Titanium oxide nanostructured films by reactive pulsed laser deposition

Nanostructured titanium oxide thin films have been grown by nanosecond UV pulsed laser deposition (PLD) performed in a reactive background atmosphere. We exploited laser ablation of a Ti target at different pressures of pure oxygen and Ar:O₂ mixtures to show that film growth can be tuned at the nanoscale from compact and dense to columnar and to porous, leading to different morphology, density and structure (oxidized fraction and degree of crystallinity). We observed that the position of the substrate relative to the time integrated visible plume front is fundamental in the determination of film structure and morphology. Film growth and film properties can be related to a non-dimensional parameter L which is the ratio between the target-to-substrate distance and the visible plume length. In particular, surface morphology and degree of structural order are strictly related to L irrespective of the oxygen content, while the latter mainly affects the oxidized fraction in the film.     

Nickel oxide thin films synthesized by reactive pulsed laser deposition: characterization and application to hydrogen sensing

Transparent nickel oxide thin films were grown by reactive pulsed laser deposition. An ArF* (λ=193 nm, τ=12 ns) excimer laser source was used to ablate the Ni targets in a controlled pressure of ambient oxygen. The substrates were either kept at room temperature or heated to a selected temperature within the 200–400 °C range. Post-deposition heat treatment, which was applied to further promote crystallization and overcome any oxygen deficiency, yielded transparent thin films. The surface morphology and crystalline status of the synthesized thin structures were analyzed in correlation with their optical properties. A significant response to several concentrations of hydrogen was demonstrated when heating the nickel oxide films at 185 °C. PACS 78.66.Hf; 81.15.Fg; 82.47.Rs     

Anatase TiO2 films fabricated by pulsed laser deposition using Ti target

TiO₂ films were prepared by pulsed laser deposition using a metallic Ti target in an O₂ gas ambient. The microstructure along with optical and photocatalytic properties of the deposited films were systematically studied by changing the deposition parameters and substrates. It was found that TiO₂ films having nearly pure anatase phase grew effectively in O₂ atmosphere. When the films were fabricated at a substrate temperature of 400°C, their phase structures were greatly affected by the O₂ gas pressure, and nearly pure anatase phase with typical (101) and (004) peaks can be obtained under an O₂ pressure of 15 Pa. For the deposition at 700°C, the crystal structure of the TiO₂ films exhibited a strong anatase (004) peak and was inert to the oxygen pressures. Two modes, namely a substrate-temperature-controlled mode and an oxygen-pressure-controlled mode, were considered for the growth of the anatase TiO₂ films under different substrate temperatures. In addition, the optical and photocatalytic properties were found to be sensitive to both the microstructure and grain size of the TiO₂ films.     

Structural characterization of AlN films synthesized by pulsed laser deposition

We obtained AlN thin films by pulsed laser deposition (PLD) from a polycrystalline AlN target using a pulsed KrF* excimer laser source (248 nm, 25 ns, intensity of ∼4 × 10⁸ W/cm², repetition rate 3 Hz, 10 J/cm² laser fluence). The target-Si substrate distance was 5 cm. Films were grown either in vacuum (10⁻⁴ Pa residual pressure) or in nitrogen at a dynamic pressure of 0.1 and 10 Pa, using a total of 20,000 subsequent pulses. The films structure was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectral ellipsometry (SE). Our TEM and XRD studies showed a strong dependence of the film structure on the nitrogen content in the ambient gas. The films deposited in vacuum exhibited a high quality polycrystalline structure with a hexagonal phase. The crystallite growth proceeds along the c-axis, perpendicular to the substrate surface, resulting in a columnar and strongly textured structure. The films grown at low nitrogen pressure (0.1 Pa) were amorphous as seen by TEM and XRD, but SE data analysis revealed ∼1.7 vol.% crystallites embedded in the amorphous AlN matrix. Increasing the nitrogen pressure to 10 Pa promotes the formation of cubic (≤10 nm) crystallites as seen by TEM but their density was still low to be detected by XRD. SE data analysis confirmed the results obtained from the TEM and XRD observations.     

