Thermoluminescence studies on Cu-doped Li2B4O7 single crystals

Lithium tetraborate (Li₂B₄O₇) is a tissue equivalent material and single crystals of this material doped with Cu are promising for dosimetric applications. In the present study highly transparent single crystals of lithium tetraborate (Li₂B₄O₇) doped with Cu (0.5 wt%) have been grown using the Czochralski technique. The Li₂B₄O₇:Cu crystals were studied using photoluminescence, X-ray diffraction (XRD), UV-vis transmission, time resolved fluorescence and thermoluminescence (TL) techniques. The TL readout of Li₂B₄O₇:Cu crystals showed two well-defined glow peaks at 402 K (peak-1) and 513 K (peak-2) for a 4 K/s heating rate. While the low temperature TL peak-1 fades completely within 24 h at room temperatures, the main dosimetric peak-2 remains the same. The TL sensitivity of the grown single crystal is found to be 3.3 times that of a conventional TL phosphor, TLD-100. The Li₂B₄O₇:Cu crystals showed a linear TL dose-response in the range from 1 mGy to 1 kGy. The TL analysis using a variable dose method revealed first order kinetics for both the peaks. Trap depth and frequency factor for peak-1 were found to be 0.81 eV and 5.2×10⁹ s⁻¹, whereas for peak-2 the values were 1.7 eV and 1.7×10¹⁶ s⁻¹, respectively.     

Thermoluminescent properties of a Li2O-B2O3-Al2O3 glass system doped with CaF2 and Mn

A Li₂O-B₂O₃-Al₂O₃ glass system doped with CaF₂ and Mn was synthesized by fusion and its physical properties were investigated using thermoluminescence (TL) and differential thermal analysis (DTA) techniques. The TL glow curve peaks, resulting from this analysis, are characteristic of metastable levels intrinsic to CaF₂ crystals that have undergone γ-ray irradiation from a colbalt-60 (⁶⁰Co) source. This provides evidence of CaF₂ crystal formation in the glass system. Furthermore, the TL glow peak at about 480 K was stable at room temperature, sensitive to ⁶⁰Co γ-rays and showed good linearity with doses ranging from 3 Gy to approximately 100 Gy, and consequently could be used to quantify radiation doses. High quality synthesis of these crystals permits control of their thermoluminescent properties.     

Growth and spectral characterization of β-Ga2O3 single crystals

Beta gallium oxide (β-Ga₂O₃) single crystals were grown by the floating zone technique. The absorption spectra and the luminescence of the crystals were measured. The absorption spectra showed an intrinsic short cutoff edge around 260 nm with two shoulders at 270 and 300 nm. Not only the characteristic UV (395 nm), blue (471 nm) and green (559 nm) lights, but also the red (692 nm) light can be seen in the emission spectra. The deep UV light was attributed to the existing of quantum wells above the valence band and the red light was owed to the electron-hole recombination via the vicinity donors and acceptors.     

Optical studies in gamma irradiated Mg doped CaF2 single crystals

Pure and Mg doped CaF₂ single crystals grown by the Bridgman method were irradiated with gamma rays (γ-rays) for doses ranging from 97 Gy to 9.72 KGy. The pristine samples showed minimal absorption indicating the purity of the samples. The γ-irradiated pure CaF₂ crystals showed prominent and strong absorption with a peak at ~ 374 nm besides three weak ones at ~ 456, 523 and 623 nm. However γ-rayed Mg doped crystals showed a prominent absorption with a strong peak at ~ 370 nm and a broad one at ~ 530 nm. The absorption indicated the generation of F and F-aggregate centers in the irradiated crystals. The photoluminescence (PL) emission spectrum of both pure and Mg doped crystals showed prominent emission at ~ 390 nm when they were excited at ~ 250 nm. Also, when the samples were excited at 323 and 363 nm strong emissions were observed at ~ 430 and 422 nm respectively. The optical absorption and PL intensities were found to increase with increase in dose.     

Crystallization of 21.25Gd2O3-63.75MoO3-15B2O3 glass induced by femtosecond laser at the repetition rate of 250 kHz

We report the formation of β′-Gd₂(MoO₄)₃ (GMO) crystal on the surface of the 21.25Gd₂O₃-63.75MoO₃-15B₂O₃ glass, induced by 250 kHz, 800 nm femtosecond laser irradiation. The morphology of the modified region in the glass was clearly examined by scanning electron microscopy (SEM). By micro-Raman spectra, the laser-induced crystals were confirmed to be GMO phases and it is found that these crystals have a strong dependence on the number and power of the femtosecond laser pulses. When the irradiation laser power was 900 mW, not only the Raman peaks of GMO crystals but also some new peaks at 214 cm⁻¹, 240 cm⁻¹, 466 cm⁻¹, 664 cm⁻¹ and 994 cm⁻¹which belong to the MoO₃ crystals were observed. The possible mechanisms are proposed to explain these phenomena.     

