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⁻.     

Mechanism of the oxidation and combustion of normal paraffin hydrocarbons: Transition from C<Subscript>1</Subscript>–C<Subscript>6</Subscript> to C<Subscript>7</Subscript>H<Subscript>16</Subscript>

A previously proposed algorithm for constructing an optimal mechanism of the high- and low-temperature oxidation and combustion of normal paraffin hydrocarbons was used, which includes the major processes that determine the rate of reaction and the formation of the main intermediate and final products. The mechanism has the status of a nonempirical detailed mechanism, since all the constituent elementary reactions have a kinetic substantiation. The mechanism has two specific features: it included no reactions of so-called double addition of oxygen and no isomeric compounds and derivatives thereof as intermediate species. Realization of this algorithm leads to fairly compact models, a circumstance important for studies of chemical processes involving paraffin hydrocarbons C _n with large n. Previously, based on this algorithm, compact mechanisms of oxidation and combustion of propane, n-butane, n-pentane, and n-hexane were constructed. In this paper, we develop a nonempirical detailed mechanism of oxidation and combustion of n-heptane. The most important feature of the new mechanism is its ability to predict the staging of the process in the form of cool and blue flames at low autoignition temperatures. A comparison of the simulation results with the available experimental data is conducted.     

Growth of β-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles by pulsed laser ablation technique

This work investigates pulsed laser ablation for Ga₂O₃ nanoparticles. Nanoparticles with diameters of 10 to 500 nm were deposited on silicon substrates in large quantities, by KrF excimer laser ablation of a GaN (99.99% purity) target in high purity nitrogen (99.9995%) background gas at room temperature, without a catalyst. The particle size and phase structure of the as-deposited nanoparticles are examined by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), and selected-area electron diffraction (SAD). FE-SEM images show that the nanoparticles aggregate to form micron-size nanoclusters at chamber pressures of 1 and 5 Torr. On the other hand, nanoparticles aggregate with chain-like nanostructures, are synthesized at high chamber pressures (10 Torr). TEM images further reveal that chain-like nanostructures are formed by the aggregation of individual spherical and ellipsoidal nanoparticles. Photoluminescence measurement shows stable and broad blue emission at 445 nm. PACS 81.20.-N; 81.15.Fg; 75.50.Vv     

Selective ablation of thin SiO<Subscript>2</Subscript> layers on silicon substrates by femto- and picosecond laser pulses

The selective ablation of thin (∼100 nm) SiO₂ layers from silicon wafers has been investigated by applying ultra-short laser pulses at a wavelength of 800 nm with pulse durations in the range from 50 to 2000 fs. We found a strong, monotonic decrease of the laser fluence needed for complete ablation of the dielectric layer with decreasing pulse duration. The threshold fluence for 100% ablation probability decreased from 750 mJ/cm² at 2 ps to 480 mJ/cm² at 50 fs. Significant corruption of the opened Si surface has been observed above ∼1200 mJ/cm², independent of pulse duration. By a detailed analysis of the experimental series the values for melting and breaking thresholds are obtained; the physical mechanisms responsible for the significant dependence on the laser pulse duration are discussed.     

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.     

A comparative study of singlet-oxygen generation by С<Subscript>60</Subscript> and С<Subscript>70</Subscript> fullerenes

The results of comparative investigations of singlet-oxygen generation by С₆₀ and С₇₀ fullerenes in tetrachloromethane solutions, aqueous suspensions, and solid-phase powders of fullerenes optically excited by cw diode arrays with different wavelengths and by pulsed xenon lamps with a band filter are presented. The measurements were performed by recording singlet-oxygen phosphorescence at the O²(¹Δ_g)–O₂(³Σ_g) transition (λ = 1270 nm).     

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.     

