Effect of XeCl laser irradiation on the defect structure of Nd:YAG crystals

This paper presents the effect of XeCl laser irradiation on Nd:YAG single crystal samples with various number of pulses at different repetition rates and laser fluences. Effects of the irradiation on the optical and structural properties of the crystal are analyzed by UV–vis-NIR spectroscopy. Annihilation of some point defects of the crystal structure is observed following laser irradiation at a fluence of 100 mJ cm⁻² with 100 and 500 pulses. Increasing the laser fluence and pulse numbers leads to saturation and new defects are found to be formed in the crystal. Additional absorption spectra of the irradiated samples show that oxygen vacancies in the Nd:YAG crystals are removed during the low-dose irradiation. The laser irradiation is compared to the thermal annealing process for Nd:YAG crystal modification. Additional absorption spectrum of an annealed sample reveals that induced negative absorption band at 236 nm is correlated with the annihilation of the oxygen vacancy center. Our results also demonstrate that XeCl laser treatment has several advantages upon annealing at high temperatures in the Nd:YAG crystal quality improvement. Thus, the present work can give a new approach to modify Nd:YAG crystals to be used in a wide variety of solid-state laser engineering.     

Quantification of local oxygen defects around Yttrium ions for yttria-doped ceria–zirconia ternary system

Local coordination structure around Yttrium ions in CeO₂–Y₂O₃ binary and [(CeO₂)_x(ZrO₂)_1?x]_0.8(YO_1.5)_0.2 (x = 0.0 ~ 1.0) ternary system has been investigated by ⁸⁹Y MAS-NMR. NMR spectra are found to be consisted of multiple peaks that can be assigned to 6-, 7- and 8-oxygen coordinated Yttrium ions. Compositional dependence of the spectrum was observed and compared with the previous results for ZrO₂–Y₂O₃ binary system. The present investigation suggested the degree of localization of the oxygen vacancy around the cation is in the order of Zr⁴⁺ > Y³⁺ > Ce⁴⁺. The degree of the oxygen vacancy preference for each cation was quantitatively determined for CeO₂–ZrO₂–Y₂O₃ ternary system the first time.     

Infrared transmission of chalcohalide glasses in the Ge–Se–Te–I system

Infrared (IR) transmission spectra in the range from 4000 to 400 cm^?1 have been measured at ambient temperature for the prepared, (Ge₂₂Se₁₄Te₆₄)_100?xI_x, glasses where x = 0, 4, 6, 8 and 10 at.%. The effects of both iodine content and the annealing of glasses at different temperatures on the transmittance and observed absorption peaks have been evaluated. Scanning electron microscope (SEM) micrographs were performed to insure the effect of annealing on the obtained IR transmission spectra.     

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.     

Modifications of structural,optical and electrical properties of nanocrystalline bismuth sulphide by using swift heavy ions

Modified chemical bath deposited (MCBD) bismuth sulphide (Bi₂S₃) thin films’ structural, optical and electrical properties are engineered separately by annealing in air for 1 h at 300 °C and irradiating with 100 MeV Au swift heavy ions (SHI) at 5 × 10¹² ions/cm² fluence. It is observed that the band gap of the films gets red shifted after annealing and irradiation from pristine (as deposited) films. In addition, there is an increase in the grain size of the films due to both annealing and irradiation, leading to the decrease in resistivity and increase in thermoemf of the films. These results were explained in the light of thermal spike model.     

Synthesis and photoluminescence properties of YVO4:Eu3+, Al3+ phosphor

The Y_0.95?xAl_xVO₄:5%Eu³⁺ (0≤x≤0.1) phosphors were successfully synthesized by solid state reaction at 900 °C for 6 h, and their luminescence properties were investigated under UV and VUV excitation. Monitoring at 619 nm, a strong broad absorption was enhanced by co-doping of Al³⁺ into the YVO₄:Eu³⁺ lattices at 256 nm under UV excitation. The VUV excitation spectra also showed the enhanced excitation bands at about 156 and 200 nm. Under 254 or 147 nm excitation, it was found that Y_0.95?xAl_xVO₄:Eu³⁺(0≤x≤0.1) phosphors showed strong red emission at about 619 nm corresponding to the electric dipole ⁵D₀^–7F₂ transition of Eu³⁺. The improvement of luminescence intensity of YVO₄:Eu³⁺ was also observed after partial substituting Y³⁺ by Al³⁺ and the optimal luminescence intensity appeared with incorporation of 2.5 mol% Al³⁺.     

