Lanthanide-doped strontium barium niobate (SBN) materials: A vibrational investigation

Vibrational Raman spectra have been measured for strontium barium niobate (Sr_0.5Ba_0.5Nb₂O₆, SBN50) single crystals and nanopowders doped with 1 mol% of the luminescent ions Eu³⁺ and Er³⁺. The nanocrystalline materials show slightly broader spectra with respect to the single crystals with the same composition. The presence of the Eu³⁺ and Er³⁺ ions at the 1 mol% doping level, and the present particle size (200 nm) do not appear to affect the ferro-to-paraelectric phase transition temperature typical of undoped SBN50 single crystals, as detected from anomalies in the dependence of the position of the Raman peak around 635 cm^?1 as a function of the temperature.     

Self and N2 collisional broadening of far-infrared methane lines measured at the SOLEIL synchrotron

Following our recent study devoted to measurements of intensities of pure rotation lines of methane, room temperature far infrared spectra of methane diluted in nitrogen at five total pressures between 100 and 800 hPa have been recorded at the AILES beamline of the SOLEIL synchrotron. One hundred and five N₂ broadening coefficients of methane pure rotation lines have been measured in the 83–261 cm^?1 spectral range using multi-spectrum non-linear least squares fitting of Voigt profiles. Pressure-induced line shifts were not needed to fit the spectra to the noise level and line mixing effects were neglected. One hundred and seventy-six self broadening coefficients have also been measured in the 59–288 cm^?1 spectral range using the pure methane spectra recorded in our previous work. The measured N₂ broadening coefficients were compared to semi-classical calculations.     

Luminescence and defect studies of YAlO3:Dy3+, Sm3+ single crystals exposed to 100 MeV Si7+ ion beam

Ionoluminescence (IL) and photoluminescence (PL) spectra for different rare earth ions (Sm³⁺ and Dy³⁺) activated YAlO₃ single crystals have been induced with 100 MeV Si⁷⁺ ions with fluence of 7.81×10¹² ions cm^?2. Prominent IL and PL emission peaks in the range 550–725 nm in Sm³⁺ and 482–574 nm in Dy³⁺ were recorded. Variation of IL intensity in Dy³⁺ doped YAlO₃ single crystals was studied in the fluence range 7.81×10¹²–11.71×10¹² ions cm^?2. IL intensity is found to be high in lower ion fluences and it decreases with increase in ion fluence due to thermal quenching as a result of an increase in the sample temperature caused by ion beam irradiation. Thermoluminescence (TL) spectra were recorded for fluence of 5.2×10¹² ions cm^?2 on pure and doped crystals at a warming rate of 5 °C s^?1 at room temperature. Pure crystals show two glow peaks at 232 (Tg₁) and 328 °C (Tg₂). However, in Sm³⁺ doped crystals three glow peaks at 278 (Tg₁), 332 (Tg₂) and 384 °C (Tg₃) and two glow peaks at 278 (Tg₁) and 331 °C (Tg₂) in Dy³⁺ was recorded. The kinetic parameters (E, b s) were estimated using glow peak shape method. The decay of IL intensity was explained by excitation spike model.     

7Li and 51V NMR study on Li+ ionic diffusion in lithium intercalated LixV2O5

Li_xV₂O₅ (0.4 < x < 1.4) prepared by solid-state reaction were studied by ⁷Li and ⁵¹V NMR spectroscopy. ⁷Li NMR spectra showed a narrowing of the line width in relation to Li⁺ionic diffusion. Analysis of Li_xV₂O₅ using a Debye-type relaxation model showed a low activation energy ∼0.07 eV in the sample of x = 0.4 below room temperature, and revealed a Li⁺ionic diffusion with larger activation energy ∼0.5 eV above 450 K in lithium-rich samples. The latter is ascribed to the existence of a multi-phase system comprising stable ɛ- and γ-phases, resulting from complicated phase transitions at high temperature. These shapes and shifts enable the classification of the β-, ɛ-, δ-, and γ-phases. The ionic diffusion of Li⁺ ions is discussed in relation to the complicated phase transitions.     

Luminescence and Scintillation Characterization of Cs2NaGdBr6: Ce3+ Single Crystal

Luminescence and scintillation properties of newly discovered bromo-elpasolites Cs₂NaGdBr₆: Ce³⁺ (CNGB: Ce³⁺) are presented. Single crystals of CNGB: Ce³⁺ with dimensions up to Ø7×10 mm³ are successfully grown by the Bridgman technique. X-ray excited luminescence measurements of the grown samples showed a broad emission band in the wavelength range from 365 to 470 nm. It offered an energy resolution of 5.1% (FWHM) at 662 keV for 10% Ce sample. The light output of the investigated samples increases along with cerium concentration. A maximum light yield of ～36,800 ph/MeV is measured for the 10% Ce sample crystal. Under γ-ray excitation, CNGB: Ce³⁺ crystals showed three exponential decay time components. The scintillation mechanism in the sample crystal is presented.     