Near-infrared luminescence of OH and Cl doped Bi4Ge3O12 crystals

OH⁻ and Cl⁻ doped Bi₄Ge₃O₁₂ (BGO) single crystals had been grown by Vertical Bridgman (VB) method. The structure of these crystals was determined by XRD, the transmittance and emission spectra in near infrared region (NIR) were measured at room temperature. 5% OH⁻ doped BGO shows a significant emission band peaking around 1181 nm under 808 nm laser diodes (LDs) excitation, and the 5% Cl⁻ doped BGO exhibits a relatively weak emission band as well. 100% and 5% OH⁻ doped BGO show noticeable emission band centered at about 1346 nm under 980 nm LDs excitation.     

Spectroscopic properties of OH doped and Bi-rich Bi4Ge3O12 crystals by vertical Bridgman method

OH⁻ doped and Bi-rich Bi₄Ge₃O₁₂ (BGO) single crystals were grown by Vertical Bridgman (VB) method. The structure of these crystals was determined by XRD, and the emission spectra in visible and near infrared region (NIR) were measured at room temperature. The emission spectrum of Bi-rich BGO has extra peaks at 385, 367 and 357 nm, Bi-rich BGO after annealing in Ar at 500 °C for 5 h shows a significant emission band peaking around 1170 nm under 808 nm laser diodes (LDs) excitation, and OH⁻ doped BGO shows a noticeable emission band centered at about 1346 nm under 980 nm LDs excitation. A brief discussion is presented.     

Growth, thermal and spectroscopic characterizations of BaNd2(MoO4)4 crystal

A new crystal, BaNd₂(MoO₄)₄, has been grown from the flux melt based on Li₂Mo₃O₁₀ by a spontaneous nucleation method. The phase structure of the obtained crystals was determined by X-ray powder diffraction. The result shows that the as-grown crystals are well crystallized and indexed in a monoclinic crystal system with space group B2/b. The specific heat of BaNd₂(MoO₄)₄ crystal at 20 °C is 0.485 J/g K. Absorption and fluorescence spectra were also measured at room temperature. There are several strong and broad absorption peaks from 200 to 1200 nm and three emission transition bands located at 890, 1060, and 1334 nm are detected.     

Spectral properties of Nd-doped Sr3Ga2Ge4O14 crystal

Neodymium doped strontium gallogermanate crystals were grown successfully by the Bridgman technique. The linear thermal expansion coefficients for the c- and a-axes were measured as 5.8 × 10⁻⁶ °C⁻¹ and 6.5 × 10⁻⁶ °C⁻¹. Absorption spectra, and fluorescence spectra, as well as fluorescence decay curves of Nd³⁺-doped Sr₃Ga₂Ge₄O₁₄ crystal, have been recorded at room temperature and used to calculate the absorption and stimulated emission cross-sections. Based on the Judd-Ofelt theory, three intensity parameters were obtained. The luminescent quantum efficiency of the ⁴F_3/2 level was determined to be approximately 73.8% for this material. Compared with other Nd³⁺-doped laser crystals, Nd³⁺-doped Sr₃Ga₂Ge₄O₁₄ crystal displays special laser properties due to its disorder structure.     

Effects of forming gas annealing on LiNbO3 single crystals

Z-cut congruent LiNbO₃ single crystals were annealed in 95%N₂+5%H₂ at high temperatures. X-ray diffraction showed that 2θ of (0 0 0 6) peak is obviously reduced by 0.6° and 1.0° for the samples annealed at 600 and 900 °C, respectively. A new peak appears at the high-energy side of O 1s spectrum in X-ray photoelelectron spectroscopy (XPS) analyses, and the leakage current is greatly increased. It is proposed that hydrogen is incorporated in LiNbO₃ single crystals through forming gas annealing at temperatures up to 900 °C and exists in LiNbO₃ as a proton bound to an oxygen ion through O-H bond with its electron donated.     

