Effect of substrate temperature on structure and electrical resistivity of laser-ablated IrO2 thin films

IrO₂ thin films were prepared on Si(1 0 0) substrates by laser ablation. The effect of substrate temperature (T_sub) on the structure (crystal orientation and surface morphology) and property (electrical resistivity) of the laser-ablated IrO₂ thin films was investigated. Well crystallized and single-phase IrO₂ thin films were obtained at T_sub = 573-773 K in an oxygen partial pressure of 20 Pa. The preferred orientation of the laser-ablated IrO₂ thin films changed from (2 0 0) to (1 1 0) and (1 0 1) depending on T_sub. With the increasing of T_sub, both the surface roughness and crystallite size increased. The room-temperature electrical resistivity of IrO₂ thin films decreased with increasing T_sub, showing a low value of (42 ± 6) × 10⁻⁸ Ω m at T_sub = 773 K.     

Optical characterization of PLD grown nitrogen-doped TiO2 thin films

Nitrogen-doped TiO₂ thin films were prepared by pulsed laser deposition (PLD) by ablating metallic Ti target with pulses of 248 nm wavelength in reactive atmospheres of O₂/N₂ gas mixtures. The layers were characterized by UV-VIS spectrophotometry and variable angle spectroscopic ellipsometry with complementary profilometry for measuring the thickness of the films. Band gap and extinction coefficient values are presented for films deposited at different substrate temperatures and for varied N₂ content of the gas mixture. The shown tendencies are correlated to nitrogen incorporation into the TiO_2-xN_x layers. It is shown that layers of significantly increased visible extinction coefficient with band gap energy as low as 2.89 eV can be obtained. A method is also presented how the spectroscopic ellipsometric data should be evaluated in order to result reliable band gap values.     

TbMnO3 epitaxial thin films by pulsed-laser deposition

Epitaxial TbMnO₃ films have been fabricated on SrTiO₃(001) and LaAlO₃(001) substrates by pulsed laser deposition (PLD), the structure and surface morphology of the films were characterized by X-ray diffraction with Cu K_α radiation and atomic force microscopy. The electrical transport and magnetic properties of the TbMnO₃ films and bulk were examined, the resistivity and the forbidden band width E_g change with epitaxial orientation, semiconductor transport properties are found in the films and bulk, the average of the E_g of the films on SrTiO₃ and on LaAlO₃ is equal to the E_g of the bulk. The two TMO films have different magnetization mode, the magnetization of the film on SrTiO₃ have an analogy to that of TbMnO₃ single crystal.     

Fabrication and characterization of TS-1 films on α-Al2O3 substrates using TiCl3 as titanium source

The continuous and highly intergrown anatase-free TS-1 film was fabricated with TiCl₃ as the titanium source for the first time. The in situ nucleation and secondary growth method was employed to synthesize the TS-1 film. By means of scanning electron microscopy (SEM) images, X-ray diffraction (XRD) patterns, and FT-IR and UV-vis spectra measurements, the resulting film was observed to be anatase-free, continuous and highly intergrown with the MFI-type structure, and the Ti atoms existed only in tetrahedral coordination.     

Epitaxial growth and structural characterization of Pb(Fe1/2Nb1/2)O3 thin films

We have grown lead iron niobate thin films with composition Pb(Fe_1/2Nb_1/2)O₃ (PFN) on (0 0 1) SrTiO₃ substrates by pulsed laser deposition. The influence of the deposition conditions on the phase purity was studied. Due to similar thermodynamic stability spaces, a pyrochlore phase often coexists with the PFN perovskite phase. By optimizing the kinetic parameters, we succeeded in identifying a deposition window which resulted in epitaxial perovskite-phase PFN thin films with no identifiable trace of impurity phases appearing in the X-ray diffractograms. PFN films having thicknesses between 20 and 200 nm were smooth and epitaxially oriented with the substrate and as demonstrated by RHEED streaks which were aligned with the substrate axes. X-ray diffraction showed that the films were completely c-axis oriented and of excellent crystalline quality with low mosaicity (X-ray rocking curve FWHM?0.09°). The surface roughness of thin films was also investigated by atomic force microscopy. The root-mean-square roughness varies between 0.9 nm for 50-nm-thick films to 16 nm for 100-nm-thick films. We also observe a correlation between grain size, surface roughness and film thickness.     