High coercivity and superparamagnetic behavior of nanocrystalline iron particles in alumina matrix

Single-domain nanoscale magnetic iron particles have been embedded uniformly in an amorphous matrix of alumina using a pulsed laser deposition technique. Structural characterization by transmission electron microscopy (TEM) reveals the presence of a crystalline iron and an amorphous alumina phase. Fine particle magnetism have been investigated by carrying out field and temperature dependence of magnetization measurements using superconducting quantum interference device magnetometer. The particle size of Fe in Al₂O₃ matrices prepared by changing the deposition time of Fe, have been found to be 9, 7 and 5 nm from TEM studies. At 10 K, the coercivities of these samples are found be 450, 350 and 150 Oe, respectively. At 300 K, the coercivity of Fe–Al₂O₃ sample decreases from 100 to 50 Oe as the particle size decreases from 9 to 7 nm and finally the sample turns superparamagnetic when the Fe particle size becomes around 5 nm. Based on the calculated value of blocking temperature, T_B, (481 K), magnetic anisotropy K (4.8×10⁵ erg/cm³) for Fe, and the Boltzmann constant k_B (1.38×10⁻¹⁶ erg/K) from T_B=KV/25k_B, the mean radius of Fe particles is found to be 9.3 nm. in one of the samples. This is in good agreement with the particle size measured using TEM studies.     

YAG laser-induced β-BaB2O4 crystalline dot formation in Sm2O3–BaO–B2O3 glasses

A continuous-wave (CW) YAG laser (power: 0.75–0.9 J/s, irradiation time: 15 s–15 min) with a wavelength of 1064 nm is irradiated to 11.1Sm₂O₃·44.4BaO·44.4B₂O₃ glass, and the formation of β-BaB₂O₄ (β-BBO) crystalline dots with a diameter of 30–150 μm is confirmed from micro-Raman spectra. β-BBO crystals with around 200 μm length grow towards the interior of the glass. The incorporation of Sm³⁺ into β-BBO crystalline dots is suggested from micro-Raman and fluorescence spectra. The second harmonic generation is detected from the array (10×10=100 dots) of β-BBO crystalline dots, indicating that each crystalline dot formed by YAG laser irradiation is a nonlinear optical crystal. CW YAG laser irradiation to glass with Sm³⁺ ions is a nice technique for a spatially controlled crystal growth.     

TiO2(110)-(1 × 1) supported Cu particles: An FT-RAIRS investigation

The morphology of TiO₂(110)-(1 × 1) supported Cu particles has been investigated by Fourier Transform Reflection Absorption Infrared Spectroscopy (FT-RAIRS), employing adsorbed CO as a probe molecule sensitive to local surface structure. For Cu coverage (deposited at 300 K) less than 2.85 MLE nucleated Cu particles in the range 2 nm–4 nm are formed, as indicated by a final state shift in the core level Cu(2p_3/2) binding energy and by the existence of only transmission bands in the FT-RAIRS spectra for adsorbed CO. ν_S(CO) indicates that these small particles expose sites similar to those of the stepped Cu surfaces Cu(211), Cu(311), and Cu(755). At Cu coverages in the range of 6 MLE and above, corresponding to particle sizes above 4.6 nm, ν_S(CO) indicates the predominance of (110), (100) and (111) adsorption sites. Annealing the Cu layers to 650 K results in the slight growth of the particle sizes, and transformation of the CO adsorption sites corresponding to the close packed facets. The transformation of the local dielectric from that of titania to that dominated by the Cu particle is shown to take place between 3.7 and 4.2 nm, and this change is also to a smaller extent sensitive to the dispersion of the particles.     

