Growth of polycrystalline La0.5Sr0.5CoO3 films by femtosecond pulsed laser deposition

In this paper we present the growth of La_0.5Sr_0.5CoO₃ (LSCO) films on MgO, quartz, and silicon substrates by pulsed laser deposition (PLD) using a Ti:sapphire laser (50 fs, 800 nm wavelength). The morphology and the structure of the films were studied by X-ray diffraction, atomic force microscopy, and scanning electron microscopy. The films were polycrystalline and exhibit a good adherence to the Si substrate. Different deposition parameters such as substrate temperature, oxygen pressure, and laser fluence were varied to achieve good surface quality and low resistivity crystalline films. We also defined the optimum conditions in which the deposited film surface is particulate free. The best films (droplets free) were grown at 625 °C, in an ambient oxygen pressure of 6 mbar, with an incident laser fluence of 0.19 J/cm². This is a mandatory step in the complex work of fabricating La_0.5Sr_0.5CoO₃/BaTiO₃/La_0.5Sr_0.5CoO₃ heterostructures for the development of thin film capacitors for non-volatile ferroelectric access memory devices. PACS 81.15 Fg; 42.62-b; 68.65.Ac     

Infrared optical properties of PbZr0.4Ti0.6O3/La0.5Sr0.5CoO3 heterostructures on platinized silicon substrate

PbZr_0.4Ti_0.6O₃/La_0.5Sr_0.5CoO₃ heterostructures have been grown on Pt/Ti/SiO₂/Si substrates by chemical solution routes. Optical properties of the PbZr_0.4Ti_0.6O₃/La_0.5Sr_0.5CoO₃ heterostructures were studied by infrared spectroscopic ellipsometry (IRSE) in the spectral range of 2.5–12.5 m. The optical constants of PbZr_0.4Ti_0.6O₃ and La_0.5Sr_0.5CoO₃ thin films were determined by fitting the IRSE data using a classical dielectric model and a Drude dielectric model, respectively. For PbZr_0.4Ti_0.6O₃ thin films, the refractive index decreases and the extinction coefficient increases as the wavelength increases. For La_0.5Sr_0.5CoO₃ thin films, the refractive index and the extinction coefficient increase as the wavelength increases. The absorption coefficient of La_0.5Sr_0.5CoO₃ thin films is greater than 10⁴ cm^-1 for the wavelength range of 2.5–12.5 m. The absorption coefficient of PbZr_0.4Ti_0.6O₃ thin films on a La_0.5Sr_0.5CoO₃/Pt/Ti/SiO₂/Si substrate is smaller than that on a Pt/Ti/SiO₂/Si substrate by a factor of two. PACS 77.84.Dy; 78.20.Ci; 81.20.Fw     

Phase equilibria in the La-Me-Co-O (Me=Ca, Sr, Ba) systems

The phase equilibria of the La-Me-Co-O systems (Me = Ca, Sr and Ba) were studied in air at 1100 °C. Two types of solid solution of general composition La_1−xMe_xCoO_3−δ and (La_1−y Me_y)₂CoO₄ were found to exist in the systems. The limiting composition of La_1−xMe_xCoO_3−δ lies at x=0.8 for Me = Sr, Ba and between 0.3–0.5 for Me = Ca. It is shown that the rhombohedral distortion of the perovskite type La_1−xMe_xCoO_3−y decreases while x increases. La_1−xMe_xCoO_3−δ (Me = Sr, Ba) shows an ideal cubic structure at x=0.5. The stability range of (La_1−yMe_y)₂CoO₄ was found to be 0.25≤y≤0.35 for Me = Ca, 0.3≤y≤0.55 for Me = Sr and 0.3≤y≤0.375 for Me = Ba. All phases have tetragonal K₂NiF₄-type crystal structure. Based on the XRD and neutron diffraction patterns of quenched samples, the phase diagrams (Gibbs triangles) are constructed for all systems. The phase equilibrium at low oxygen pressure is shown for the example of the La-Sr-Co-O system. The decomposition mechanism of La_1−xSr_xCoO_3−δ at 1100 °C for the samples with 0.5<x<0.8 within the oxygen pressure range −0.678>log(Po₂)>−2.25 can be written as follows: La_1−x′ Sr_x′CoO_3−δ′=n La_1−x″Sr_x″CoO_3−δ″+m SrCoO_2.5+q/2 O₂ where x′>x″. The decomposition mechanism of La_1−xSr_xCoO_3−δ for the samples with x < 0.5 within the oxygen pressure range −2.25>log(Po₂)>−3.55 changes and can be written as follows: La_1−xSr_xCoO_3−δ′=r La_1−x′Sr_x′CoO_3−δ″+w (La_1−y′Sr_y′)₂CoO₄+v CoO+f/2 O₂. The results are shown in “logPo₂-composition” diagrams. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Structure, ferroelectric and piezoelectric properties of?(Bi0.98?xLa0.02Na1?x)0.5BaxTiO3 lead-free ceramics