Preparation and characterization of organic–inorganic hybrid compound [N(C<Subscript>4</Subscript>H<Subscript>9</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>Cu<Subscript>2</Subscript>Cl<Subscript>6</Subscript>

Organic–inorganic hybrid sample [N(C₄H₉)₄]₂Cu₂Cl₆ was prepared via the reaction between copper chloride and tetrabutylammonium chloride. The compound was characterized by X-ray powder diffraction, IR, Raman, differential scanning calorimetry (DSC), DTA-TGA analysis and electrical impedance spectroscopy. DSC studies indicate a presence of one-phase transition at 343 K. The complex impedance of compound [N(C₄H₉)₄]₂Cu₂Cl₆ have been investigated in temperature and frequency ranges 300–380 K and 200 Hz–5 MHz, respectively. The Z′ and Z″ versus frequency plots are well fitted to an equivalent circuit model. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements CPE. The frequency dependence of the conductivity is interpreted in term of Jonscher's law: s(w) = s_dc + Awⁿ \sigma (\omega ){ } = {\sigma_{\rm{dc}}} + { }A{\omega^n} . The conductivity follows the Arrhenius relation. The variation of the value of these elements with temperatures confirmed the availability of the phase transition at 343 K detected by DSC and electrical measurements.     

Specific physical properties of nanocrystalline (La<Subscript>0.65</Subscript>Sr<Subscript>0.35</Subscript>)<Subscript>0.8</Subscript>Mn<Subscript>1.2</Subscript>O<Subscript>3 ± Δ</Subscript> samples obtained by cold isostatic pressing

Single-phase powders of manganites (La_0.65Sr_0.35)_0.8Mn_1.2O_{3 ± Δ} with average crystallite sizes of 30, 50, and 500 nm were produced by co-precipitation. The samples studied were obtained by cold isostatic pressing of powders at a pressure of 1 GPa without subsequent sintering. It is shown that the size of particles has a significant effect on the electromagnetic properties of the manganite samples. As the crystallite size decreases, the electrical resistance and coercive force increase and the tunneling magnetoresistance of the samples and the Curie temperature decrease.     

Heat capacity of the [N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CdBr<Subscript>4</Subscript> crystal in the temperature range 80–300 K

The heat capacity of the [[N(C₂H₅)₄]₂CdBr₄ crystal is measured by the calorimetric method in the temperature range from 80 to 300 K. It is revealed for the first time that the temperature dependence of the heat capacity C _p (T) exhibits an anomaly associated with the first-order phase transition occurring at the temperature T ₁ = 226.5 K. A long relaxation of the temperature of the crystal is observed in the temperature range 150–165 K.     

Magnetic characteristics of MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles obtained by glycine–nitrate synthesis

The magnetic properties of magnesium–iron spinel (MgFe₂O₄) powdered nanoparticles obtained by glycine–nitrate synthesis are investigated by X-ray phase analysis and the NMR method. According to the results of X-ray phase analysis, the average size of the crystalline part of nanoparticles of the powder under investigation is 45 ± 4 nm. Magnetization J is determined using the formula J = (B/μ0)–H, where B and H are the induction and strength of the magnetic field in the sample, which are measured by the NMR method. The magnetic characteristics of MgFe₂O₄ are as follows: specific saturation magnetization J_sat = 17.52 A m²/kg, specific residual magnetization J_r = 5.73 A m2/kg, coercive force H_c = 4600 A/m, and magnetic moment P_sat = 371 × 10^–20 A m² in the magnetic saturation state and P_r = 121 × 10^–20 A m² in the residual magnetization state.     

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.     