N-methylpyrrolidine-based precursors for chemical vapor deposition of GaNx particles

An attempt to prepare a metalorganic precursor of gallium with reactivity at low temperature in chemical vapor deposition (CVD) systems was done by reacting N-methylpyrrolidine with metal gallium or gallium nitrate under mild conditions. The precursors were bubbled into a CVD assemblage and then reacted with ammonia at temperatures between 400 and 700 °C. The depositions onto silicon substrates were pyramidal particles of 100 nm width at the base and up to 55 nm in height. The rise in growth temperature increased particle density from 0.9 to 27.1 particles per square micron, but reduced the height from 50 to 10 or 2 nm. XPS spectra showed the presence of gallium and nitrogen. The intensity of the gallium spectrum decreased as the process temperature increased indicating that GaN_x particles were deposited rather than the stoichiometric gallium nitride (GaN). An additional N1s band of impurities appeared whose intensity increases with the reaction temperature. The lower impurity content corresponded to the sample prepared with Ga(NO₃)₃ at 400 °C.     

H2 splitting on Pt,Ru and Rh nanoparticles supported on sputtered HOPG

The equilibrium hydrogen exchange rate between adsorbed and gas phase hydrogen at 1 bar is measured for Pt, Ru and Rh nanoparticles supported on a sputtered HOPG substrate. The particles are prepared by Electron Beam Physical Vapor Deposition and the diameter of the particles varies between 2 and 5 nm. The rate of hydrogen exchange is measured in the temperature range 40–200 °C at 1 bar, by utilization of the H–D exchange reaction. We find that the rate of hydrogen exchange increases with the particle diameter for all the metals, and that the rate for Ru and Rh is higher than for Pt. In the case of Pt, the equilibrium dissociative sticking probability, S, is found to be nearly independent of particle diameter. For Ru and Rh, S is found to depend strongly on particle diameter, with the larger particles being more active. The apparent energy of desorption at equilibrium, E_app, shows a dramatic increase with decreasing particle diameter for diameters below 5 nm for Ru and Rh, whereas E_app is only weakly dependent on particle diameter for Pt. We suggest that the strong variation in the apparent desorption energy with particle diameter for Ru and Rh is due to the formation of compressed hydrogen adlayers on the terraces of the larger particles. Experiments are also carried out in the presence of 10 ppm CO. Pt is found to be very sensitive to CO poisoning and the H–D exchange rate drops below the detection limit when CO is added to the gas mixture. In the case of Ru and Rh nanoparticles, CO decreases the splitting rate significantly, also at 200 °C. The variation of the sensitivity to CO poisoning with particle diameter for Ru and Rh is found to be weak.     

Structural evolution,growth mechanism and photoluminescence properties of CuWO4 nanocrystals

Copper tungstate (CuWO₄) crystals were synthesized by the sonochemistry (SC) method, and then, heat treated in a conventional furnace at different temperatures for 1 h. The structural evolution, growth mechanism and photoluminescence (PL) properties of these crystals were thoroughly investigated. X-ray diffraction patterns, micro-Raman spectra and Fourier transformed infrared spectra indicated that crystals heat treated and 100 °C and 200 °C have water molecules in their lattice (copper tungstate dihydrate (CuWO₄·2H₂O) with monoclinic structure), when the crystals are calcinated at 300 °C have the presence of two phase (CuWO₄·2H₂O and CuWO₄), while the others heat treated at 400 °C and 500 °C have a single CuWO₄ triclinic structure. Field emission scanning electron microscopy revealed a change in the morphological features of these crystals with the increase of the heat treatment temperature. Transmission electron microscopy (TEM), high resolution-TEM images and selected area electron diffraction were employed to examine the shape, size and structure of these crystals. Ultraviolet–Visible spectra evidenced a decrease of band gap values with the increase of the temperature, which were correlated with the reduction of intermediary energy levels within the band gap. The intense photoluminescence (PL) emission was detected for the sample heat treat at 300 °C for 1 h, which have a mixture of CuWO₄·2H₂O and CuWO₄ phases. Therefore, there is a synergic effect between the intermediary energy levels arising from these two phases during the electronic transitions responsible for PL emissions.     

Photoluminescence characterization of beryllium-implanted 6H–silicon carbide

Beryllium has been implanted into both n- and p-type 6H–SiC with post-implantation annealing at 1600 °C. Photoluminescence (PL) measurements have been performed, and PL lines at 420.5, 431 nm, and a broad band at around 505 nm have been observed. The line at 420.5 nm is attributed to an intrinsic defect D_II-center induced by beryllium implantation. The effects of excitation intensity and temperature during the PL experiments are investigated. Based on the excitation laser dependence PL result, the new doublet lines at around 431 nm are thought to be associated with beryllium related bound excitons. The broad band corresponding to the green luminescence at room temperature has been attributed to the recombination of free carriers to beryllium bound levels.     