Synthesis,characterisation, luminescence and defect centres in solution combustion synthesised CaZrO3:Tb3+ phosphor

Tb³⁺ doped CaZrO₃ has been prepared by an easy solution combustion synthesis method. The combustion derived powder was investigated by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy techniques. A room temperature photoluminescence study showed that the phosphors can be efficiently excited by 251 nm light with a weak emission in the blue and orange region and a strong emission in green light region. CaZrO₃:Tb³⁺ exhibits three thermoluminescence (TL) glow peaks at 126 °C, 200 °C and 480 °C. Electron Spin Resonance (ESR) studies were carried out to study the defect centres induced in the phosphor by gamma irradiation and also to identify the centres responsible for the TL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0233 is identified as an O^? ion. Centre II with an axial symmetric g-tensor with principal values g_=1.9986 and g_?=2.0023 is assigned to an F⁺ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F⁺ centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F centre and also the F⁺ centre appear to correlate with the observed high temperature TL peak in CaZrO₃:Tb³⁺ phosphor.     

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.     

Enhancement of blue holographic properties in Zr4+-doped near stoichiometric Fe:LiNbO3 crystals

The near stoichiometric LiNbO₃ crystals co-doped with ZrO₂ and Fe₂O₃ have been grown from a Li-rich melt (Li/Nb=1.38, atomic ratio) by the Czochralski method in air atmosphere at the first time. The OH^? absorption and UV–vis absorption spectra were characterized to investigate the defect structure of the crystals. The appearances of the 3479 cm^?1 absorption peak and 358 nm absorption edge manifest that the composition of the grown crystal is close to the stoichiometric ratio. The blue holographic properties were also measured by the two-wave coupling experiments. As a result, in the near stoichiometric Zr:Fe:LiNbO₃ crystals, photorefractive response speed, recording sensitivity, and two-wave coupling gain coefficient are significantly enhanced. Meanwhile, the high saturation diffraction efficiency is still maintained. These findings prove that the material of near stoichiometric Zr:Fe:LiNbO₃ crystals are a promising candidate for blue photorefractive holographic recording.     

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.     

EPR and UV spectroscopic investigations of sucrose irradiated with heavy-ion particles

Crystalline sucrose irradiated with C and Si ions is investigated with EPR and UV spectroscopy. Samples are treated at different doses of radiation in the region 20–300 Gy and linear energy transfer (LET) values of 39.6, 49 and 58 keV μm^?1 for C ions and 60 keV μm^?1 for Si ions. All samples exhibit identical EPR spectra due to radiation-induced stable sucrose radicals. At given constant LET the EPR signal responses are linear to the absorbed doses of Si and C ions. Water solutions of irradiated sucrose exhibit UV absorption maximum at 267 nm due to the product of radical recombination. The intensity of this band is stronger at irradiation with Si than with C ions. UV absorption is more sensitive to heavy-ion species irradiation than the EPR signals.     

Spectroscopic properties of Tm3+/Ho3+ co-doped NaLa(WO4)2 single crystal

Tm³⁺/Ho³⁺ co-doped NaLa(WO₄)₂ single crystal was successfully grown by the Czochralski method. The crystal was characterized by room temperature absorption spectra, fluorescence spectra around 2 μm, up-conversion fluorescence and luminescence decay measurements. Spectroscopic properties related to the laser operation around 2 μm of Ho³⁺ ions have been evaluated. The energy level scheme and energy transfer processes of Tm³⁺ and Ho³⁺ were analyzed. The obtained spectroscopic results show the crystal is a potentially host for Ho³⁺ 2 μm infrared laser.     

Scintillation properties of Cs2LiGdCl6: Ce3+

In this communication, we investigated the scintillation properties of Cs₂LiGdCl₆:10% Ce³⁺ single crystal. This scintillation crystal is grown by using the vertical Bridgman technique. X-rays induced emission spectra show that, Cs₂LiGdCl₆:10% Ce³⁺ emits into the Ce³⁺ band, spanning from 365 nm to 450 nm wavelengths. Under γ-ray excitation, the sample crystal shows three main decay time components of 129 ns (51%), 573 ns (32%) and 8.9 μs (17%). It offers an energy resolution of 5.0% (FWHM) for the 662 keV full absorption peak at room temperature. We measured an absolute light yield of 20,000 photons/MeV of absorbed γ-ray energy. We found that with a little exposure to the air, the scintillation properties of the Cs₂LiGdCl₆:10% Ce³⁺ crystal deteriorate, which is attributed to the highly hygroscopic nature of this material. We believe that the Cs₂LiGdCl₆:10% Ce³⁺ crystal can be a promising material for medical imaging and radiation detection. Moreover due to the presence of Li and Gd constituents, this scintillation crystal can also be the possible candidate for thermal neutron detection.     