Electrical and electrochemical properties of glass-ceramic electrolytes in the systems Li2S-P2S5-P2S3 and Li2S-P2S5-P2O5

Electrical and electrochemical properties of the 70Li₂S·(30 − x)P₂S₅·xP₂S₃ and the 70Li₂S·(30 − x)P₂S₅·xP₂O₅ (mol%) glass-ceramics prepared by the mechanical milling technique were investigated. Glass-ceramics with 1 mol% P₂S₃ and 3 mol% P₂O₅ showed the highest conductivity of 5.4 × 10^− 3 S cm^− 1 and 4.6 × 10^− 3 S cm^− 1, respectively. Moreover, these glass-ceramics showed higher electrochemical stability than the 70Li₂S·30P₂S₅ (mol%) glass-ceramic. From the XRD patterns of the obtained glass-ceramics, trivalent phosphorus and oxygen were incorporated into the Li₇P₃S₁₁ crystal. We therefore presume that the Li₇P₃S₁₁ analogous crystals, which were formed by incorporating trivalent phosphorus and oxygen into the Li₇P₃S₁₁ crystal, improve the electrical and electrochemical properties of the glass-ceramics. An all-solid-state cell using the 70Li₂S·29P₂S₅·1P₂S₃ (mol%) glass-ceramic as solid electrolyte operated under the high current density of 12.7 mA cm^− 2 at the high temperature of 100 °C. The cell showed an excellent cyclability of over 700 cycles without capacity loss.     

Growth and characterization of Nd:Lu3ScxGa5 − xO12 series laser crystals

A new series Nd:Lu₃Sc_xGa_5 − xO₁₂ (x = 0.5, 0.8, 1, 1.2 and 1.5) laser crystals have been successfully grown by the optical floating zone method. Their absorption and luminescence spectra were measured at room temperature and spectral parameters were systemically calculated using Judd-Ofelt (JO) theory. The fluorescence τ_f lifetimes were experimentally measured and compared with the theoretical results. Diode-pumped continuous-wave (CW) laser performance at 1.06 μm with mixed crystals was demonstrated. The influence of different x values on laser performance and spectral parameters was also discussed. All the results show that Nd:Lu₃Sc_xGa_5 − xO₁₂ series crystals should be suitable for laser application.     

Blue luminescence in Tm-doped KGd(WO4)2 single crystals

Up-conversion blue emissions of trivalent thulium ions in monoclinic KGd(WO₄)₂ single crystals at 454 and 479 nm are reported for a single pump laser source at 688 nm. We grew thulium-doped KGd(WO₄)₂ single crystals at several concentrations from 0.1% to 10%. We recorded a polarized optical absorption spectrum for the ³F₂+³F₃ energy levels of thulium at room temperature and low temperature (6 K). From the low temperature emission spectra we determined the splitting of the ³H₆ ground state. The blue emissions are characterized as a function of the dopant concentration and temperature from 10 K to room temperature. To our knowledge, this is the first time that sequential two-photon excitation process (STEP) generated blue emissions in thulium-doped single crystals with a single excitation wavelength.     

AgGaS2- and Al-doped GaSe Crystals for IR Applications

We report a systematic study of AgGaS₂- and Al-doped GaSe crystals in comparison with pure GaSe and S-doped GaSe crystals. AgGaS₂-doped GaSe (GaSe:AgGaS₂) crystal was grown by Bridgman technique from the melt of GaSe:AgGaS₂ (10.6 wt.%). Its real composition was identified as GaSe:S (2 wt.%). Al-doped GaSe (GaSe:Al) crystals were grown from the melt of GaSe and 0.01, 0.05, 0.1, 0.5, 1, 2 mass % of aluminium. Al content in the grown crystals is too small to be measured. The hardness of GaSe:S (2 wt.%) crystal grown from the melt of GaSe:AgGaS₂ is 25% higher than that of GaSe:S (2 wt.%) crystal grown by a conventional S-doping technique and 1.5- to 1.9-times higher than that of pure GaSe. GaSe:Al crystals are characterized by 2.5- to 3-times higher hardness than that of pure GaSe and by extremely low conductivity of ≤ 10^− 7 Om^− 1 cm^− 1. A comparative experiment on SHG in AgGaS₂-, Al-, S-doped GaSe and pure GaSe is carried out under the pumps of 2.12-2.9 μm fs OPA and 9.2−10.8 μm ns CO₂ laser. It was found that GaSe:S crystals possess the best physical properties for mid-IR applications among these doped GaSe crystals. GaSe:Al crystals have relatively low conductivity which have strong potential for THz application.     

X-ray diffraction, vibrational and photoluminescence studies of the self-organized quantum well crystal H3N(CH2)6NH3PbBr4

We have prepared new semiconductor H₃N(CH₂)₆NH₃PbBr₄ crystals which are self-assembled organic-inorganic hybrid materials. The grown crystals have been studied by X-ray diffraction, infrared absorption and Raman spectroscopy scattering. We found that the title compound, abbreviated 2C₆PbBr₄, crystallizes in a two-dimensional (2D) structure with a P2₁/a space group. In the inorganic semiconductor sub-lattice, the corner sharing PbBr₆ octahedra form infinite 2D chains. The organic C₆H₁₈N₂⁺ ions form the insulator barriers between the inorganic semiconductor layers. Such a packing leads to a self-assembled multiple quantum well structure. Raman and infrared spectra of the title compound were recorded in the 50-500 and 400-4000 cm⁻¹ frequency regions, respectively. The assignment of the observed Raman lines was performed by comparison with the homologous compounds. Transmission measurements on thin films of 2C₆PbBr₄, obtained by the spin coating method, revealed a strong absorption peak at 380 nm. Luminescence measurements showed an emission line at 402 nm associated with radiative recombinations of excitons confined within the PbBr₆ layers. The electron-hole binding energy is estimated at 180 meV.     

