92 μC/cm² at 417 kV/cm.     

Imposed layer-by-layer growth of ZnO on GaN/sapphire substrates using pulsed laser interval deposition

The oxide semiconductor ZnO is of high interest for electrooptical applications due to its direct and wide band gap in the UV region. We present our results on pulsed laser deposition growth of ZnO on GaN-buffered Al₂O₃ substrates. Using in-situ reflection high energy electron diffraction, intensity oscillations were recorded and used to apply the technique of interval deposition. A significant improvement of structural thin film quality was achieved due to the expansion of the high quality from the first layers to the whole film thickness.     

Effect of inert gas on pulsed laser deposition of rare earth doped fluoride thin films

The realization of crystalline sub micrometric films of Nd³⁺:LiYF₄ fluorides on pure LiYF₄ substrates by pulsed laser deposition is reported. The films were obtained by laser ablation with 355 nm photons of a bulk LiYF₄ crystal doped with Nd³⁺ ions at 1.5% atomic concentration. Both low and high laser ablation fluency regimes were checked. The fundamental contribution of He inside a vacuum chamber to obtain crystalline Nd³⁺:LiYF₄ films was demonstrated. The optical characteristics of the films were analyzed via recording the emission spectra following IR excitation, polarized both with E || and E to the substrate c-axis. Lifetime measurements of the fundamental Nd³⁺ ion transition in the films were also performed. All the results were compared with those obtained in the Nd³⁺:LiYF₄ bulk crystal under the same experimental conditions. The scanning electron microscope pictures of the depositions gave indications about the film surface morphology.     

Rietveld X-ray diffraction analysis of nanostructured rutile films of titania prepared by pulsed laser deposition

Rietveld powder X-ray diffraction analysis of the rutile films of titanium oxide prepared by pulsed laser deposition was carried out. The crystallite size increased with increase of substrate temperature, while the strain showed a reverse trend. The films synthesized at temperature ≥573 K showed that the crystal structure was almost close to that of bulk rutile structure. The influence of the substrate temperature on the lattice parameters and oxygen coordinates were also studied in the present work.     

Dissimilar welding of carbon steel to 5754 aluminum alloy by Nd:YAG pulsed laser

Laser welding of low carbon steel to 5754 aluminum alloy was studied in keyhole welding mode in steel-on-aluminum overlap configuration. In order to decrease formation of intermetallic components during laser welding, effect of laser power, pulse duration and overlapping factor was investigated. Tensile test was performed to identify the effect of each parameter on the weld. The phase composition was characterized by energy dispersive spectrometry and Vickers microhardness test and microstructure by optical and scanning electronic microscopes. Results obtained show that increasing peak power (in constant pulse energy), pulse duration (in constant peak power) and overlapping factor (in constant pulse energy and peak power) will increase percentage of intermetallic components (PIC). On the other hand, decreasing the mentioned parameters will cause destructive effects such as inadequate penetration depth, spattering and cavity formation. Improvement in the tensile strength was attributed to low values of intermetallic components in weld metal. Finally, an optimized peak power, pulse duration and overlapping factor were reported.     

Growth and characterization of Bi2Se3 thin films by pulsed laser deposition using alloy target

Bi₂Se₃ thin films were deposited on the (100) oriented Si substrates by pulsed laser deposition technique at different substrate temperatures (room temperature −400 °C). The effects of the substrate temperature on the structural and electrical properties of the Bi₂Se₃ films were studied. The film prepared at room temperature showed a very poor polycrystalline structure with the mainly orthorhombic phase. The crystallinity of the films was improved by heating the substrate during the deposition and the crystal phase of the film changed to the rhombohedral phase as the substrate temperature was higher than 200 °C. The stoichiometry of the films and the chemical state of Bi and Se elements in the films were studied by fitting the Se 3d and the Bi 4d5/2 peaks of the X-ray photoelectron spectra. The hexagonal structure was seen clearly for the film prepared at the substrate temperature of 400 °C. The surface roughness of the film increased as the substrate temperature was increased. The electrical resistivity of the film decreased from 1 × 10⁻³ to 3 × 10⁻⁴ Ω cm as the substrate temperature was increased from room temperature to 400 °C.     