The spectroscopic properties of Yb3+ doped α-BBO crystal

2.0 mol% (relative to Ba²⁺) Yb³⁺ doped α-BaB₂O₄ (α-BBO) crystal was obtained by the Czochralski method. The doped crystal structure was determined by means of an X-ray diffraction analysis. The absorption, near-infrared (NIR) luminescence spectra and fluorescence decay curve of Yb³⁺ doped α-BBO crystal were investigated. NIR emission under 940 nm and 980 nm LDs (laser diodes) excitation was observed in the Yb doped α-BBO crystal.     

Synthesis,crystal structure,spectroscopic characterization and optical properties of bis(4-acetylanilinium) tetrachlorocobalt (II)

The chemical preparation, crystal structure, spectroscopic investigations and optical features are given for a novel organic–inorganic hybrid material [C₈H₁₀NO]₂CoCl₄.The compound is crystallized in the orthorhombic space group Cmca, with the following unit cell parameters: a=19.461(2) Å, b=15.523(2) Å, c=13.7436(15) Å, and Z=8. The atomic arrangement shows an alternation of organic and inorganic layers along the b-axis. The cohesion between these entities is performed by N–H…Cl and N–H…O hydrogen bonds and π–π stacking interactions.Infrared and Raman spectra at room temperature are recorded in the 4000−400 and 4000−0 cm⁻¹ frequency regions, respectively and analyzed on the basis of literature data. This study confirms the presence of the organic cation [C₈H₁₀NO]⁺ and of the [CoCl₄]²⁻ anion. UV–vis spectroscopy results showed the indirect transition with band gap energy 2.98 eV.     

Growth and characterization of Nd:Bi12SiO20 single crystal

A Nd:Bi₁₂SiO₂₀ crystal was grown by the Czochralski method. The thermal properties of the crystal were systematically studied. The thermal expansion coefficient was measured to be α=11.42×10^?6 K^?1 over the temperature range of 295–775 K, and the specific heat and thermal diffusion coefficient were measured to be 0.243 Jg^?1 k^?1 and 0.584 mm²/s, respectively at 302 K. The density was measured to be 9.361 g/cm³ by the buoyancy method. The thermal conductivity of Nd:Bi₁₂SiO₂₀ was calculated to be 1.328 Wm^?1 K^?1 at room temperature (302 K). The refractive index of Nd:Bi₁₂SiO₂₀ was measured at room temperature at eight different wavelengths. The absorption and emission spectra were also measured at room temperature. Continuous-wave (CW) laser output of a Nd:Bi₁₂SiO₂₀ crystal pumped by a laser diode (LD) at 1071.5 nm was achieved with an output power of 65 mW. To our knowledge, this is the first time LD pumped laser output in this crystal has been obtained. These results show that Nd:Bi₁₂SiO₂₀ can serve as a laser crystal.     

Electronic transport in the novel SOFC anode material La1−xSrxCr0.5Mn0.5O3±δ

Electronic conductivity in the potential SOFC anode material La_1−xSr_xCr_0.5Mn_0.5O_3±δ has been investigated in the range 0.2 < x < 0.3. log(σT) vs. 1/T plots indicate conduction via thermally activated polaron hopping. At 900 °C, conductivity in air increases with Sr²⁺ via an increase in [B_B] holes (B—transition metal). X-ray absorption spectroscopy (XAS) studies indicate that compensation for A-site Sr substitution and oxygen vacancy formation is via the Mn cation only; Cr maintains a 3+ oxidation state and 6-fold oxygen coordination. Electronic transport occurs by percolation between Mn cations in a disordered B-site sub-lattice. Conductivity decreases with p(O₂), which is indicative of p-type conduction behaviour, but the relationship cannot be explained by a simple redox equilibrium involving Mn³⁺, Mn⁴⁺ and oxygen, possibly due to co-existence of Mn²⁺, Mn³⁺ and Mn⁴⁺ via disproportionation as with La_1−xSr_xMnO_3±δ.     