Parallel syntheses and thermoelectric properties of Ce-doped SrTiO3 thin films

Thermoelectric properties of single crystalline Ce_xSr_1−xTiO₃ films (0 ≤ x ≤ 0.5) have been studied by using combinatorial pulsed-laser deposition. Temperature gradient method was used for identifying an optimum growth temperature for SrTiO₃ homoepitaxial growth, at which both oxygen stoichiometry and persisting layer-by-layer growth mode could be accomplished. Electrical conductivity (σ) and Seebeck coefficient (S) were measured at room temperature for the composition-spread films grown at the optimized temperature and found to be considerably higher than those reported for bulk poly-crystalline compounds. Hall measurement revealed that carrier density linearly increased with increasing x, suggesting that a trivalent Ce ions substituted divalent Sr ions to supply electrons. A maximum power factor (S²σ) was obtained for the x = 0.2 film, being 7 and 14 μW/K² cm at 300 and 900 K, respectively.     

Atomic layer deposition of PbZrO3 thin films

In this paper, we report on the preparation of lead zirconate films for the first time using atomic layer deposition in an attempt to investigate some of the film properties and also to evaluate possible use of the precursor combination to prepare more complex lead titanate zirconate. In the depositions tetraphenyl lead (Ph₄Pb) was used as the lead and zirconium 2,2,6,6-tetramethyl-3,5-heptadionato (Zr(thd)₄) as the zirconium precursor, while ozone was used as the oxygen source. Film growth, stoichiometry and quality were studied using different pulsing ratios at deposition temperatures of 275 and 300 °C. According to X-ray diffraction, the crystalline perovskite phase was observed when films deposited on SrTiO₃(1 0 0) were annealed at 600 °C. Surface roughness was reduced for lead deficient films as well as in annealed samples.     

Thermochromic VO2 thin films synthesized by rf-inverted cylindrical magnetron sputtering

The novel physical vapor deposition called inverted cylindrical magnetron sputtering (also known as hollow cathode sputtering) is commonly used to coat wires, fibers, ribbons as well as all sides of three-dimensional substrates. It is a reproducible method for the production of nano-structured systems onto complex shapes substrates. This paper reports the first synthesis and feasibility of reliably reproduced stoichiometric pure textured VO₂ nano-structures by the rf-inverted cylindrical magnetron sputtering. Morphological, structural, elemental analysis and optical properties of synthesized VO₂ under optimized conditions are reported.     

Growth and thermal stability of epitaxial BiFeO3 thin films

We have investigated the oxygen pressure and the temperature dependence on BiFeO₃ thin films deposited on SrTiO₃ substrates by pulsed laser deposition. Reflection high energy electron diffraction (RHEED), atomic force microscopy (AFM) and X-ray diffraction measurements indicate that high-quality epitaxial thin films are obtained for and T=650 °C. Outside of this pressure-temperature window, parasitic peaks attributed to β-Bi₂O₃ appear. We find an increase of the out-of-plane lattice parameter with oxygen pressure that we ascribe to Bi-deficiency due to its high volatility at low pressure. Ex-situ anneals have been performed and results show that as-grown single-phase BiFeO₃ thin films degrade after annealing, whereas as-grown BiFeO₃ containing impurity phases evolve toward a single-phase structure. These experiments demonstrate that parasitic phases can stabilize compounds which are usually unstable in air at elevated temperatures.     

Optical and structural studies on Ba(Mg1/3Ta2/3)O3 thin films obtained by radiofrequency assisted pulsed plasma deposition

Single-phase Ba(Mg_1/3Ta_2/3)O₃ thin films were prepared by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) starting from a bulk ceramic target synthesized by solid state reaction. Atomic force microscopy, X-ray diffraction and spectroscopic ellipsometry were used for morphological, structural and optical characterization of the BMT thin films. The X-ray diffraction spectra show that the films exhibit a polycrystalline cubic structure. From spectroscopic ellipsometry analysis, the refractive index varies with the thin films deposition parameters. By using the transmission spectra and assuming a direct band to band transition a band gap value of ≈4.72 eV has been obtained.     

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.     

