Dielectric investigations in Sr<Subscript>0.75</Subscript>Ba<Subscript>0.25</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> relaxor ferroelectric thin films

The dielectric properties of Sr_0.75Ba_0.25Nb₂O₆ relaxor ferroelectric thin films were carefully analyzed. In contrast to bulk samples which present three distinct dielectric relaxation phenomena Sr_0.75Ba_0.25Nb₂O₆ thin films present only two of them. The suppression of the third anomaly can be mainly attributed to the narrow grain size distribution of nanograins and weak tensile strains imposed to the film from the substrate. The whole set of results point to the interpretation of a dielectric response characteristic of mesoscopic structure, which is composed of clusters and nanodomains.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Microstructures and impedance studies of Bi<Subscript>3.15</Subscript>Nd<Subscript>0.85</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

Microstructures and impedance characteristics of chemical-solution-derived Bi_3.15Nd_0.85Ti₃O₁₂ thin films were studied as functions of temperature. A dielectric anomaly was found at around 450°C, corresponding to the paraelectric to ferroelectric transition. Via complex impedance studies, grain and grain boundary contributions to the impedance were separated. The resistance of grain and grain boundaries is found governed by the same kind of space charge with an activation energy around 1.1 eV, close to that of oxygen vacancies in perovskite ferroelectrics. The low temperature ac conductance of BNdT thin films shows a frequency dispersion, which can also be ascribed to space charges mainly due to oxygen vacancies. The results were compared with SrBi₂Ta₂O₉ in terms of oxygen vacancy conductivity.     

Deposition and stoichiometry control of Nd-doped gadolinium gallium garnet thin films by combinatorial pulsed laser deposition using two targets of Nd:Gd<Subscript>3</Subscript>Ga<Subscript>5</Subscript>O<Subscript>12</Subscript> and Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>

We have demonstrated pulsed laser deposition of Nd-doped gadolinium gallium garnet on Y₃Al₅O₁₂ by the simultaneous ablation of two separate targets of Nd:Gd₃Ga₅O₁₂ (GGG) and Ga₂O₃. Such an approach is of interest as a method of achieving stoichiometry control over films whilst the growth parameters are kept constant and optimal for high quality crystal growth. We show here how the stoichiometry and resultant lattice parameter of a film can be controlled by changing the relative deposition rates from the two targets. Films have been grown with enough extra Ga to compensate for the deficiency that commonly occurs when depositing only from a GGG target. We have also grown crystalline GGG films with an enriched Ga concentration, and this unconventional approach to film stoichiometry control may have potential applications in the fabrication of films with advanced compositionally graded structures.     

Piezoelectric coefficients of multilayer Pb(Zr,Ti)O<Subscript>3</Subscript> thin films

Sol–gel techniques were used to prepare thin films of Pb(Zr _x ,Ti_1−x )O₃ (PZT) with three different Zr/Ti ratios and a graded PZT film with three different compositional layers. A Michelson interferometer was used to measure the thickness strains due to an applied ac electric field. Effective d ₃₃ piezoelectric strain coefficients were computed from the experimental data. Interfacial pinning caused these coefficients to differ from the true ones. They were corrected for the pinning using both an analytical model and finite-element analysis. The corrected coefficients of the PZT (52/48) sample were in excellent agreement with values of bulk materials. The coefficients of the multilayer sample were very low, probably due to insufficient poling or domain switching.     

Role of growth temperature on nanostructure and field emission properties of PLD thin carbon films

Thin carbon films have been deposited in vacuum (∼10⁻⁴ Pa) on Si substrates by pulsed laser ablation of a graphite target using a Nd:YAG laser operating in the near infrared region (λ=1064 nm). The samples have been deposited at different substrate temperatures (T _sub) ranging from room temperature (RT) to 800°C. X-ray diffraction analysis established the progressive formation of nanosized graphene structures as T _sub increased. In fact, film structure evolves from almost amorphous to nanostructured phase characterized by graphene layers oriented perpendicularly to the film plane. The film density, evaluated by X-ray reflectivity measurements, is strongly affected by T _sub. At RT the film density is similar to the graphite one, while it decreases at higher T _sub. The electrical properties of the samples have been characterized by field emission measurements. The parameters describing the emitter properties (threshold field E _th and field enhancement factor β) have been evaluated using variable anode-to-cathode distance method. Samples deposited at low T _sub have shown the best emission properties, presenting lower E _th and larger β values than those deposited at higher T _sub. This is mainly attributed to the sensible density variation, which is in competition with the slighter augment of mean nanoparticle size.     

