Electron diffraction study of various lattice defects in a Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> crystal

Lattice defects in a scintillation detector made of Bi₄Ge₃O₁₂ (BGO) could severely impact detector efficiency via non-radiative transfer of electron excitation, thus making thorough investigations of these defects highly important. Here we present a combined experimental and theoretical study of two- and three-dimensional defects in a Czochralski-grown BGO crystal. Upon examination by transmission electron microscopy the selected-area electron diffraction (SAED) patterns in two neighboring parts of the specimen reveal different kinds of two- and three-dimensional defects. Three sub-grains misoriented at 2.47° with reference to each other and probable presence of stacking faults lying in {011} planes were observed in the first examined local area. The SAED image taken from an area in the close neighborhood is much more complicated and is explained in terms of the superposition of reflections from: (i) a partially textured GeO₂ second-phase inclusion; (ii) the basic lattice of BGO and (iii) a superlattice-like structure based on the BGO lattice. The atomic structure of such a superlattice-like structure was theoretically modeled and the corresponding simulated SAED patterns were found to be in good agreement with the experimentally observed one.     

Effect of annealing temperature on microstructures and optical properties of Ba<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> films

Evolution of microstructure and optical property with annealing temperature has been examined for Ba_0.9Sr_0.1TiO₃ films derived from one single precursor solution containing polyethylene glycol polymer. The films sintered below 750°C exhibit a uniform phase structure across the cross-sections and an ordinary optical thin film feature, while the Ba_0.9Sr_0.1TiO₃ films crystallized at 750°C or higher temperature render a lamellar texture consisting of dense and porous Ba_0.9Sr_0.1TiO₃ layers and a good performance as a one-dimensional photonic crystal. The discrepancy in cross-sectional morphology and reflectance property observed in these Ba_0.9Sr_0.1TiO₃ films has been preliminarily explained.     

Orientation dependence of electrical properties of 0.96Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-0.04BaTiO<Subscript>3</Subscript> lead-free piezoelectric single crystal

In this paper, a single crystal of 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ with dimensions of Φ 30×10 mm was grown by the top-seeded-solution growth method. X-ray powder diffraction results show that the as-grown crystal possesses the rhombohedral perovskite-type structure. The dielectric, piezoelectric and electrical conductivity properties were systematically investigated with 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples. The room-temperature dielectric constants for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples are found to be 650, 740 and 400 at 1 kHz. The (T _m, ε _m) values of the dielectric temperature spectra are almost independent of the crystal orientations; they are (306°C, 3718), (305°C, 3613) and (307°C, 3600) at 1 kHz for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal. The optimum poling conditions were obtained by investigating the piezoelectric constants d ₃₃ as a function of poling temperature and poling electric field. For the 〈001〉 and 〈110〉 crystal samples, the maximum d ₃₃ values of 146 and 117 pC/N are obtained when a poling electric field of 3.5 kV/mm and a poling temperature of 80°C were applied during the poling process. The as-grown 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ crystal possesses a relatively large dc electrical conductivity, especially at higher temperature, having a value of 1.98×10⁻¹¹ Ω⁻¹⋅m⁻¹ and 3.95×10⁻⁹ Ω⁻¹⋅m⁻¹ at 25°C and 150°C for the 〈001〉 oriented crystal sample.     

Synthesis of SmAlO<Subscript>3</Subscript> nanocrystalline powders by polymeric precursor method

SmAlO₃ nanocrystalline powders were successfully synthesized by the polymeric precursor method using ethylenediaminetetraacetic acid as a chelating agent. The precursor and the derived powders were characterized by thermogravimetry analysis (TG) and differential scanning calorimetry analysis (DSC), infrared spectroscopy (IR), X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The results showed that pure SmAlO₃ powder with orthorhombic perovskite structure could be synthesized at 800°C for 2 h without formation of any intermediate phase. The average particle size of the powder synthesized at 900°C was as low as 28 nm. Subsequently, the bulk SmAlO₃ ceramics were prepared at various sintering temperatures using the synthesized powders calcined at 900°C for 2 h as starting materials. The sintering experiments indicated that the sample sintered at 1550°C for 2 h exhibited the highest relative density of 97.2% and possessed the best microwave dielectric properties of ε _r=20.94, Q×f=78600 GHz and τ _f=−71.8 ppm/°C.     