Z-Scan studies of KYW, KYbW, KGW, and Ba(NO3)2 crystals

We present the studies of nonlinear refraction and nonlinear absorption in promising crystals which are extensively used in Raman lasers or as solid-state laser host materials: Ba(NO₃)₂, KGW, KYW, and KYbW. The single-beam z-scan technique with 1 ps laser pulses at 790 and 395 nm has been applied for the study. Nonlinear refraction-index intensity-coefficients and two-photon absorption coefficients have been determined for the crystals. The considerable enhancement of nonlinear refraction is observed in the crystals at 395 nm.     

Trapping center parameters in In6S7 crystals

Thermally stimulated current measurements were carried out on In₆S₇ single crystals in the temperature range of 10-225 K with a constant heating rate of 0.8 K/s. The study of trapping centers was accomplished by the measurements of current flowing along the c-axis of crystals. The analysis of the glow curve according to various methods, such as curve fitting, initial rise and peak shape methods, gives results in good agreement with each other and revealed two trapping centers in In₆S₇ with activation energies of 157 and 290 meV. Their capture cross sections have been determined as 7.5×10⁻²³ and 7.1×10⁻²⁰ cm²,respectively. The good agreement between the experimental results and the theoretical predictions of the model that assumes slow retrapping has confirmed that retrapping is negligible in these centers.     

Atomic force microscopy study on surface morphology of {0 0 1} faces of [MnHg(SCN)4(H2O)2]·2C4H9NO crystals

The growth morphologies of the {0 0 1} faces of [MnHg(SCN)₄(H₂O)₂]·2C₄H₉NO (MMTWD) crystals grown at 17 °C at a supersaturation of σ = 0.5 have been investigated by ex situ atomic force microscopy (AFM).Various spiral growth hillocks are described and discussed. Surface morphology changes as a result of dissolving the surface materials by absorbed moisture in air are also detected. The microcrystals are suggested to be as a result of the reconstruction of amorphous aggregates on the surfaces.     

Orbital fluctuations and orbital order in FeCr2S4

Heat-capacity investigations on the ferrimagnetic spinel FeCr₂S₄ poly- and single crystals provide experimental evidence of orbital liquid and orbital glass states. The low-temperature transition in the polycrystals at 10 K arises from orbital order and is very sensitive to the sample stoichiometry. In the single crystals the orbital order is fully suppressed resulting in an orbital glass state with the heat capacity following a strict T² dependence towards zero temperature. At elevated temperatures, FeCr₂S₄ exhibits an unexpected large linear term of about 100 mJ mol⁻¹ K⁻² as the fingerprint of the orbital liquid.     

Origin of green luminescence in PbWO4 crystals

Characteristics of two green emission bands, G(I) and G(II), and their origin were investigated within 0.4-300 K under photoexcitation in the 3.4-6.0 eV energy range for undoped and Mo⁶⁺-, Mo⁶⁺ , Y³⁺-, Mo⁶⁺, Nb⁵⁺-, Mo⁶⁺, Ce³⁺-, Cr⁶⁺-, La³⁺-, Ba²⁺- and Cd²⁺-doped PbWO₄ crystals with different concentrations of impurity and intrinsic defects, grown by different methods and annealed at different conditions. The G(I) emission band, observed at low temperatures, located around 2.3-2.4 eV and excited around 3.9 eV, is usually a superposition of many closely positioned bands. The G(I) emission of undoped crystals is assumed to arise from the WO₄²⁻ groups located in the crystal regions of lead-deficient structure. In Mo⁶⁺-doped crystals, this emission arises mainly from the MoO₄²⁻ groups themselves. The G(II) emission band located at 2.5 eV is observed only in the crystals, containing the isolated oxygen vacancies — WO₃ groups. This emission appears at T>160 K under excitation around 4.07 eV as a result of the photo-thermally stimulated disintegration of localized exciton states and subsequent recombination of the produced electron and hole centres near WO₃ groups. The G(II) emission accompanies also thermally stimulated recombination processes in PbWO₄ crystals above 150 K. Mainly the G(II) emission is responsible for the slow decay of the green luminescence in PbWO₄ crystals.