Evaluation of rheological behavior of 10W40 lubricant containing hybrid nano-material by measuring dynamic viscosity

In the present paper, the dynamic viscosity of 10W40 lubricant containing hybrid nano-materials has been examined. Hybrid nano-materials were composed of 90% of silica (SiO₂) with 20–30 nm mean particle size and 10% of multi-walled carbon nanotubes (MWCNTs) with inner diameter of 2–6 nm and outer diameter of 5–20 nm. Nano-lubricant samples were prepared by two-step method with solid volume fractions of 0.05%, 0.1%, 0.25%, 0.5%, 0.75% and 1%. Dynamic viscosity of the samples was measured at temperatures between 5 and 55 °C and at shear rates of 666.5 s⁻¹ up to 11,997 s⁻¹. Experimental results indicated that the nano-lubricant had non-Newtonian behavior at all temperatures, while 10w40 oil was non-Newtonian only at high temperatures. With the use of the curve fitting technique of experimental data, power law and consistency indexes were obtained; furthermore, these coefficients were assessed by shear stress and viscosity diagram.     

Magneto-optical properties of α-Fe2O3@ZnO nanocomposites prepared by the high energy ball-milling technique

Magnetic–fluorescent nanocomposites (NCs) with 10 wt% of α-Fe₂O₃ in ZnO have been prepared by the high energy ball-milling. The crystallite sizes of α-Fe₂O₃ and ZnO in the NCs are found to vary from 65 nm to 20 nm and 47 nm to 15 nm respectively as milling time is increased from 2 to 30 h. XRD analysis confirms presence of α-Fe₂O₃ and ZnO in pure form in all the NCs. UV–vis study of the NCs shows a continuous blue-shift of the absorption peak and a steady increase of band gap of ZnO with increasing milling duration that are assigned to decreasing particle size of ZnO in the NCs. Photoluminescence (PL) spectra of the NCs reveal three weak emission bands in the visible region at 421, 445 and 485 nm along with the strong near band edge emission at 391 nm. These weak emission bands are attributed to different defect – related energy levels e.g. Zn-vacancy, Zn interstitial and oxygen vacancy. Dc and ac magnetization measurements show presence of weakly interacting superparamagnetic (SPM) α-Fe₂O₃ particles in the NCs. ⁵⁷Fe-Mössbauer study confirms presence of SPM hematite in the sample milled for 30 h. Positron annihilation lifetime measurements indicate presence of cation vacancies in ZnO nanostructures confirming results of PL studies.     

Crystal growth,spectral and NMR studies of nonlinear optical crystal: L-valinium picrate

Organic nonlinear optical material, L-valinium picrate (LVP) was synthesized by slow evaporation solution growth method. The synthesized material was purified by repeated recrystallization. Single crystals of LVP were grown by slow evaporation method using water as solvent. The cell dimensions were obtained by X-ray diffraction study and crystal system was confirmed as monoclinic. The transmission spectrum of LVP was recorded by UV–Vis-NIR spectrometer in the range between 190 nm and 1100 nm which addressed the high percentage of transmission of the sample in the entire visible region. The presence of functional groups was studied by FT-IR analysis. The chemical environment of carbon and hydrogen in the proposed structure of LVP crystal was confirmed by FT NMR studies. The Kurtz-Perry powder SHG measurement was confirmed the frequency doubling of the crystal.     

Effect of erbium concentration on optical properties of Er:YLF laser crystals

Four Er-doped LiYF₄ crystals with different Er-concentrations were grown by Czochralski method. The laser crystals were characterized by measurements of ICP-AES, XRD, absorption spectra, up-conversion fluorescence spectra, near-infrared (NIR) and mid-infrared (Mid-IR) fluorescence spectra, as well as luminescence decays. It was found that the heavily 15 at% Er-doped YLF crystal is more proper in up-conversion or ∼3 μm laser applications; while the 5 at% Er-doped YLF is a better candidate for ∼1.5 μm lasers within these four crystals.     

Hydrothermal synthesis and the enhanced blue upconversion luminescence of NaYF4:Nd3+,Tm3+,Yb3+

Nd³⁺, Tm³⁺ and Yb³⁺ co-doped NaYF₄ upconversion (UC) material was synthesized by the hydrothermal method. The structure of the sample was characterized by the X-ray diffraction, and its UC luminescence properties were investigated in detail. Under the 980 nm semiconductor laser excitation, its UC spectra exhibited distinct emission peaks at 451 nm, 475 nm and 646 nm respectively. On the basis of the comparison of UC spectra between NaYF₄:Nd³⁺,Tm³⁺,Yb³⁺ and NaYF₄:Tm³⁺,Yb³⁺, it was indicated that the existence of Nd³⁺ ion enhanced the blue emission intensity. The law of luminescence intensity versus pump power proved that the blue emission at 475 nm, and the red emission at 646 nm were the two-photon processes, while the blue emission at 451 nm was a three-photon process.     