Amorphous hydrogenated carbon synthesized by pulsed laser deposition from cyclohexane

It is demonstrated that a liquid hydrocarbon precursor, cyclohexane, is appropriate for laser-induced carbon deposition. Amorphous hydrogenated carbon films (a-C:H) were deposited by KrF excimer laser irradiation of single-crystal silicon surface immersed under cyclohexane. The technique is simple and easy to operate. IR absorption spectra of the deposited films confirmed the presence of carbon in the diamond phase. Raman and XPS studies showed diamond-like character of the deposited films. Moreover, these two studies provided strong evidence that laser fluence played an important role in the formation of DLC bondings and the quality of the deposited films. Received: 15 September 1998 / Accepted: 5 January 1999 / Published online: 5 May 1999     

Preparation of Co:TiO2 thin films by crossed-beam pulsed laser deposition

Co:TiO₂ thin films were deposited using two interacting plasmas produced from different targets, TiO₂ and cobalt. By keeping constant the laser ablation conditions on the TiO₂ target and changing them on the Co target, it was possible to vary in a controlled way the Co content in the films. The cobalt plasma parameters, such as the ion kinetic energy and plasma density, were determined for each deposition condition in an attempt to correlate them with the material’s properties. The cobalt ion mean kinetic energy was varied from 36 to 789 eV, resulting in films with Co content from 1.2 up to 5.1 at.%, respectively, revealing that the cobalt content can be controlled by the Co⁺ kinetic energy. The study of the optical properties showed that the optical band gap decreased from 2.9 to 2.0 eV as the Co content increased. Raman spectroscopy was used to characterize the microstructure of the deposits, and the obtained results suggest the formation of two coexisting phases: TiO₂ in its rutile phase and CoTiO₃. It was found that as the Co⁺ energy increases, the CoTiO₃ phase develops in a greater quantity. XPS measurements confirm the Raman spectroscopy results.     

Raman characteristics of carbon nitride synthesized by nitrogen-ion-beam-assisted pulsed laser deposition

Raman characteristics of carbon nitride films synthesized by nitrogen-ion-beam-assisted pulsed laser deposition were investigated. In addition to the D (disorder) band and G (graphitic) band commonly observed in carbon nitride films, two Raman bands located at 1080–1100 and 1465–1480 cm^-1 were found from our carbon nitride films. These two bands were well matched with the predicted Raman frequencies for βC₃N₄ and the observed Raman bands reported for carbon nitride films, indicating their relation to carbon-nitrogen stretching vibrations. Furthermore, the relative intensity ratio of the two Raman bands to the D and G bands increased linearly with increasing nitrogen content of the carbon nitride films. Received: 30 October 2000 / Accepted: 5 February 2001 / Published online: 2 October 2001     

TiCN thin films grown by reactive crossed beam pulsed laser deposition

In this work, we used a crossed plasma configuration where the ablation of two different targets in a reactive atmosphere was performed to prepare nanocrystalline thin films of ternary compounds. In order to assess this alternative deposition configuration, titanium carbonitride (TiCN) thin films were deposited. Two crossed plasmas were produced by simultaneously ablating titanium and graphite targets in an Ar/N₂ atmosphere. Films were deposited at room temperature onto Si (100) and AISI 4140 steel substrates whilst keeping the ablation conditions of the Ti target constant. By varying the laser fluence on the carbon target it was possible to study the effect of the carbon plasma on the characteristics of the deposited TiCN films. The structure and composition of the films were analyzed by X-ray Diffraction, Raman Spectroscopy and non-Rutherford Backscattering Spectroscopy. The hardness and elastic modulus of the films was also measured by nanoindentation. In general, the experimental results showed that the TiCN thin films were highly oriented in the (111) crystallographic direction with crystallite sizes as small as 6.0 nm. It was found that the hardness increased as the laser fluence was increased, reaching a maximum value of about 33 GPa and an elastic modulus of 244 GPa. With the proposed configuration, the carbon content could be easily varied from 42 to 5 at.% by changing the laser fluence on the carbon target.     