Large optical nonlinearity in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully prepared on LaAlO₃ substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ ⁽³⁾, of the CCTO film were obtained to be 2.79×10⁻⁸ esu and 3.30×10⁻⁶ esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO₃ substrates are promising candidate materials for applications in nonlinear optical devices.     

Structure and electrical properties of HfO<Subscript>2</Subscript> high-<Emphasis Type="Italic">k</Emphasis> films prepared by pulsed laser deposition on Si (100)

High-k gate dielectric hafnium dioxide films were grown on Si (100) substrate by pulsed laser deposition at room temperature. The as-deposited films were amorphous and that were monoclinic and orthorhombic after annealed at 500°C in air and N₂ atmosphere, respectively. After annealed, the accumulation capacitance values increase rapidly and the flat-band voltage shifts from −1.34 V to 0.449 V due to the generation of negative charges via post-annealing. The dielectric constant is in the range of 8–40 depending on the microstructure. The I–V curve indicates that the films possess of a promising low leakage current density of 4.2×10⁻⁸ A/cm² at the applied voltage of −1.5 V.     

Pulsed laser deposition of TiO<Subscript>2</Subscript>: diagnostic of the plume and characterization of nanostructured deposits

Promising applications of TiO₂ nanostructures include the development of optical devices, sensors, photocatalysts and self-cleaning coatings. In view of their importance, research on the synthesis of nanosized TiO₂ is a particularly active field. In this work we report on the investigation of the effect of laser irradiation wavelength (Q-switched Nd:YAG laser at 532, 355 and 266 nm), the temperature of the substrate and the atmosphere of deposition (vacuum, Ar and O₂) that are suitable for obtaining nanostructured deposits from TiO₂ sintered targets. The ablation plume emission is characterized with spectral and temporal resolution by optical emission spectroscopy (OES), while the surface morphology and chemical states of the material deposited on a Si (100) substrate are examined by environmental scanning electron microscopy (ESEM) and atomic force microscopy (AFM) and by X-ray photoelectron spectroscopy (XPS), respectively. Deposits with nanostructured morphology with grain size down to 40 nm and keeping the stoichiometry of the targets were obtained at high temperature, while the highest concentration of particulates was observed at the longest laser wavelength of 532 nm on a substrate heated up to 650°C. In situ characterization of the ablation plume, carried out by OES, indicated the presence of emissions assigned to Ti I, Ti II and O I.     

Incubation in the UV irradiation of condensed CHCl<Subscript>3</Subscript> solids

Matrix-Assisted-Pulsed-Laser-Evaporation (MAPLE) has emerged as a very promising technique for the deposition of polymers and biopolymers in intact and functional form. However, our understanding of the mechanism of the procedure is still limited. Here, we examine laser-induced (248 nm) desorption from condensed CHCl₃ solid, which has been employed as a potential matrix in MAPLE. We find that the absorption of the condensed halocarbon increases significantly with successive laser pulses, as a result of the formation and accumulation of strongly absorbing products. This results in a significant increase of the ejection efficiency in the irradiation with successive laser pulses. Thus, in studies employing multi-pulse irradiation protocols, the attained laser-induced temperatures are considerably higher than what is estimated on the basis of the absorption coefficient of CHCl₃. Thus, contrary to previous suggestions, ablation of CHCl₃ frozen solid at 248 nm may be due to explosive boiling. A number of additional implications are also discussed.     