Temperature dependence of thermal properties of Ag<Subscript>8</Subscript>In<Subscript>14</Subscript>Sb<Subscript>55</Subscript>Te<Subscript>23</Subscript> phase-change memory materials

The dependence of thermal properties of Ag₈In₁₄Sb₅₅Te₂₃ phase-change memory materials in crystalline and amorphous states on temperature was measured and analyzed. The results show that in the crystalline state, the thermal properties monotonically decrease with the temperature and present obvious crystalline semiconductor characteristics. The heat capacity, thermal diffusivity, and thermal conductivity decrease from 0.35 J/g K, 1.85 mm²/s, and 4.0 W/m K at 300 K to 0.025 J/g K, 1.475 mm²/s, and 0.25 W/m K at 600 K, respectively. In the amorphous state, while the dependence of thermal properties on temperature does not present significant changes, the materials retain the glass-like thermal characteristics. Within the temperature range from 320 K to 440 K, the heat capacity fluctuates between 0.27 J/g K and 0.075 J/g K, the thermal diffusivity basically maintains at 0.525 mm²/s, and the thermal conductivity decreases from 1.02 W/m K at 320 K to 0.2 W/m K at 440 K. Whether in the crystalline or amorphous state, Ag₈In₁₄Sb₅₅Te₂₃ are more thermally active than Ge₂Sb₂Te₅, that is, the Ag₈In₁₄Sb₅₅Te₂₃ composites bear stronger thermal conduction and diffusion than the Ge₂Sb₂Te₅ phase-change memory materials.     

Electronic excitation energies in TiO<Subscript>2</Subscript> in the fluorite phase

The ab initio pseudopotential method within the generalized gradient approximation (GGA) and quasiparticle approximation has been used to investigate the electronic properties of titanium dioxide in the rutile, anatase, and fluorite structures, respectively. Here we present the GW approximation for the electronic self-energy, which allows to calculate excited-state properties, especially electronic band structures. For this calculation, good agreement with the experimental results for the minimum band gaps in rutile and anatase phase is obtained. In the fluorite phase we predict that titanium dioxide will be an indirect (Γ to X) wide band-gap semiconductor (2.367 or 2.369 eV) and the properties remain to be confirmed by experiment.     

Role of A-site deficiency in the magneto-transport properties of Pr<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> relaxed films

The magneto-transport properties of thick relaxed A-site deficient films having the composition Pr Sr_0.3MnO₃ (P_□SMO with the □ symbol for the Pr vacancy) and Pr_0.7Sr MnO₃ (PS_□MO) are studied. A direct comparison with a Pr_0.7Sr_0.3MnO₃ (PSMO)completely relaxed film, deposited under the same growth conditions, shows a reduction of the in-plane parameter a₁₀₀ associated to an enhancement of the out-plane parameter. The strains (bulk strain ε_B and biaxial Jahn-Teller strain ε_J-T) do vary with the nature of the cationic vacancy. For example, an enhancement of ε_B of 9% in the PS_□MO film (Sr deficient) produces a decrease of T_C of 30 K, whereas the Pr deficient P_□SMO film exhibits a large reduction of both ε_B (-16%) and ε_J-T (divided by a factor of 5), which enhances T_C of 12 K, similarly to previous observations on bulk ceramics. With a reduced resistivity (ρ<0.02 Ω cm), the obtained Pr-deficient film, P_□SMO, exhibits the best magneto-transport properties with a decreasing magnetoresistance sensitivity at low field.     

Effect of process parameters and post-deposition annealing on the microwave dielectric and optical properties of pulsed laser deposited Bi<Subscript>1.5</Subscript>Zn<Subscript>1.0</Subscript>Nb<Subscript>1.5</Subscript>O<Subscript>7</Subscript> thin films

Bismuth Zinc niobate (Bi_1.5Zn_1.0Nb_1.5O₇) thin films were deposited by pulsed laser deposition (PLD) method on fused silica substrates at different oxygen pressures. The structural, microwave dielectric and optical properties of these thin films were systematically studied for both the as-deposited and the annealed films at 600°C. The as-deposited films were all amorphous in nature but crystallized on annealing at 600°C in air. The surface morphology as studied by atomic force microscopy (AFM) reveals ultra-fine grains in the case of as-deposited thin films and cluster grain morphology on annealing. The as-deposited films exhibit refractive index in the range of 2.36–2.53 (at a wavelength of 750 nm) with an optical absorption edge value of 3.30–3.52 eV and a maximum dielectric constant of 11 at 12.15 GHz. On annealing the films at 600°C they crystallize to the cubic pyrochlore structure accompanied by an increase in band gap, refractive index and microwave dielectric constant.     