Nanostructured tungsten oxide thin films by the reactive pulsed laser deposition technique

Preparation of nanostructured tungsten oxide thin films using the reactive pulsed laser ablation technique is reported. The structural, morphological, optical and electrical properties of deposited films are systematically studied by changing the ambient oxygen pressure (pO₂). Structural dependence of tungsten oxide films on ambient oxygen pressure is discussed using grazing incidence X-ray diffraction (GIXRD) and micro-Raman spectra. The section analysis using atomic force microscopy exposed the smooth surface features of the deposited films. The blue shift in optical bandgap with an increase in ambient oxygen pressure is expounded in terms of electronic band structure of tungsten oxide. The influence of oxygen pressure on optical constants like extinction coefficient, band edge sharpness, refractive index and optical bandgap is also conveyed. The temperature variation of electrical resistance for films deposited at 0.12 mbar furnishes evidence for its semiconducting nature. PACS 68.55-a; 72.80.Ga; 81.15.Fg; 81.07.Bc; 78.68.+m; 78.20.Ci     

Nitrogen-doped ZnO prepared by capillaritron reactive ion beam sputtering deposition

Nitrogen-doped ZnO thin films have been prepared by reactive ion beam sputtering deposition utilizing a capillaritron ion source. X-ray diffraction (XRD) analysis of the as-deposited film exhibits a single strong ZnO (002) diffraction peak centred at 34.40°. Post-growth annealing causes increase of grain size and decrease of c-axis lattice constant. Micro-Raman spectroscopy analysis of the as-deposited film shows strong nitrogen-related local vibration mode at 275, 582, 640 and 720 cm⁻¹, whereas the E₂ mode of ZnO at 436 cm⁻¹ can barely be identified. Annealing at 500-800 °C causes decrease of 275, 582, 640 and 720 cm⁻¹ and increase of 436 cm⁻¹ intensity, indicating out-diffusion of nitrogen and improvement of ZnO crystalline quality. Unlike un-doped ZnO, the surface roughness of nitrogen-doped ZnO deteriorates after annealing, which is also attributed to the out-diffusion of nitrogen. A nitrogen concentration of ∼10²¹/cm³ was observed while type conversion from n-type to p-type was not achieved, which is likely due to the formation of Zn_I-N_O or (N₂)_O that act as donor/double donors.     

Fabrication of one-dimensional photonic crystals with Al2O3/TiO2 by pulsed laser deposition

One-dimensional photonic crystal (1D PC) mirrors consisting of Al₂O₃/TiO₂ stacks are theoretically and experimentally investigated at visible frequencies. In our experiments the refractive index of Al₂O₃ is tunable from 1.43 to 1.68. We found that the Al₂O₃/TiO₂ combination can be adopted to fabricate both broad- and narrow-band 1D PC mirrors: Substituting nanoporous Al₂O₃ for dense SiO₂ in an SiO₂/TiO₂ broad-band mirror yields the same spectral properties, while using dense Al₂O₃ in the combination can reduce the band-gap width to as low as 30 nm. The experimentally measured reflection and transmission spectra agree with the numerical results obtained by the transfer matrix method.     

