Growth and EPR properties of KSm(WO4)2 and KEr(WO4)2 single crystals

Growth conditions and electron paramagnetic resonance investigations of two well oriented KSm(WO₄)₂ and KEr(WO₄)₂ single crystals have been presented and discussed. Hyperfine structure of Sm³⁺ ion was detected and analyzed for angular and temperature dependences. EPR spectra of KEr(WO₄)₂ and its angular dependence showed the presence of 5 magnetically nonequivalent Er centers in the crystal. A change in the type of magnetic interactions was analyzed using mixed (Gaussian and Lorentzian) fits of the EPR spectra.     

Elastic and photo-elastic characteristics of laser crystals potassium rare-earth tungstates KRE(WO4)2, where RE = Y,Yb, Gd and Lu

The elastic and photo-elastic characteristics of four laser crystals KY(WO₄)₂, KGd(WO₄)₂, KYb(WO₄)₂, and KLu(WO₄)₂ are presented. The first pair was reported early, and the last two materials have been investigated for the first time. The full matrix of elastic constants of these monoclinic crystals has been determined. Also, acousto-optical figure of merit for all the basic geometries of isotropic diffraction has been measured. It is proved that potassium rare-earth tungstates has rather good acousto-optical properties and particularly can take place of fused silica in technical applications required high power laser radiation. All the results demonstrate good prospect of these optically bi-axial laser crystals for development of new effective acousto-optical devices.     

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.     

Spectroscopic properties of Yb ions in La2(WO4)3 crystal

Yb³⁺-doped La₂(WO₄)₃ single crystals were grown by the Czochralski technique. Absorption and fluorescence spectra of the crystal were recorded at the room temperature. The stimulated emission cross-sections of Yb³⁺ ions were calculated using the reciprocity method and Fuchtbauer-Ladenburg formula, respectively. The fluorescence decay curves of ²F_5/2 manifold of Yb³⁺ ions were recorded at room temperature for both crystal and powder samples. The effect of radiation trapping on the spectroscopic properties is discussed. Comparison with other Yb³⁺-doped laser crystals is made. The results show that Yb³⁺:La₂(WO₄)₃ crystal is a promising laser material.     

Yb-and Er-Doped single crystals of double tungstates NaGd(WO4)2, NaLa(WO4)2, and NaBi(WO4)2 as active media for lasers operating in the 1.0 and 1.5 μm ranges

Ytterbium-and erbium-doped single crystals of scheelite-like double tungstates NaGd(WO₄)₂, NaLa(WO₄)₂, and NaBi(WO₄)₂ and scheelite CaWO₄ have been grown by the Czochralski method. The dopant concentrations in crystals are measured, and the coefficients of dopant distribution are determined to range from 0.45 to 3. The lifetimes of the Er³⁺ states ⁴ I _11/2 and ⁴ I _13/2 and the Yb³⁺ state ²F_5/2 are measured, and the absorption and luminescence spectra of the crystals are studied in the vicinity of 1.0 and 1.5 μm. The data obtained are compared with the corresponding characteristics of other crystals. The possible use of the crystals studied as active media of solid-state lasers operating in the range 1.0 and 1.5 μm is discussed. __________ Translated from Optika i Spektroskopiya, Vol. 92, No. 4, 2002, pp. 657–664. Original Russian Text Copyright ? 2002 by Subbotin, Zharikov, Smirnov.     

Low-temperature vibrational properties of KGd(WO4)2: (Er, Yb) single crystals studied by Raman spectroscopy

Temperature-dependent polarized Raman spectra of KGd(WO₄)₂: (Er, Yb) single crystals have been analyzed over the 77-292 K temperature range. The A_g and B_g spectra obtained are discussed in terms of factor group analysis. The spectra have been found to reveal the bands related to internal and external vibrations of WO₄²⁻, WOW and WOOW molecular groups. Strong depolarization of the majority of the Raman bands has been observed in the whole temperature range. Some anomalies in the spectral parameters of selected Raman bands below 175 K have been discussed in terms of the local distortion of WO₄²⁻ ions in KGd(WO₄)₂: (Er, Yb) crystals.     