Mass and kinetic energy distribution of the species generated by laser ablation of La<Subscript>0.6</Subscript>Ca<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript>

The mass distributions of the species generated by laser ablation from a La_0.6Ca_0.4MnO₃ target using laser irradiation wavelengths of 193 nm, 266 nm and 308 nm have been investigated with and without a synchronized gas pulse of N₂O. The kinetic energies of the species are measured using an electrostatic deflection energy analyzer, while the mass distributions of the species were analyzed with a quadrupole mass filter. In vacuum (pressure 10⁻⁷ mbar), the ablation plume consists of metal atoms and ions such as La, Ca, Mn, O, LaO, as well as multiatomic species, e.g. LaMnO⁺. The LaO⁺ diatomic species are by far the most intense diatomic species in the plume, while CaO and MnO are only detected in small amounts. The interaction of a reactive N₂O gas pulse with the ablation plume leads to an increase in plume reactivity, which is desired when thin manganite films are grown, in order to incorporate the necessary amount of oxygen into the film. The N₂O gas pulse appears to have a significant influence on the oxidation of the Mn species in the plume, and on the creation of negative ions, such as LaO⁻,O⁻ and O₂⁻.     

Continuous-wave intracavity Raman laser at 1179.5 nm with SrWO<Subscript>4</Subscript> Raman crystal in diode-end-pumped Nd:YVO<Subscript>4</Subscript> laser

We report a continuous-wave intracavity Raman laser at 1179.5 nm with a SrWO₄ Raman crystal in a diode-end-pumped Nd:YVO₄ laser. The highest output power of 2.23 W is obtained at the laser diode power of 21.2 W corresponding to the slope efficiency of 17.3% and a diode-to-stokes optical conversion efficiency of 10.5%. The dependence of the Raman laser performance on the pump polarization is also studied. The measured Raman thresholds are about 9.3 and 8.3 W in the diode pump laser power for the a- and b-polarized configurations, respectively. The Raman gain coefficients of the c-cut SrWO₄ crystal for a- and b-polarized pumps are estimated to be about 4.9 and 4.7 cm/GW, respectively.     

Effect of the ceramic grain size and concentration on the dynamical mechanical and dielectric behavior of poly(vinilidene fluoride)/Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> composites

Laser-induced backside wet and dry etching (LIBWE and LIBDE) methods were developed for micromachining of transparent materials. Comparison of these techniques is helpful in understanding the etching mechanism but was not realized due to complications in setting up comparable experimental conditions. In our comparative investigations we used a solid tin film for dry and molten tin droplets for wet etching of fused-silica plates. A tin–fused-silica interface was irradiated through the sample by a KrF excimer laser beam (λ=248 nm, FWHM=25 ns); the fluence was varied between 400 and 2100 mJ/cm². A significant difference between the etch depths of the two investigated methods was not found. The slopes of the lines fitted to the measured data (sl_LIBDE=0.111 nm/mJ cm⁻², sl_LIBDE=0.127 nm/mJ cm⁻²) were almost similar. Etching thresholds for LIBDE and LIBWE were approximately 650 and 520 mJ/cm², respectively. To compare the dependence of etch rates on the pulse number, target areas were irradiated at different laser fluences and pulse numbers. With increasing pulse number a linear rise of depth was found for wet etching while for dry etching the etch depth increase was nonlinear. Secondary ion mass spectroscopic investigations proved that this can be due to the reconstruction of a new thinner tin-containing surface layer after the first pulse.     