Superconducting molybdenum nitride epitaxial thin films deposited on MgO and α-Al2O3 substrates by molecular beam epitaxy

Molybdenum nitride Mo₂N_x films were grown on MgO(0 0 1) and on α-Al₂O₃(0 0 1) substrates by molecular beam epitaxy under nitrogen radical irradiation. X-ray photoelectron spectroscopy revealed that the composition of the film varied in the range of Mo₂N_1.4-Mo₂N_2.8 depending on the growth temperature. The deposition at 973 K gave well-crystallized films on both substrates. The high-resolution reciprocal space mapping by X-ray diffraction showed that the nitrogen-rich γ-Mo₂N crystalline phase (the composition: Mo₂N_1.4) was epitaxially grown on MgO at 923 K with a slight tetragonal distortion (a = 0.421 and c = 0.418 nm) to fit the MgO lattice (a = 0.421 nm). On α-Al₂O₃(0 0 1), nitrogen-rich γ-Mo₂N (Mo₂N_1.8) was grown at 973 K with (1 1 1) planes parallel to the substrate surface. X-ray diffraction analysis with a multi-axes diffractometer revealed that the γ-Mo₂N on α-Al₂O₃(0 0 1) had a slight rhombohedral distortion (a = 0.4173(2) and α = 90.46(3)°). Superconductivity was observed below 2.8-3 K for the films grown at 973 K on MgO and on α-Al₂O₃(0 0 1).     

Pulsed-laser crystallization and epitaxial growth of metal-organic films of Ca-doped LaMnO3 on STO and LSAT substrates

Ca-doped LaMnO₃ (LCMO) thin films have been successfully prepared on SrTiO₃ (STO) and [(LaAlO₃)_0.3-(SrAlTaO₆)_0.7] (LSAT) substrates using the excimer laser assisted metal-organic deposition (ELAMOD) process. The crystallization and the epitaxial growth of the amorphous metal-organic LCMO thin films have been achieved using a KrF excimer laser irradiation while the substrates were kept at constant temperature of 500 °C. Epitaxial films were obtained using laser fluence in the interval of 50-120 mJ/cm². The microstructure of the LCMO films was studied using cross-section transmission electron microscopy. High quality of LCMO films having smooth surfaces and sharp interfaces were obtained on both the STO and the LSAT substrates. The effect of the laser fluence on the temperature coefficient of resistance (TCR) was investigated. The largest values of TCR of the LCMO grown on the LSAT and the STO substrates of 8.3% K⁻¹ and 7.46% K⁻¹ were obtained at different laser fluence of 80 mJ/cm² and 70 mJ/cm², respectively.     

Synthesis and characterization of Gd0.1Ce0.9O1.95 thin films by spray pyrolysis technique

The Gd doped ceria (CGO) in thin layers is of great interest for low temperature operation. In the present investigation, we report on the use of spray pyrolysis technique for the synthesis of CGO thin films. The process parameters were optimized for synthesizing Gd_0.1Ce_0.9O_1.95 films. Films were characterized by XRD, EDS, SEM, and AFM and are observed to be phase pure and dense with surface roughness of the order of ∼5 nm. The d.c. conductivity was also measured and is observed to be ∼0.5 S/cm at 623 K.     

Microstructure of epitaxial SrRuO3 thin films on MgO substrates

SrRuO₃ thin films have been grown on singular (1 0 0) MgO substrates using pulsed laser deposition (PLD) in 30 Pa oxygen ambient and at a temperature of 400-700 °C. Ex situ reflection high-energy electron diffraction (RHEED) as well as X-ray diffraction (XRD) θ/2θ scan indicated that the films deposited above 650 °C were well crystallized though they had a rough surface as shown by atom force microscopy (AFM). XRD Φ scans revealed that these films were composed of all three different types of orientation domains, which was further confirmed by the RHEED patterns. The heteroepitaxial relationship between SrRuO₃ and MgO was found to be [1 1 0] SRO//[1 0 0] MgO and 45°-rotated cube-on-cube [0 0 1] SRO//[1 0 0] MgO. These domain structures and surface morphology are similar to that of ever-reported SrRuO₃ thin films deposited on the (0 0 1) LaAlO₃ substrates, and different from those deposited on (0 0 1) SrTiO₃ substrates that have an atomically flat surface and are composed of only the [1 1 0]-type domains. The reason for this difference was ascribed to the effect of lattice mismatch across the film/substrate interface. The room temperature resistivity of SrRuO₃ films fabricated at 700 °C was 300 μΩ cm. Therefore, epitaxial SrRuO₃ films on MgO substrate could serve as a promising candidate of electrode materials for the fabrication of ferroelectric or dielectric films.     