Structural characteristics of a single-crystalline Sr<Subscript>0.75</Subscript>Ba<Subscript>0.25</Subscript>NbO<Subscript>3</Subscript> electro-optic material

Sr_0.75Ba_0.25NbO₃ (SBN-75) has the tungsten-bronze structure with a tetragonal unit cell and exhibits electro-optic properties that are important for sensors. Due to its quaternary nature, its structural uniformity, integrity, and homogeneity become important for these applications. In this paper, we present high-resolution X-ray diffraction studies of the crystalline quality and lattice parameter variation across the surface of single crystals of SBN-75. Using rocking curves, topographs, and point-wise measurements of lattice parameters, we show that these crystals have a high degree of crystalline quality and microscopic homogeneity for any electro-optic application.     

Pulsed laser deposition of BaGa<Subscript>2</Subscript>O<Subscript>4</Subscript>

This paper reports the first results obtained on monobarium gallate thin films grown on silicon and platinum coated substrates by pulsed laser deposition. The influence of oxygen background pressure and substrate (or post-annealing) temperature on the film properties was studied. The films were characterized by XRD, RHEED, AFM, photoelectron and electrical impedance spectroscopy. The structure analysis showed that the films crystallized into a hexagonal phase, most probably into (metastable) α-BaGa₂O₄. Depending on deposition conditions, films with different (from nearly epitaxial to polycrystalline) textures were obtained.     

Energy level alignment at interfaces between organic semiconductors and clean ferromagnetic La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> thin film contacts for spin injection

We have studied the energy level alignment at interfaces between clean ferromagnetic La_0.7Sr_0.3MnO₃ and two archetype organic semiconductors, α-sexithiophene and copper-phthalocyanine, by combined X-ray and ultraviolet photoelectron spectroscopy. We observe the formation of a large interface dipole at both studied interfaces and small hole injection barriers. In addition, our results indicate a small chemical interaction between the organic materials and the La_0.7Sr_0.3MnO₃ surface which leads to a pinning of the Fermi level and the relatively small hole injection barriers.     

A sonochemical-assisted synthesis and annealing temperature effect of La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> nanoparticles

This paper reports on the sonochemical-assisted synthesis of La_0.7Sr_0.3MnO₃ (LSMO) nanoparticles (NPs) which have a single-crystalline perovskite structure. The average particle size of LSMO NPs was controlled from about 40 to 120 nm by changing the annealing temperatures from 750 to 1050°C. The particle size, electrical resistivity, and ferromagnetic transition temperature of LSMO NPs were strongly dependent on the annealing temperature. A substantial decrease in resistivity and an enhancement in the insulator–metal transition temperature were found on increasing the annealing temperature. Furthermore, the enhancement in magnetization and paramagnetic–ferromagnetic (PM–FM) transition temperatures was observed as the annealing temperature increases.     

InTaO<Subscript>4</Subscript>-based nanostructures synthesized by reactive pulsed laser ablation

Nanostructured Ni-doped indium–tantalum–oxides (InTaO₄) were synthesized by a reactive pulsed laser ablation process, aiming at the final goal of direct splitting of water under visible sunbeam irradiation. The third harmonics beam of a Nd:YAG laser was focused onto a sintered In_0.9Ni_0.1TaO_4−δ target in pure oxygen background gases (0.05–1.00 Torr). Increasing the oxygen gas pressure, via thin films having nanometer-sized strong morphologies, single-crystalline nanoparticles were synthesized in the reactive vapor phases. The nanostructured deposited materials have the monoclinic layered wolframite-type structure of bulk InTaO₄, without oxygen deficiency.     

Thermo-optic coefficients of monoclinic KLu(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The three thermo-optic coefficients of the biaxial laser host KLu(WO₄)₂ are measured at 633 nm by a deflection method. Their values at 300 K amount to ∂ n _g /∂ T=−7.4×10⁻⁶ K⁻¹; ∂ n _m /∂ T=−1.6×10⁻⁶ K⁻¹ and ∂ n _p /∂ T=−10.8×10⁻⁶ K⁻¹. Nearly athermal propagation directions are found for polarizations along the N _m and N _p dielectric axes.     