Optical spectroscopy of Yb/Er codoped NaY(WO4)2 crystal

Erbium and ytterbium codoped double tungstates NaY(WO₄)₂ crystals were prepared by using Czochralski (CZ) pulling method. The absorption spectra in the region 290-2000 nm have been recorded at room temperature. The Judd-Ofelt theory was applied to the measured values of absorption line strengths to evaluate the spontaneous emission probabilities and stimulated emission cross sections of Er³⁺ ions in NaY(WO₄)₂ crystals. Intensive green and red lights were measured when the sample were pumped by a 974 nm laser diode (LD), especially, the intensities of green upconversion luminescence are very strong. The mechanism of energy transfer from Yb³⁺ to Er³⁺ ions was analyzed. Energy transfer and nonradiative relaxation played an important role in the upconversion process. Photoexcited luminescence experiments are also fulfilled to help analyzing the transit processes of the energy levels.     

Polarized spectroscopic properties of Nd-doped KGd(WO4)2 single crystal

The polarized absorption spectra, infrared fluorescence spectra, upconversion visible fluorescence spectra, and fluorescence decay curve of orientated Nd³⁺:KGd(WO₄)₂ crystal were measured at room-temperature. Some important spectroscopic parameters were investigated in detail in the framework of the Judd-Ofelt theory and the Fuchtbauer-Ladenburg formula. The effect of the crystal structure on the spectroscopic properties of the Nd³⁺ ions was analyzed. The relation among the spectroscopic parameters and the laser performances of the Nd³⁺:KGd(WO₄)₂ crystal was discussed.     

Spectroscopic studies of Nd and Er in KGd(WO4)2 single crystals

Single crystals of KGd(WO₄)₂ doped with Nd³⁺ and Er³⁺ ions were grown by the top seeded solution growth method. Detailed analysis of the room-temperature absorption spectra was performed using the conventional Judd-Ofelt theory and actual dependence of the refractive index on the wavelength. In addition to the intensity parameters Ω_2,Ω_4,Ω₆, the branching ratios and radiative lifetimes were estimated for all possible transitions in the studied spectral region. Those transitions which can be potentially used for laser applications have been identified for both ions.     

Thermo-optical properties of pure and Yb-doped monoclinic KY(WO4)2 crystals

The thermo-optic coefficients, dn/dT, were determined for pure and Yb(20 at.%)-doped monoclinic KY(WO₄)₂ crystals for light polarized along the optical indicatrix axes (N _p,N _m and N _g) in the wavelength range of 0.36–1.06 μm by a laser beam deviation method. The absolute values of thermo-optic coefficients satisfy the relation |dn _p/dT|>|dn _g/dT|>|dn _m/dT| and increase with the wavelength increasing. In the long-wavelength range, all the dn/dT values are negative: dn _p/dT=−14.6, dn _m/dT=−8.9, dn _g/dT=−12.4 [10⁻⁶ K⁻¹] for pure KY(WO₄)₂ at 1.06 μm. The dependency of thermo-optic coefficients on the wavelength was modeled using an approach that takes into account contribution of volumetric thermal expansion and change of electronic bandgap with temperature. Large volumetric expansion of KY(WO₄)₂ plays a key role in the observed negative dn/dT values. Electronic bandgap and its temperature coefficient were determined for KY(WO₄)₂ crystals from thermo-optic dispersion curves as E _g=4.8–5.0 eV and −dE _g/dT=0.7–1.1×10⁻⁴ eV/K. Athermal propagation directions were calculated for KY(WO₄)₂ crystals at the wavelength of 1.06 μm for light polarizations E∥N _m and N _p.     