Terahertz spectroscopy of central and soft phonon modes in LuFe<Subscript>2</Subscript>O<Subscript>4</Subscript>

The terahertz dielectric response of LuFe₂O₄ is investigated by terahertz time-domain spectroscopy over a temperature range of 6–290 K. It is revealed that besides the central mode associated with the charge-ordered state, a soft TO₁ mode at below ∼240 K is identified indicating the existence of displacing ferroelectricity, in addition to the charge-ordering-induced ferroelectricity at below 320 K. The anomaly of the soft mode at ∼180 K reflects the magnetoelectric correlation between the soft TO₁ mode and the spin/charge fluctuations revealed recently. Finally, the magnetic property at below ∼240 K is discussed.     

Quantitative analysis of dilute mixtures of SO<Subscript>2</Subscript> in N<Subscript>2</Subscript> at 7.4 μm by difference frequency spectroscopy

We describe a 7.4-μm source based on difference frequency generation with 6.5 mW of 1278-nm radiation from an extended cavity laser and 66 mW of 1544-nm radiation from another extended cavity laser, amplified in an erbium-doped fibre amplifier. Optimum focusing of the input beams in the 5×5×10-mm³ AgGaSe₂ crystal, and the spatial and temporal characteristics of the output beam, are determined. The source is used for accurate determination of line parameters for selected lines of the ν₃ band of SO₂, centred at 1361 cm^-1. Subsequently, these lines are used for performing quantitative analysis of gas mixtures containing SO₂ at concentration levels down to 4 ppm without relying on any calibration with certified gas mixtures. This demonstrates the potential of infrared spectroscopy as a primary method for low-concentration gas analysis. Received: 16 January 2003 / Revised version: 19 February 2003 / Published online: 9 April 2003 RID="*" ID="*"Corresponding author. Fax: +45-4593/1137, E-mail: jh@dfm.dtu.dk     

Physical property characterization of single step synthesized NdFeAsO<Subscript>0.80</Subscript>F<Subscript>0.20</Subscript> bulk 50 K superconductor

We report an easy single step synthesis route of title compound NdFeAsO_0.80F_0.20 superconductor having bulk superconductivity below 50 K. The title compound is synthesized via solid-state reaction route by encapsulation in an evacuated (10^-3 Torr) quartz tube. Rietveld analysis of powder X-ray diffraction data shows that compound crystallized in tetragonal structure with space group P4/nmm. R(T)H measurements showed superconductivity with T _c (R = 0) at 48 K and a very high upper critical field (H _c2) of up to 345 T. Magnetic measurements exhibited bulk superconductivity in terms of diamagnetic onset below 50 K. The lower critical field (H _c1) is around 1000 Oe at 5 K. In normal state i.e., above 60 K, the compound exhibited purely paramagnetic behavior and thus ruling out the presence of any ordered FeO _x impurity in the matrix. In specific heat measurements a jump is observed in the vicinity of superconducting transition (T _c ) along with an upturn at below T = 4 K due to the AFM ordering of Nd⁺³ ions in the system. The Thermo-electric power (TEP) is negative down to T _c , thus indicating dominant carriers to be of n-type in NdFeAsO_0.80F_0.20 superconductor. The granularity of the bulk superconducting NdFeAsO_0.8F_0.2 sample is investigated and the intra and inter grain contributions have been individuated by looking at various amplitude and frequencies of the applied AC drive magnetic field.     

Efficient continuous-wave YVO<Subscript>4</Subscript>/Nd:YVO<Subscript>4</Subscript> Raman laser at 1176 nm

We present a simple and compact continuous-wave (CW) 1176 nm laser based on self-frequency Raman conversion in continuous-grown YVO₄/Nd:YVO₄ composite crystal. With a composite crystal 30 mm in length, a maximum output power up to 1.84 W was achieved at the incident diode pump power of 23.6 W. Corresponding to overall optical conversion, the efficiency was 7.8% and the slope efficiency was 8.5%. The conversion efficiency has been doubled compared with the conventional Nd:YVO₄ CW self-frequency Raman laser. The excellent performance of this laser shows that the long continuous-grown YVO₄/Nd:YVO₄ composite crystal is promising in the application of CW Raman lasers and ideal for miniaturization.     