Lead-free (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics have been prepared by an ordinary sintering technique and their structure, ferroelectric and piezoelectric properties have been studied. The results of X-ray diffraction show that La²⁺ and Ba²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) exists at 0.04<x<0.10. Compared with pure Bi_0.5Na_0.5TiO₃ ceramics, the (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics possess much smaller coercive field E _c and larger remanent polarization P _r. Because of the low E _c (3.38 kV/mm), large P _r (46.2 μC/cm²) and the formation of the MPB of rhombohedral and tetragonal phases, the piezoelectric properties of the ceramics are significantly enhanced at x=0.06: d ₃₃=181 pC/N and k _p=36.3%. The depolarization temperature T _d reaches a minimum value near the MPB. The ceramics exhibit relaxor characteristic, which is probably a result from the cation disordering in the 12-fold coordination sites. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both polar and non-polar regions at the temperatures above T _d.     

Crystal electric field effects in Pr0.5Sr0.5CoO3

The energy structure and temperature evolution of the magnetic excitation spectra of Pr_0.5Sr_0.5CoO₃ are studied by inelastic neutron scattering. The measurements are performed on a polycrystalline sample of Pr_0.5Sr_0.5CoO₃ and its non-magnetic analogue La_0.5Sr_0.5CoO₃ on the high intensity time-of-flight spectrometer IN4 (ILL, Grenoble) in the temperature range 10 K < T < 300 K. The crystal electric field parameters in Pr_0.5Sr_0.5CoO₃ are calculated and the splitting scheme of the 4f ground multiplet of Pr³⁺ ions is determined based on the experimental data.     

Effects of La–Zn substitution on microstructure and magnetic properties of strontium ferrite nanofibers

Sr_1−x La _x Zn _x Fe_12−x O₁₉/poly(vinylpyrrolidone) (PVP) (0.0≤x≤0.5) precursor nanofibers were prepared by the sol–gel assisted electrospinning method from starting reagents of metal salts and PVP. Subsequently, the Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers with diameters of around 100 nm were obtained by calcination of the precursor at 800 to 1000°C for 2 h. The precursor and resultant Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometer and vibrating sample magnetometer. The grain sizes of Sr_0.8La_0.2Zn_0.2Fe_11.8O₁₉ nanofibers are in a nanoscale from 40 to 48 nm corresponding to the calcination temperature from 800 to 1000°C. With La–Zn substitution content increase from 0 to 0.5, the grain size and lattice constants for the Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers obtained at 900°C show a steady reduction trend. With variations of the ferrite particle size arising from the La–Zn substitution, the nanofiber morphology changes from the necklace-like structure linking by single elongated plate-like particles to the structure building of multi-particles on the nanofiber cross-section. The specific saturation magnetization of Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers initially increases with the La–Zn content, reaching a maximum value 72 A m² kg⁻¹ at x=0.2, and then decreases with a further La–Zn content increase up to x=0.5, while the coercivity exhibits a continuous reduction from 413 (x=0) to 219 kA m⁻¹ (x=0.5). The mechanism for the La–Zn substitution and the nanofiber magnetic property are analyzed.     

Effect of Sr addition to La-based perovskite-type oxide as an electrode material for zirconia-based amperometric-type NOx sensor

The sensing characteristics of an amperometric NOx sensor with yttria-stabilized zirconia and a La-based perovskite-type oxide sensing electrode were examined. La_1-xSr_xMO₃ (M = Co, Mn, x = 0, 0.2, 0.4, 0.6) were synthesized using the spray pyrolysis method. The NO₂ response of a sensor fabricated with La_1-xSr_xMnO₃ increased with increasing amount of Sr, and the trend was in contrast to that of the sensors fabricated with La_1-xSr_xCoO₃. LaSr_0.2MnO₃ was determined to be the most appropriate material for the sensor in terms of a high NO₂ response and low O₂ current. In order to discuss the effects of Sr addition to La-based perovskite oxides for the sensor, NO adsorption and desorption properties of oxides and the relationship between the oxidation number of the B-site cation and Sr substitution were examined using temperature-programmed desorption and X-ray photoelectron spectroscopy, respectively.     