Biocompatible and bioactive coatings of Mn-doped β-tricalcium phosphate synthesized by pulsed laser deposition

The extension of pulsed laser deposition to the synthesis on Ti substrates of β-tricalcium phosphate (β-TCP) coatings doped with manganese is reported. Targets sintered from two crystalline Mn-doped β-TCP powders (with the composition Ca_2.9Mn_0.1(PO₄)₂ and Ca_2.8Mn_0.2(PO₄)₂) were ablated with an UV KrF* (λ = 248 nm, τ ∼ 7 ns) laser source. X-ray diffraction and energy dispersive X-ray spectroscopy investigations showed that the films, while prevalently amorphous, had a Ca/P ratio of about 1.50-1.52. Scanning electron microscopy analyses revealed a rather homogeneous aspect of the coatings which were molded to the relief of the chemically etched Ti substrate. Fluorescence microscopy was applied to test the proliferation of mesenchymal stem cells grown on the obtained biostructures. Our investigations found that, even 14 days after cultivation, the synthesized films were not cytotoxic. On the contrary, they showed excellent bioactivity, as demonstrated by the neat spread of the cells over the entire surface of Mn-doped β-TCP. When tested in osteoprogenitor cell culture, the Ca_2.8Mn_0.2(PO₄)₂ samples revealed a higher potential for proliferation and better viability compared with Ca_2.9Mn_0.1(PO₄)₂.     

Effect of deposition parameters on morphology and size of FeCo nanoparticles synthesized by pulsed laser ablation deposition

The experimental parameters that control the surface morphology and size of iron cobalt nanoparticles synthesized at room temperature by pulsed laser ablation deposition (PLAD) technique have been systematically investigated. The nanoparticle synthesis has been achieved at higher operating gas pressures of argon. It was found that nanoparticles upon deposition formed small clusters, the size of which increases with decreasing pressure, increasing laser-energy density, and decreasing target-to-substrate distance. This trend could be attributed to change in the kinetic energy of deposited nanoparticles with varying argon pressure, laser-energy, and target-to-substrate distance. The nanoparticles size and size distribution showed strong dependence on argon pressure and weak dependence on laser-energy density and target-to-substrate distance.     

Preparation of Bi:TiO2 thin films by an hybrid deposition configuration: pulsed laser deposition and thermal evaporation

The aim of this work was to report the application of an hybrid deposition configuration to deposit Titanium dioxide (TiO₂) thin films modified with different amounts of bismuth (Bi:TiO₂). The samples were synthesized combining a TiO₂ laser ablation plasma with a flux of vapor of bismuth produced by thermal evaporation. By varying the deposition rate of Bi it was possible to control the amount of Bi incorporated in the film and consequently the film properties. A detailed compositional, structural, and optical characterization by XPS, RBS, Raman spectroscopy, and UV–Vis spectrometry techniques is discussed. Photocatalytic response of the deposited thin films was studied through the degradation of a malachite green solution.     

Influence of the substrate temperature on BCN films deposited by sequential pulsed laser deposition

The influence of substrate temperature on the composition and crystallinity of boron carbonitride (BCN) thin films deposited on (100) Si substrates by sequential pulsed laser deposition (PLD) has been investigated. A correlation between the target composition, the nitrogen pressure involved in the process, and the amount of B, C, and N elements (at % ) in the deposited films is established from energy dispersive spectroscopy (EDS) analysis. Electron microscopy studies show that the films deposited on heated substrates are mainly amorphous. Fourier-transform infrared spectroscopy (FTIR) analysis confirms the BCN-compound formation: the peak of C-BN and the peaks from B-N-B bending vibrations and C-N C-bond vibrations are present in the spectra. SEM studies show that the deposited films have a smooth surface, with no cracks and few droplets. Results were compared with those obtained on films deposited at room temperature under similar experimental conditions.     