Growth and structure of Bi0.5(Na0.7K0.2Li0.1)0.5TiO3 thin films prepared by pulsed laser deposition technique

Bi_0.5(Na_0.7K_0.2Li_0.1)_0.5TiO₃ (BNKLT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition (PLD) technique. The films prepared were examined by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effects of the processing parameters, such as oxygen pressure, substrate temperature and laser power, on the crystal structure, surface morphology, roughness and deposition rates of the thin films were investigated. It was found that the substrate temperature of 600 °C and oxygen pressure of 30 Pa are the optimized technical parameters for the growth of textured film, and all the thin films prepared have granular structure, homogeneous grain size and smooth surfaces.     

AlCl3-induced crystallization of amorphous silicon thin films

It is reported that the direct contact between Al and amorphous silicon (a-Si) enhances the crystallization of a-Si films. But the polycrystalline silicon (poly-Si) films crystallized by the direct contact of Al metal film suffer the problems of rough surface. In our study, we utilized the AlCl₃ vapor during the a-Si films deposition instead of Al metal film to enhance crystallization. X-ray diffraction (XRD) shows that the AlCl₃ vapor so successfully enhanced the crystallization of a-Si films that the crystallization was completed in 5 h at 540 °C. And the orientation of the poly-Si film deposited with AlCl₃ vapor is much more random than that of annealed with Al metal under layer. But the average grain size is much larger than that. Moreover, the surface of the AlCl₃-induced crystallized poly-Si film was much smoother than that of the Al-induced poly-Si film. The Al and Cl incorporation into the poly-Si film was confirmed using X-ray photoelectron spectroscopy (XPS) and found that the quantity of Al and Cl incorporated into the Si film was below the detection limit of XPS.     

Magnetic properties of the bilayer manganese oxide (Pr0.6La0.4)1.2Sr1.8Mn2O7 under pressure

We investigated the effect of pressure on the magnetic properties of a single crystal of the bilayer manganese oxide (Pr_0.6La_0.4)_1.2Sr_1.8Mn₂O₇ by means of DC magnetization measurements under pressure. The ferromagnetic transition, which is accompanied by a metal-insulator transition, is highly sensitive to pressure. The pressure causes a structural variation, which affects the magnetic properties. We discuss the pressure dependence of the 3d electronic state of the Mn ion in this system.     

Structural and morphological characterization of TiO2 nanostructured films grown by nanosecond pulsed laser deposition

TiO₂ has attracted a lot of attention due to its photocatalytic properties and its potential applications in environmental purification and self cleaning coatings, as well as for its high optical transmittance in the visible-IR spectral range, high chemical stability and mechanical resistance. In this paper, we report on the growth of TiO₂ nanocrystalline films on Si (1 0 0) substrates by pulsed laser deposition (PLD). Rutile sintered targets were irradiated by KrF excimer laser (λ = 248 nm, pulse duration ∼30 ns) in a controlled oxygen environment and at constant substrate temperature of 650 °C. The structural and morphological properties of the films have been studied for different deposition parameters, such as oxygen partial pressure (0.05-5 Pa) and laser fluence (2- 4 J/cm²). X-ray diffraction (XRD) shows the formation of both rutile and anatase phases; however, it is observed that the anatase phase is suppressed at the highest laser fluences. X-ray photoelectron spectroscopy (XPS) measurements were performed to determine the stoichiometry of the grown films. The surface morphology of the deposits, studied by scanning electron (SEM) and atomic force (AFM) microscopies, has revealed nanostructured films. The dimensions and density of the nanoparticles observed at the surface depend on the partial pressure of oxygen during growth. The smallest particles of about 40 nm diameter were obtained for the highest pressures of inlet gas.     

Femtosecond Z-scan measurement of third-order optical nonlinearities in anatase TiO2 thin films

Anatase phase TiO₂ films have been grown on fused silica substrate by pulsed laser deposition technique at substrate temperature of 750 °C under the oxygen pressure of 5 Pa. From the transmission spectra, the optical band gap and linear refractive index of the TiO₂ films were determined. The third-order optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. The real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ were determined to be −7.1 × 10⁻¹¹esu and −4.42 × 10⁻¹²esu, respectively. The figure of merit, T, defined by T=βλ/n₂, was calculated to be 0.8, which meets the requirement of all-optical switching devices. The results show that the anatase TiO₂ films have great potential applications for nonlinear optical devices.