Effects of deposition temperature and post-annealing on structure and electrical properties in (La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>)CoO<Subscript>3</Subscript> films grown on silicon substrate

(La_0.5Sr_0.5)CoO₃ (LSCO) thin films have been fabricated on silicon substrate by the pulsed laser deposition method. The effects of substrate temperature and post-annealing condition on the structural and electrical properties are investigated. The samples grown above 650°C are fully crystalline with perovskite structure. The film deposited at 700°C has columnar growth with electrical resistivity of about 1.99×10⁻³ Ω cm. The amorphous films grown at 500°C were post-annealed at different conditions. The sample post-annealed at 700°C and 10⁻⁴ Pa has similar microstructure with the sample in situ grown at 700°C and 25 Pa. However, the electrical resistivity of the post-annealed sample is one magnitude higher than that of the in situ grown sample because of the effect of oxygen vacancy. The temperature dependence of resistivity exhibits semiconductor-like character. It was found that post-annealing by rapid thermal process will result in film cracks due to the thermal stress. The results are referential for the applications of LSCO in microelectronic devices.     

Multilevel resistance switching of Ag/Nb-doped SrTiO<Subscript>3</Subscript>/Ti structure

Rectifying and photovoltaic properties of a La_0.7Sr_0.3CoO_3−σ /Si heterostructure have been experimentally studied. The heterostructure exhibits a rectifying behavior, similar to that of the traditional diode. A photovoltaic effect is observed when the heterostructure is exposed to the laser with a wavelength of 532 nm and a power of 6 mW/mm². It is interesting to note that the peak photovoltages initially increase with decreasing temperature, followed by a decrease at T<220 K. This reveals that the photovoltaic effect can be modulated by the intrinsic properties of the La_0.7Sr_0.3CoO_3−σ layer.     

Structure and magnetic properties of colossal magnetoresistance compound Tb0.5Sr0.5CoO3

The structure and the magnetic properties of the doped rare earth cobaltite systems are of recent interest owing to the CMR phenomenon that occur in them. In this paper, we investigate the structure and magnetic properties of Tb_0.5Sr_0.5CoO₃ solid solution, for the first time, using neutron powder diffraction technique. The sample Tb_0.5Sr_0.5CoO₃ is found to crystallize in orthorhombic (Pbnm) symmetry. The unit cell volume and Co—O bond length reduce with temperature. The calculatede _g bandwidth obtained from structural parameters turns out to be 0.989 eV. Low temperature neutron diffraction profiles exhibit a magnetic contribution to the fundamental Bragg peaks indicating a ferromagnetic ordering belowT _c. The results are compared with Co—O—Co bond angles and Co—O bond length of La_0.5Sr_0.5CoO₃, highlighting the ionic size effects on substitution of Tb ion for La in the compound.     

Synthesis and field emission of two kinds of ZnO nanotubes: taper-like and flat-roofed tubes

Two kinds of ZnO nanotubes, including taper-like and flat-roofed tubes, have been successfully fabricated using a simple aqueous solution route by changing the experimental conditions. All the obtained nanotubes have a uniform size of 500 nm in diameter, 10–50 nm in wall thickness, and 2–5 μm in length. The growth mechanism of two kinds of ZnO nanotubes was investigated. Field emission measurements showed that tapering nanotubes have the good field emission performance with a low turn-on field of ∼ 2.1 V μm^-1 and a low threshold field of ∼ 3.8 V μm^-1, which suggests the possible applications of the ZnO tubular structures in field emission microelectronic devices. PACS 73.61.Ga; 73.63. Fg; 85.45.Db     

Structural and electrical properties of polycrystalline PbZr0.5Ti0.5O3 films deposited on La0.5Sr0.5CoO3 coated silicon by sol-gel process

La_0.5Sr_0.5CoO₃ (LSCO) films have been grown on Si (100) by a metalorganic chemical liquid deposition (MOCLD) technique using lanthanum acetate, strontium acetate and cobalt acetate as the starting materials. Subsequent PbZr_0.5Ti_0.5O₃ (PZT) films were deposited onto LSCO films by a modified sol-gel method. Field-emission scanning electron microscopy and X-ray diffraction analysis show that PZT and LSCO films are polycrystalline and entirely perovskite phase. At an applied electric field of 250 kV/cm, the Pt/PZT/LSCO capacitor shows no polarization fatigue after 3×10⁹ switching cycles and an internal electric field; the remnant polarization P_r and the coercive field E_c are about 22 μC/cm² and 73 kV/cm, respectively. The dielectric constant of PZT films is 650 at a frequency of 1 kHz. Received: 20 February 2001 / Accepted: 6 June 2001 / Published online: 30 August 2001     

Investigation of oxidation resistance of Ni-Ti film used as oxygen diffusion barrier layer