VO2-WO3 nanocomposite thin films synthesized by pulsed laser deposition technique

Pure VO₂ and VO₂-WO₃ composite thin films were grown on quartz substrate by pulsed laser deposition (PLD) technique. The influence of varying WO₃ molar concentration in the range from x = 0.0 to x = 0.4 on structural, electrical and optical properties of VO₂-WO₃ nanocomposite thin films has been systematically investigated. X-ray diffraction studies reveal the single crystalline monoclinic VO₂ phase (m-VO₂) up to 10% of WO₃ content whereas both m-VO₂ as well as h-WO₃ (hexagonal WO₃) phases were present at higher WO₃ content (0.2 ≤ x ≤ 0.4). Optical transmittance spectra of the films showed blue shift in the absorption edge with increase in WO₃ content. Temperature dependence of resistivity (R-T) measurements indicates significant variation in metal-insulator transition temperature, width of the hysteresis, and shape of the hysteresis curve. Cyclic Voltammetry measurements were performed on VO₂-WO₃ thin films. A direct correlation between V/W ratio and structure-property relationship was established. The present investigations reveal that doping of WO₃ in VO₂ is effective to increase the optical transmittance and to reduce the semiconductor to metal phase transition temperature close to room temperature.     

Chemical analysis of a-CNx thin films synthesized by nanosecond and femtosecond pulsed laser deposition

An ArF excimer laser (22 ns, 193 nm) and a hybrid dye/excimer laser system (500 fs, 248 nm) are used to deposit amorphous carbon nitride films at room temperature by ablation of a graphite target in nitrogen atmosphere. The chemical composition and structure of the films is characterized by X-ray photoelectron spectroscopy. In the nanosecond case, the nitrogen content increases with reactive gas pressure up to 45 atomic %, while in the subpicosecond case it remains below 7 at. %. When processed with nanosecond pulses, the films' nitrogen content steeply increases with fluence up to a maximum. The target-to-substrate distance has only minor influence on the amount of nitrogen incorporated into the films. The dependence of the carbon-carbon and carbon-nitrogen bond configurations on the processing parameters is also given.     

AgAsS2 amorphous chalcogenide films prepared by pulsed laser deposition

A pulsed laser deposition technique has been applied to prepare amorphous ternary Ag–As–S films without an annealing process after the deposition. The films were prepared from AgAsS₂ bulk glass using a KrF excimer laser. Energy-dispersive X-ray analysis and Rutherford backscattering were used to obtain the composition of the studied films. VASE ellipsometry has been used to determine optical properties and homogeneity of the index of refraction. Comparison of two models is presented. PACS 78.66.Jg; 81.15.Fg; 81.40.Wx     

Microstructural characterization of Ti-C-N thin films prepared by reactive crossed beam pulsed laser deposition

In this work, Raman spectroscopy has been used to characterize Ti-C-N thin films in order to obtain information about the microstructure of the deposited materials, and in particular to study the effects due to the carbon incorporation into the TiN lattice. Ti-C-N thin films were prepared using a crossed plasma configuration in which the ablation of two different targets, titanium and carbon, in a reactive atmosphere was performed. With this configuration, the carbon content in the films was varied in an easy way from 5.0 at% to 40.0 at%. Thin film composition was determined from Non-Rutherford Backscattering Spectroscopy (NRBS) measurements. X-ray photoelectron spectroscopy and X-Ray diffraction measurements were also carried out in order to characterize the films in more detail, with this being used to give support to the interpretation of the Raman spectra. The Raman results revealed that at lower carbon concentrations a solid solution Ti(C, N) is formed, whilst at higher carbon concentrations a nanocomposite, consisting of nanocrystalline TiCN and TiC immersed in an amorphous carbon matrix is obtained.     

脉冲激光沉积法制备的Ni1-xFexO稀磁半导体的结构和磁性研究

利用脉冲激光沉积方法制备出了具有室温铁磁性的Ni1-1-xFexO(x=0.02,O.05)稀磁半导体.X射线衍射(XRD)结果表明Ni,1-xFexO的品体结构为Nacl结构,并且在Fe含量较高的Ni095Fe0.05O中出现了少量的a-Fe2O3物相.X射线吸收近边结构谱(XANFS)和X射线光电子能谱(XPs)进一步表明了掺杂的Fe原子替代Ni0日格中Ni原子,并且样品中不存在能够诱导室温磁性的第二相.这些研究结果表明Ni1-xFexO的室温铁磁性是本征的.