Synthesis,characterization and magnetic properties of lightly doped La2−xSrxCuO4 (x = 0.04) nanoparticles

Lightly doped La_2−xSr_xCuO₄ (x = 0.04) nanoparticles with different particle sizes have been successfully prepared by a sol–gel method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared transmission (IR) spectra and superconducting quantum interference device (SQUID) magnetometer. All samples are single phase and have an orthorhombic unit cell. As the particle size reduces, it is found that the IR band at around 685 cm⁻¹ corresponding to the in-plane Cu–O asymmetrical stretching mode shifts to higher frequency and the magnetization exhibits a large enhancement at low temperature. The magnetic susceptibility of all samples follows a modulated Curie law between ∼20 K and ∼100 K and the Curie constant displays a strong dependence on the particle size. It is suggested that as the particle size decreases surface effects should play an important role in the magnetic properties of the nanoparticles.     

High performance batch production of LREBa2Cu3Oy using novel thin film Nd-123 seed

A batch production for fabrication of LREBa₂Cu₃O_y (LRE: Sm, Gd, NEG) “LRE-123” pellets are developed in air and Ar-1% O₂ using a novel thin film Nd-123 seeds grown on MgO crystals. The SEM and XRD results conformed that the quality and orientation of the seed crystals are excellent. On the other hand, new seeds can withstand temperatures >1100 °C, as a result, the cold seeding process was applied even to grow Sm-123 material in Air. The trapped field observed in the best 45 mm single-grain puck of Gd-123 was in the range of 1.35 T and 0.35 T at 77.3 K and 87.3 K, respectively. The average trapped field at 77.3 K in the 24 mm diameter NEG-123 samples batch lies between 0.9 and 1 T. The maximum trapped field of 1.2 T was recorded at the sample surface. Further, the maximum trapped field of 0.23 T at 77 K was recorded in a sample with 16 mm diameter of Sm-123 with 3 mol% BaO₂ addition. As a result we made more then 130 single grain pucks within a couple of months. Taking advantage of the single grain batch processed material, we constructed self-made chilled levitation disk, which was used on the open day of railway technical research Institute. More then 150 children stood on the levitation disk and revel the experience of levitation. The present results prove that a high-performance good-quality class of LREBa₂Cu₃O_y material can be made by using a novel thin film Nd-123 seeds.     

The absorption spectrum of methane at 80 and 294 K in the icosad (6717–7589 cm−1): Improved empirical line lists,isotopologue identification and temperature dependence

Using a cryogenic cell and a series of Distributed Feed Back (DFB) diode lasers, new high resolution spectra of methane have been recorded at 80 K and room temperature by differential absorption spectroscopy (DAS) between 6717 and 7589 cm^?1 (1.49–1.32 μm). The investigated spectral region corresponds to the very congested icosad, which is not tractable by theory. Empirical lists of 19,940 and 24,001 lines were constructed from the 80 K and room temperature spectrum, respectively. The room temperature list adds about 8500 features to the empirical list of 15,375 lines at 296 K adopted in the HITRAN database from the original work of L. Brown (Brown, L. Empirical line parameters of methane from 1.1 to 2.1 μm. JQSRT 2005;96:251–70). A number of relatively strong CH₄ lines located near strong water lines were found missing in the HITRAN line list. The improved sensitivity allowed adding more than 7000 lines to our previous list of about 12,000 transitions at 80 K (Campargue A, Wang L, Kassi S, Ma?át M, Votava O. Temperature dependence of the absorption spectrum of CH₄ by high resolution spectroscopy at 81 K: (II) The Icosad region (1.49–1.30 μm). JQSRT 2010;111:1141–51). In order to facilitate identification of the transitions of the different methane isotopologues present in “natural” isotopic abundance, spectra of highly enriched CH₃D and ¹³CH₄ samples were recorded with the same experimental setup, both at room temperature and at 80 K.From the variation of the line strengths between 80 K and 294 K, the low energy values of about 12,000 transitions were determined. They allow accounting for the temperature dependence of 84 and 93% of the methane absorbance in the region, at room temperature and 80 K, respectively. As a result, we provide as supplementary material two complete line lists at 80 K and 294 K, including CH₃D and ¹³CH₄ identification and lower state energy values.