Ni-Ti films prepared at 10 W and 70 W by rf magnetron sputtering are investigated as the oxygen diffusion barrier layer, it is found that crystallinity of Ni-Ti film does not greatly depend on the deposition power. X-ray photoelectron spectroscopy indicates that Ni is still in the form of metallic state from the binding energies of both Ni 2p_3/2 and Ni 2p_1/2 spectra for the sample with 10 W prepared Ni-Ti, however, Ni is oxidized for 70 W prepared Ni-Ti film. Moreover, the (La_0.5Sr_0.5)CoO₃/Pb(Zr_0.40Ti_0.60)O₃/(La_0.5Sr_0.5)CoO₃ capacitor grown on high power prepared Ni-Ti film is leaky, however, the capacitor on low power prepared Ni-Ti film possesses very promising physical properties (i.e. remnant polarization of ∼27 μC/cm² at 5 V and maximum dielectric constant of 940). Leakage current density of the capacitor grown on low power prepared Ni-Ti film is further investigated, it meets ohmic behavior (<1.0 V) and agrees well with the space-charge-limited current theory (>1.0 V).     

Application of photocatalytic technology for NO<Subscript>x</Subscript> removal

Materials that contain a photocatalyst have a semi-permanent capacity for removing harmful gases from the ambient air. It is the purpose of this study to investigate the photocatalytic activity of commercial paints containing TiO₂ nanoparticles towards NO and NO₂. Experiments were carried out in a stainless steel (30 m^-3) walk-in type environmental chamber (Indoortron), under “real world setting” conditions of temperature, relative humidity, irradiation and pollutant concentrations. Two types of nanoparticle TiO₂-containing paints were tested for their depolluting properties: a mineral silicate paint and a water-based styrene acrylic paint. The results showed a significant effect of TiO₂-materials in reducing NO_x. It was found that up to 74% of NO and 27% of NO₂ were photo-catalytically degraded by the mineral silicate paint, while degradation percentage using the styrene acrylic paint reached 91% and 71% for NO and NO₂, respectively. The photo-catalytic rate of NO on the mineral and styrene acrylic paint was calculated to 0.11 μg m^-2 s and 0.18 μg m^-2 s, respectively, indicating higher photocatalytic performance of the organic based material. The effect of relative humidity (RH) was also investigated. An increase of RH from 20% to 50% inhibited the NO_x photocatalysis on the surface of the samples. PACS 81.16.Hc; 81.65.Mq; 82.33.Tb; 82.50.Hp; 82.65.+r     

Effect of high pressure on the crystal and magnetic structures of La<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> cobaltite

The atomic and magnetic structures of La_0.5Ca_0.5CoO₃ cobaltite have been studied by the neutron diffraction technique at high pressures of up to 4 GPa in the 10- to 300-K temperature range. The pressure dependences of the structural parameters have been obtained. The Curie temperature increases with the pressure with the coefficient dT _C/dP = 1 K/GPa, demonstrating the stability of the ground ferromagnetic (FM) state. The pressure dependence of the ground FM state in La_0.5Ca_0.5CoO₃ is in drastic contrast with that for La_{1 − x} Ca _x CoO₃ at a lower calcium content (x < 0.3). For the latter compound, the pressure suppressed the ground FM state and a large negative pressure coefficient of the Curie temperature (dT _C/dP ∼ −10 K/GPa) was observed. The nature of such a phenomenon is analyzed in the framework of the double exchange model also taking into account the changes in the electron configuration of Co³⁺ ions.     

An EIS study of La2 − x Sr x NiO4 + δ SOFC cathodes

La_2 − x Sr _x NiO_{4 +  δ} materials were investigated as cathodes for the electrochemical reduction of oxygen on a Ce_1.9Gd_0.1O_1.95 (CGO10) electrolyte using cone-shaped electrodes together with electrochemical impedance spectroscopy. The area-specific resistance (ASR) of the La_2 − x Sr _x NiO_{4 +  δ} nickelates towards the reduction of oxygen is equal to the ASR of perovskites; however, it is not as low as for the best Fe–Co-based perovskites. The lowest ASR is found for the compound La_1.75Sr_0.25NiO_{4 +  δ} with an ASR of 23.8 Ωcm² measured on a cone-shaped electrode in air at 600 °C. It is suggested that difference in oxide ionic conductivity of the nickelates is the main cause for the different activity of the nickelates towards the electrochemical reduction of oxygen.     