Recent developments in the doping of LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode material for 5 V lithium-ion batteries

LiMn₂O₄ has been considered a promising cathode material for lithium-ion batteries in electric vehicles. However, there are still a number of problems of severe capacity fading before any materials modifications. Among all doped LiMn₂O₄, spinel LiNi_0.5Mn_1.5O₄ material is seen as a potential cathode material for use in electric vehicles and energy storage systems in the future because of its high working potential (4.7 V), high energy density (the energy density of LiNi_0.5Mn_1.5O₄ is 20% higher than that of LiCoO₂), acceptable stability, and good cycling performance. In the presented paper, the structure and electrochemical performance of doped LiNi_0.5Mn_1.5O₄ are reviewed. The rate capability, rate performance and cyclic life of various doped LiNi_0.5Mn_1.5O₄ materials are described. This review also focuses on the present status of doped LiNi_0.5Mn_1.5O₄, then on its near future developments.     

Visualization of focusing–refocusing cycles during filamentation in BaF<Subscript>2</Subscript>

Filamentation occurs within a 1.5 cm-long crystal of BaF₂ during the propagation of intense, ultrashort (40 fs) pulses of 800 nm light; a systematic study as a function of incident power enables us to extract quantitative information on laser intensity within the condensed medium, the electron density and the six-photon absorption cross section. At low incident power, a single filament is formed within the crystal; two or more filaments are observed along the direction transverse to laser propagation at higher incident powers. Further, due to fluorescence from six-photon absorption (6PA), we are able to map the intensity variation in the focusing–refocusing cycles along the direction of laser propagation. At still higher incident powers, we observe splitting of multiple filaments. By measuring the radius (L _min) of single filament inside BaF₂, we obtain estimates of peak intensities (I _max) and electron densities (ρ _max) to be 3.26×10¹³ W cm⁻² and 2.81×10¹⁹ cm⁻³, respectively. Use of these values enables us to deduce that the 6PA cross-section in BaF₂ is 0.33×10⁻⁷⁰ cm¹² W⁻⁶ s⁻¹.     

The development of the physical and electrical characteristics of multi-layer TiO<Subscript>2</Subscript>–W–TiO<Subscript>2</Subscript> thin films

In this study, two different thin films, TiO₂ thin film and TiO₂–W–TiO₂ multi-layer thin films (W, tungsten), are prepared by RF magnetron sputtering onto glass substrates. The crystal structure, morphology, and transmittance of TiO₂ and TiO₂–W–TiO₂ multi-layer thin films are investigated by X-ray diffraction, SEM, and UV-Vis spectrometer, respectively. The amorphous, rutile, and anatase TiO₂ phases are observed in the TiO₂ thin film and in the TiO₂–W–TiO₂ multi-layer thin films. The deposition of tungsten as the inter-layer will have large effect on the transmittance and phase ratios of rutile and anatase phases in the TiO₂–W–TiO₂ multi-layer thin films. The crystal intensities of amorous TiO₂ will decrease as the tungsten is used as the middle layer in the multi-layer structure. The band gap energy values of TiO₂ thin film and TiO₂–W–TiO₂ multi-layer thin films are evaluated from (αhν)^1/2 versus energy plots, and the calculated results show that the energy gap decreases from 3.21 eV (TiO₂ thin film) to 3.08∼3.03 EV (TiO₂–W–TiO₂ multi-layer thin films).     

Temporal pulsewidth and the wavelength dependences of the product ions obtained by laser ablation of solid C<Subscript>60</Subscript>

By ablating solid C₆₀ with a laser pulse, we observe various processes such as the prompt- and the delayed-ionization of C₆₀, the fragmentation into molecular ions and the formation of cluster ions. We found these processes show distinct dependences on the temporal pulse width, the power and the wavelength of the ablation laser. From the observations, we could confirm efficient coupling of laser energy to C₆₀ through the molecular absorption even with a laser pulse width less than the electron-phonon coupling time of the C₆₀ molecule.     

Preparation of epitaxial orthorhombic YMnO<Subscript>3</Subscript> thin films and the current–voltage rectifying effect

Epitaxial orthorhombic YMnO₃(YMO) thin films on (001) Nb:SrTiO₃(NSTO) substrates were prepared by pulsed laser deposition. The weak ferromagnetism at low temperature, probably ascribed to the stretched Mn-spin configuration along [010] direction, was identified. The dielectric anomaly at the spin–glass freezing point indicates clearly a spin–phonon (magnetoelectric) coupling which can be modulated by electric field. The as-prepared YMO/NSTO heterostructure exhibits significant current–voltage (I–V) rectifying effect over a broad temperature range.