Line defects, planar defects and voids in SrTiO3 films grown on MgO by pulsed laser and pulsed laser interval deposition

Two and three dimensional growth of SrTiO₃ films on (001) MgO substrate was achieved by pulsed laser interval and pulsed laser deposition respectively. The growth mode was monitored by in-situ reflection high energy electron diffraction. Interval deposition forces layer-by-layer growth of materials even with such a large lattice misfit (~ 7.9%). A titanium dioxide buffer monolayer was deposited to allow the film to wet the substrate to encourage two dimensional growth of the strontium titanate. A variety of defects was investigated using transmission electron microscopy and high resolution scanning transmission electron microscopy. Misfit dislocations, steps at the interface, Ti-rich defects and regularly shaped nano-holes connected by anti-phase boundaries were found to be the dominant defects in these films grown layer by layer. The edges of the nano-holes were mainly along [010] and [100] for a [001] growth direction. The large strain between the two crystal systems with large lattice mismatch leads to in-plane tensile stress during the layer-by-layer growth. The stress is relieved in part by the holes. The films with a three dimensional growth mode possess a uniform surface with dislocations as the dominant defects. The individual densities of the various defects, including a Ti-rich phase and misfit and threading dislocations, are determined by the kinetics of the deposition method.     

Pulsed laser deposition of La0.67Ca0.33MnO3 thin films on LiNbO3 and surface acoustic wave studies

Surface Acoustic Waves on piezoelectric substrates can be used to investigate the dynamic conductivity of thin films in a non-contact and very sensitive way, especially at low conductivities. Here, we report on such surface acoustic wave studies to characterize thin manganite film like La_0.67Ca_0.33MnO₃, exhibiting a Jan Teller effect with a strong electron phonon interaction and a metal insulator transition at high temperatures.

We report on the deposition of La_0.67Ca_0.33MnO₃ on piezoelectric substrates (LiNbO₃ in different crystal cuts, employing a pulsed laser deposition technique. The structural quality of the thin films are examined by X-Ray Diffraction, Scanning Electron Microscope and Energy Dispersive X-ray spectroscopy. For the electrical characterization, we employ the surface acoustic wave technique, accompanied by conventional direct current resistance measurements for comparison.     

Photocatalytic activity of vanadium-doped titania-activated carbon composite film under visible light

A V-doped titania-activated carbon composite film was prepared by a modified sol-gel method under mild condition. X-ray diffraction analysis revealed that the titania was a pure anatase phase. From scanning electron microscopy and N₂ adsorption-desorption measurements, we found that the composite film was porous since it formed a micro-nano structure. The photocatalytic activity of such film was evaluated through degradation of azo-dye Reactive Brilliant Red under visible light, and was compared to commercially available TiO₂, pure titania and vanadium-doped titania films. Results showed that the photocatalytic activity was enhanced a lot. It was due to expansion of the absorption edge by vanadium doping, and the synergistic effect of activated carbon with titania. Furthermore, the hydrophilic property of the as-prepared composite film was superior to other samples.     

Structural properties of cobalt ferrite thin films deposited by pulsed laser deposition: Effect of the reactive atmosphere

Cobalt ferrite thin films have been elaborated by pulsed laser ablation of a CoFe₂ metallic target on Si (100) substrates. The films were deposited at low temperature (300 °C) in various pressures of two different reactive atmospheres (O₂/N₂, 20:80 and O₂). We present the influence of the nature of the reactive gas and of the deposition pressure on the crystallisation. It has been shown that a strong (111) preferential orientation is obtained for intermediate pressures of the O₂/N₂ reactive gas. The degree of orientation is higher for the O₂/N₂ mixture than for pure O₂. This behaviour is explained in terms of kinetic energy of the deposited species.     

Effect of the electrolyte composition on the anatase fraction of photocatalytic active TiO2 coatings prepared by plasma assisted anodic oxidation

Titanium dioxide is one of the most commonly used semiconductors for photocatalytic applications. In the majority of experimental studies, titanium dioxide is used in a powder form. In the present investigations titanium dioxide layers were formed by the plasma assisted anodic oxidation process SOLECTRO®. In this process a titanium substrate (anode) is dipped into an electrolyte bath containing a titanium precursor. Impressing a voltage greater than 100 V, a titanium dioxide layer is deposited on the substrate in several minutes. The titanium dioxide is formed from the constituents of the electrolyte. For this reason, the composition of the electrolyte influences the deposition process and also the phase fractions and the layer morphology. It is known that the photocatalytic activity of titanium dioxide layers depends strongly on the anatase volume fraction, the layer morphology and therefore the specific surface area. The standard SOLECTRO® process generates titanium dioxide layers consisting of nearly 25 vol.% anatase and 75 vol.% rutile. In the present study, the electrolyte's constituents, especially the chelating agent, were varied to increase the anatase percentage. The results show that the anatase fraction and the specific surface area can be increased by substitution of ethylendiammintetraacetic acid by dieethylenetriaminepentaacetic acid. The anatase fraction amounts to 44 vol.% using the new electrolyte composition.