Growth and electric properties of (100)-oriented Mn-doped (Bi0.5Na0.5)TiO3-BaTiO3 thin film by pulsed laser deposition

Mn-doped (Bi_0.5Na_0.5)TiO₃-BaTiO₃ (BNBMT) thin film with the composition near the morphotropic phase boundary was grown on (La_0.6Sr_0.4)CoO₃-electroded SrTiO₃ single-crystal substrate by using pulsed laser deposition method. Ascribed to the crystal structure and lattice similarity, (100)-oriented BNBMT film with pure single-phase perovskite structure was obtained through carefully controlling the growth conditions. Enhanced ferroelectric and dielectric properties were obtained with large remanent polarization P _r of ～21 μC/cm², coercive field E _c of ～7.4 kV/mm and dielectric constant $\varepsilon_{33}^{T}/\varepsilon_{0}$ of ～750 at 1 kHz. The excellent global electrical properties of the BNBMT film are promising for environmentally friendly ferroelectric devices.     

Structural and electrochemical characterization of Ce0.85Ca0.05Sm0.1O1.9 oxide ion electrolyte with Sr-doped LaMnO3 and SmCoO3 cathodes

This paper reports on the electrochemical properties and chemical stability of a recently developed Ca²⁺ and Sm³⁺-doped oxide ion conducting electrolyte, Ce_0.85Ca_0.05Sm_0.1O_1.9 (CCS), employed in an intermediate temperature solid oxide fuel cell (IT-SOFC) using conventional Sm_0.5Sr_0.5CoO₃ (SSC) and La_0.8Sr_0.2MnO₃ (LSM) cathodes in air at elevated temperatures. The materials were prepared by conventional solid-state reactions using their corresponding metal oxides and salts in the temperature range of 1,200–1,450 °C in air. Powder X-ray diffraction (PXRD) and impedance spectroscopy were employed for phase formation, chemical compatibility, and electrochemical characterization. PXRD studies on 1:1 weight ratio of heat-treated (1,000 °C for 3 days) mixtures of SSC or LSM and CCS revealed the presence of fluorite-type and perovskite-like phases. The area-specific resistance (ASR) value in air was lower for SSC cathodes (4.3–0.15 Ω cm²) compared to those of LSM (407–11 Ω cm²) over the investigated temperature range of 600–800 °C. As expected, a significant increase in ASR was observed in Ar as compared to air.     

Research on charge-ordering state in La0.5Sr0.5MnO2.88 and La0.5Sr0.5Mn0.5Ti0.5O3 systems

The structural, magnetic and transport properties of La_0.5Sr_0.5MnO_2.88 and La_0.5Sr_0.5Mn_0.5Ti_0.5O₃ samples have been investigated systematically. Indeed, this series has been considered to understand the influence of physical parameters such as oxygen deficiency and titanium doping effect in undoped La_0.5Sr_0.5MnO₃ sample. Ceramic material based on La_0.5Sr_0.5MnO_2.88 exhibits interesting behaviours of charge-ordering (CO), ferromagnetic (FM) states and a good conductivity down to the lowest temperatures. The substitution of Ti for Mn destroyed drastically the CO, damaged the motion of itinerant e_g electrons and changed the local parameters of perovskite cell. A change of the structure from tetragonal to rhombohedral symmetry is observed causing a weakening of double-exchange interaction. The experiment results show that the suppression of the CO is sensitive to the variety of Mn³⁺/Mn⁴⁺ ratio. In a field of 8 T at 10 K, FM and CO phase can be evaluated to be ∼20:80 according to the μ_exp/μ_cal ratio for La_0.5Sr_0.5MnO_2.88, whereas the CO state is suppressed for La_0.5Sr_0.5Mn_0.5Ti_0.5O₃ sample, FM and anti-ferromagnetic (AFM) phase are coexisted and evaluated to be ∼54:46, respectively.     

Short- and long-range order in La1−xSrxCoO3 and La1−xBaxCoO3

The short- and long-range order correlations of the crystal structure in the distorted perovskites La_1−xSr_xCoO₃ and La_1−xBa_xCoO₃ (0.0?x?0.5) have been studied by the neutron powder diffraction (NPD) and the Co K-edge X-ray absorption spectroscopy (XAS) measurements. The results of XAS and NPD indicate a local distortion around the Co³⁺ ions in LaCoO₃ at room temperature. The substitution of the La³⁺ ions by the Sr²⁺(Ba²⁺) ions leads to a gradual increase of the Co-O-Co angle and is accompanied by an increase of the mean square relative displacement (MSRD) of the Co-O bond. These results correlate with an increase of the oxygen amplitude vibration in the direction perpendicular to the Co-O bond. The possible explanation of the observed changes of the crystal and electronic structures in the above-mentioned cobaltites is discussed.