Electrical and structural investigations of perovskite structure reactively sputter deposited coatings

Sr(Zr_0.84Y_0.16)_0.91O_3 ? δ (SZY) and Ba(Zr_0.84Y_0.16)_0.96O_3 ? δ (BZY) protonic conductor coatings were co-sputter deposited from metallic targets in argon–oxygen reactive gas mixtures. The chemical and structural features were investigated by energy dispersive X-ray spectroscopy and X-ray diffraction, and their morphology was assessed by scanning electron microscopy of the surface and of brittle fracture cross sections. The electrical properties of the coating were determined by complex impedance spectroscopy as a function of temperature in air. Relationships are established between the electrical properties and the morphology of the coatings. The SZY as deposited coatings is amorphous and crystallises under the convenient perovskite structure after annealing treatment at 873 K under air. The BZY as deposited coatings is crystallised at 523 K in situ under perovskite structure and a further annealing treatment increases the grain size. Conductivities and activation energies of crystallised coatings were 3.1 · 10^? 5 S cm^? 1/2 · 10^? 5 S cm^? 1 and 0.65 eV/0.71 eV after stabilization at 773 K for strontium and barium zirconate, respectively.     

Crystal structure and photoluminescence correlations in white emitting nanocrystalline ZrO2:Eu3+ phosphor: Effect of doping and annealing

White emitting nanocrystalline ZrO₂:Eu³⁺ phosphors were synthesized by a simple precipitation route without using a capping agent. X-ray diffraction (XRD) study of ZrO₂ and ZrO₂:Eu³⁺samples revealed the presence of monoclinic and tetragonal phases. The monoclinic phase increases with increase in the annealing temperature while the tetragonal phase increases with increase in the concentration of Eu³⁺. This can be attributed to the presence of oxygen vacancy evolved when Zr⁴⁺ is replaced by Eu³⁺. Photoluminescence (PL) emission peaks of Eu³⁺ are observed at 591, 596, 606 and 613 nm on monitoring excitation wavelengths at 250, 286, 394 and 470 nm. The peaks at 591 and 606 nm were found to correlate with the tetragonal phase and those at 596 and 613 nm with the monoclinic phase. Intensities of these peaks are found to change as the crystal structure changes. The lifetime value corresponding to 591 nm peak increases with Eu³⁺ concentration at a particular heating temperature indicating increase of tetragonal phase with respect to monoclinic phase. The CIE co-ordinates of the doped samples were found to be close to that of white color (0.33, 0.33). The changes in the crystal structure of the doped samples due to doping and annealing did not affect the white color emission.     

Photo-induced isomerization of poly 4′-(6-acryloxy) hexyloxy-4-methoxyazobenzene ultra-thin solid film prepared by Langmuir–Blodgett technique

The photo-induced response of an ultra thin polymeric film of poly 4′-(6-acryloxy) hexyloxy-4-methoxyazobenzene (P5) is investigated. A monolayer of P5 at a gas–water interface possesses a mean molecular area of 28.0 Å²/monomer-repeat. Multilayer films of P5 were prepared by horizontal deposition at a surface pressure of 25 mN/m². The uniformity of the transfer process is shown by UV–vis absorption spectra where a linear relationship between the absorption maxima and the number of transferred layer was observed. The average layer thickness of the transferred film determined by XRD measurements is 34.0 Å. This is longer than the length of the azobenzene side group. The transferred film shows a blue shift of the π–π¹ transition from 357 nm for the P5 in solution to 340 nm for the P5 in the film. This suggests the formation of H-aggregate with a head-to-head arrangement of the dipole within the film. The optical property of the transferred film is changed by the irradiation of the film with the UV light at 385 nm. An irreversible change in its molecular packing in the film is seen in the shift of the UV–vis absorption maxima and the change in morphology as observed by AFM. The film morphology changes from being a smooth film into an island-like surface when exposed to the UV irradiation. The layer structure in the film is destroyed. A mass transport is observed during the cis–trans thermal back isomerization process. This suggests that movement of the P5 took place in both the trans–cis isomerization process and the cis–trans back isomerization process. The first movement leads to a molecular expansion while the second, to a molecular contraction.