新型激光晶体Yb:KY(WO4)2的结构与光谱

采用顶部籽晶提拉法，以K₂W₂O₇为助溶剂，生长了Yb:KY(WO₄)₂新型激光晶体.经热重-差热分析，确定晶体熔点为1045℃，相变温度为1010℃.X射线粉末衍射测试，验证所生长的晶体为β-Yb:KY(WO₄)₂.晶体结构分析确定Yb:KY(WO₄)₂晶体由WO₆八面体连接而成，WO₆八面体是由双氧桥(WOOW)及单氧桥(WOW)构成.晶体粉末样品室温下的红外及拉曼光谱测试，确定WO₆原子基团、双氧桥及单氧桥的振动频率.晶体的吸收峰位于940nm，980nm，发射峰位于989nm—1030nm. 关键词： 晶体结构 光谱 晶体生长     

Synthesis and spectroscopic properties of LiIn(WO4)2 nanopowders and single crystals doped with chromium(III) ions

LiIn(WO₄)₂ single crystals and nanopowders doped with chromium(III) ions were synthesized and investigated, including their EPR spectra and magnetic properties. The EPR spectra have shown low and high field lines attributed to isolated chromium ions with an electron spin S=3/2 and complex chromium centers with higher spin value, respectively. Magnetic susceptibility measurements revealed an almost linear dependence on the magnetic field. The electron resonance and magnetic properties have been related to the structural and spectroscopic data of the studied material.     

Intrinsic polyatomic defects in Sc2(WO4)3

The intrinsic formation of polyatomic defects in Sc₂(WO₄)₃-type structures is studied by Mott Littleton calculations and Molecular Dynamics simulations. Defects involving the WO₄²⁻ tetrahedron are found to be energetically favorable when compared to isolated W and O defects. WO₄²⁻ Frenkel and (2Sc³⁺, 3WO₄²⁻) Schottky defects exhibit formation energies of 1.23 eV and 1.97 eV, respectively and therefore may occur as intrinsic defects in Sc₂(WO₄)₃ at elevated temperatures. WO₄²⁻ vacancy and interstitial migration processes have been simulated by classical Molecular Dynamics simulations. The interstitial defect exhibits a nearly 10 times higher mobility (with a migration energy of 0.68 eV), than the vacancy mechanism (with a slightly higher migration energy of 0.74 eV) and thus should dominate the overall ionic conduction. Still both models reproduce the experimental activation energy (0.67 eV) nearly within experimental uncertainty.     

Up-conversion emission in triply-doped Ho/Yb/Tm KGd(WO4)2 single crystals

Detailed spectroscopic studies of the triply doped KGd(WO₄)₂:Ho³⁺/Yb³⁺/Tm³⁺ single crystals (which exhibit multicolor up-conversion fluorescence) are reported for the first time. The absorption spectra of crystals were measured at 10 and 300 K; the room temperature luminescence spectra were excited at 980 nm wavelength. The dependence of the intensity of luminescence on the excitation power for three different concentration of Ho³⁺, Yb³⁺ and Tm³⁺ ions was investigated. Efficient green and red up-converted luminescence of Ho³⁺ ions and weak blue up-conversion luminescence of Tm³⁺ ions were observed in spectra. The red emission of Ho³⁺ ions is more intensive than their green emission. Dependence of the up-conversion luminescence intensity on the excitation power and impurities concentration was also studied; the number of phonon needed for efficient up-conversion was determined for each case. All possible energy transfer processes between different pairs of the impurity ions' energy levels are also discussed.     

The ground state and EPR spectrum in monoclinic KY(WO4)2:Nd single crystal

The electron paramagnetic resonance (EPR) of Nd³⁺ ion in KY(WO₄)₂ single crystal was investigated at T=4.2 K using an X-band spectrometer. The observed resonance absorption represents the complex superposition of three spectra corresponding to neodymium isotopes with different nuclear momenta. The EPR spectrum is characterized by a strong g-factor anisotropy. The temperature dependences of the g-factor were caused by strong spin-orbit and orbit-lattice coupling. The resonance lines become broader as temperature increases due to the short spin-lattice relaxation time.     