Magnetotransport properties of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> with different grain sizes

The magnetotransport and magnetoresistive (MR) properties of manganese-based La_0.67Ca_0.33MnO₃ perovskite with different grain sizes are reported. The electrical resistivity was measured as a function of temperature in magnetic fields of 0.5 and 1 T. The insulator–metal transition temperature, T _IM, shifted to a higher temperature with the application of the magnetic field. In zero field, T _IM is almost constant (∼271 K) for all samples except for the sample with the largest grain size, where T _IM=265 K. The temperature dependence of resistivity was fitted with several equations in the metallic (ferromagnetic) region and the insulating (paramagnetic) region. The density of states at the Fermi level, N(E _F), and the activation energy of electron hopping were estimated by fitting the resistivity versus temperature curves. The ρ–T ² curves are nearly linear in the metallic regime, but the ρ–T ^2.5 curves exhibit a deviation from linearity. The variable range hopping model and small polaron hopping model fit the data well in the high-temperature region, indicating the existence of the Jahn–Teller distortion that localizes the charge carriers. MR was found to increase with an increase in the magnetic field, an effect which is attributed to the intergrain spin tunneling effect.     

The structure and photoluminescence properties of TiO<Subscript>2</Subscript>-coated ZnS nanowires

The structure and photoluminescence properties of TiO₂-coated ZnS nanowires were investigated. ZnS nanowires were synthesized by thermal evaporation of ZnS powder and then coated with TiO₂ by using the metal organic chemical vapor deposition (MOCVD) technique. We performed scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy, and photoluminescence (PL) spectroscopy to characterize the as-synthesized and TiO₂-coated ZnS nanowires. TEM and XRD analyses revealed that the ZnS core and the TiO₂ coatings had crystalline zinc blende and crystalline anatase structures, respectively. PL measurement at room temperature showed that the as-synthesized ZnS nanowires had two emissions: a blue emission centered in the range from 430 to 440 nm and a green emission at around 515 nm. The green emission was found to be dominant in the ZnS nanowires coated with TiO₂ by MOCVD at 350°C for one or more hours, while the blue emission was dominant in the as-synthesized ZnS nanowires. Also the mechanisms of the emissions were discussed.     

Application of MEH-PPV/SnO<Subscript>2</Subscript> bilayer as hybrid solar cell

The effects of oxygen content in the sputtering gas on the crystallographic and optoelectronic properties of 210 nm-thick Zr–doped In₂O₃ (Zr–In₂O₃) films by rf magnetron sputtering were initially studied. The results of X-ray diffraction show that the Zr–In₂O₃ films grown on glass substrates exhibit mixed crystallographic orientations. Moreover, the Zr–In₂O₃ film grown in an Ar atmosphere promotes the appearance of crystallographic orientation of (222). The surface of the Zr–In₂O₃ film becomes rougher as the oxygen content in the sputtering gas decreases; the current images obtained by conductive atomic force microscopy reveal that the surfaces of the Zr–In₂O₃ films exhibit a distribution of coexisting conducting and nonconducting regions, and that the area of the nonconducting surface increases with the oxygen content in the sputtering gas. The resistivity is minimized to 3.51×10⁻⁴ Ω cm when the Zr–In₂O₃ film is grown in an Ar atmosphere and the average transmittance in the visible light region is ∼85%. The optical band gap decreases as the oxygen content in the sputtering gas increases.     

Orientation ordering of N<Subscript>2</Subscript> molecules in vertically aligned CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanotubes

Arrays of vertically aligned nitrogen-doped carbon (CN _x ) nanotubes have been synthesized by decomposition of aerosol mixture of acetonitrile and ferrocene at 850°C. Nitrogen concentration in the outer shells of the CN _x nanotubes was found from X-ray photoelectron spectroscopy (XPS) data to reach ∼6%. The XPS N 1s spectra and N 1s near-edge X-ray absorption fine structure (NEXAFS) spectra identified three chemical forms of nitrogen in the CN _x nanotube arrays: pyridine-like, graphitic, and molecular nitrogen. The π ^* resonance of molecular nitrogen showed clear polarization dependence that indicates predominant orientation of N₂ molecules along the nanotubes axis. The estimated range of the polar angle distribution of the N₂ molecules orientation in the CN _x nanotube array amounts to 15°.