Influence of Matrix Nature on the Structural Characteristics of In<Subscript>2</Subscript>O<Subscript>3</Subscript>–CeO<Subscript>2</Subscript> and SnO<Subscript>2</Subscript>–CeO<Subscript>2</Subscript> Composites Fabricated by the Impregnation Method

The structural characteristics, valence states, and distribution of cerium ions between the components in In₂O₃–CeO₂ and SnO₂–CeO₂ nanocomposites fabricated using the impregnation method were studied. X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX) were used to show that, during impregnation, cerium ions are not included into In₂O₃ crystals and are disposed only on their surface in the form of nano-sized crystallites or amorphous clusters. On the other side, under the contact of CeO₂ clusters with a surface of SnO₂ matrix crystals, cerium ions penetrate into the surface layer of these crystals. In contrast to an In₂O₃–CeO₂ system, where the addition of CeO₂ does not affect the conduction activation energy, where cerium oxide is added to SnO₂, the observed increase in the resistance of a SnO₂–CeO₂ composite is accompanied by a sufficient increase in activation energy. These data and the XPS spectra confirm the modification of the surface layers of conductive SnO₂ crystals as, a result of the penetration of cerium ions into these layers.     

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.     

Crystal structure and ionic conductivity of the soft solid crystal: isoquinoline<Subscript>3</Subscript>•(LiCl)<Subscript>2</Subscript>

A soft solid crystal composed of isoquinoline (IQ) and LiCl was prepared based on the concept of Pearson’s hard-soft acid-base (HSAB) theory. Single-crystal X-ray diffraction best described the isoquinoline₃?(LiCl)₂ as consisting of molecular Li₄Cl₄(isoquinoline)₆ units, where the LiCl cluster is an array of edge-fused Li₂Cl₂ rhombs. Electrochemical impedance measurements on pressed pellets showed that conductivity occurs mainly through the bulk via a hopping mechanism, with a calculated activation energy of E_a = 67 kJ/mol. The high value of the activation energy was due to Li₄Cl₄ clusters that were well separated by intervening IQ ligands in the crystal structure, requiring large hops for ions to migrate through the lattice.     

Generation of CdS clusters using laser ablation: the role of wavelength and fluence

The formation of cationic clusters in the laser ablation of CdS targets has been investigated as a function of wavelength and fluence by mass spectrometric analysis of the plume. Ablation was carried out at the laser wavelengths of 1064, 532, 355, and 266 nm in order to scan the interaction regimes below and above the energy band gap of the material. In all cases, the mass spectra showed stoichiometric Cd _n S _n ⁺ and nonstoichiometric Cd _n S _n−1⁺, Cd _n S _n+1⁺, and Cd _n S _n+2⁺ clusters up to 4900 amu. Cluster size distributions were well represented by a log-normal function, although larger relative abundance for clusters with n=13, 16, 19, 34 was observed (magic numbers). The laser threshold fluence for cluster observation was strongly dependent on wavelength, ranging from around 16 mJ/cm² at 266 nm to more than 300 mJ/cm² at 532 and 1064 nm. According to the behavior of the detected species as a function of fluence, two distinct families were identified: the “light” family containing S₂⁺ and Cd⁺ and the “heavy” clusterized family grouping Cd₂⁺ and Cd _n S _m ⁺. In terms of fluence, it has been determined that the best ratio for clusterization is achieved close to the threshold of appearance of clusters at all wavelengths. At 1064, 532, and 355 nm, the production of “heavy” cations as a function of fluence showed a maximum, indicating the participation of competitive effects, whereas saturation is observed at 266 nm. In terms of relative production, the contribution of the “heavy” family to the total cation signal was significantly lower for 266 nm than for the longer wavelengths. Irradiation at 355 nm in the fluence region of 200 mJ/cm² has been identified as the optimum for the generation of large clusters in CdS.     

Luminescent properties of solid solutions in the PbF<Subscript>2</Subscript>–Euf<Subscript>3</Subscript> system and lead fluoroborate glass ceramics doped with Eu<Superscript>3+</Superscript> ions

Lead fluoroborate glasses doped with Eu³⁺ are synthesized, studied, and used to produce glassceramics by heat treatment. The structure of glass-ceramics is determined by X-ray diffraction. The optical, mechanical, and luminescent properties of the glass-ceramics are studied. The structure and spectral-luminescent properties of solid solutions in the PbF₂–EuF₃ system obtained by both solid-phase reaction and coprecipitation from solutions are investigated.