Photoluminescence studies of red-emitting NaEu(WO4)2 as a near-UV or blue convertible phosphor

Sodium europium double tungstate [NaEu(WO₄)₂] phosphor was prepared by the solid-state reaction method. Its crystal structure, photoluminescence properties and thermal quenching characteristics were investigated aiming at the potential application in the field of white light-emitting diodes (LEDs). The influences of Sm doping on the photoluminescence properties of this phosphor were also studied. It is found that this phosphor can be effectively excited by 394 or 464 nm light, which nicely match the output wavelengths of near-ultraviolet (UV) or blue LED chips. Under 394 or 464 nm light excitation, this phosphor exhibits stronger emission intensity than the Y₂O₂S:Eu³⁺ or Eu²⁺-activated sulfide phosphor. The introduction of Sm³⁺ ions can broaden the excitation peaks at 394 and 464 nm of the NaEu(WO₄)₂ phosphor and significantly enhance its relative luminance under 400 and 460 nm LEDs excitation. Furthermore, the relative luminance of NaEu(WO₄)₂ phosphor shows a superior thermal stability compared with the commercially used sulfide or oxysulfide phosphor, and make it a promising red phosphor for solid-state lighting devices based on near-UV or blue LED chips.     

Photoluminescence and energy transfer of Tm doped LiIn (WO4)2 blue phosphors

Room temperature steady and time resolved emission spectra of LiIn_1−xTm_x(WO4)2 (where thulium concentration is 0, 0.5, 1, 5 and 10 at%) blue phosphors, under UV excitation energy have been investigated. The concentration quenching effect on the blue emission, due to the (WO₄)⁻² groups and ¹G₄→³H₆ emission transition of Tm³⁺ were studied. Two energy transfer mechanisms are shown. The first takes place between excited (WO₄)⁻² groups and the ¹G₄ energy level of Tm³⁺, and is mainly analyzed by phonon-assisted energy transfer. The second mechanism is due to an energy transfer from the excited Tm³⁺ ions to the surrounding ground state Tm³⁺ ions. The non-exponential decay curves of the ¹G₄ level observed for higher concentrations are analyzed by the Inokuti–Hirayama model. We think that the quenching effect between Tm³⁺ ions is mainly linked to the dipole–dipole interactions.     

准二维电荷密度波导体磷酸钨青铜(PO2)4(WO3)2 m(m=6)的磁电阻研究

对准二维电荷密度波导体磷酸钨青铜(PO₂)₄(WO₃)_2m(m=6)在2—300K温区内的磁电阻及在2K时的Δρ/ρ_０-B关系进行了 实验研究.利用电子磁击穿模型对其低温端的磁阻增强行为进行了分析解释,理论和实验相 符合,并估算出高温端第一个Peierls能隙的大小为3.0meV,电子在低温下的迁移率为0.0 42m²V^-1s^-1 关键词： 低维导体磁电阻 电荷密度波     

Combustion synthesis and luminescence properties of NaY1−xEux(WO4)2 phosphors

The red phosphors NaY_1−xEu_x(WO₄)₂ with different concentrations of Eu³⁺ were synthesized via the combustion synthesis method. As a comparison, NaEu(WO₄)₂ was prepared by the solid-state reaction method. The phase composition and optical properties of as-synthesized samples were studied by X-ray powder diffraction and photoluminescence spectra. The results show that the red light emission intensity of the combustion synthesized samples under 394 nm excitation increases with increase in Eu³⁺ concentrations and calcination temperatures. Without Y ions doping, the emission spectra intensity of the NaEu(WO₄)₂ phosphor prepared by the combustion method fired at 900 °C is higher than that prepared by the solid-state reaction at 1100 °C. NaEu(WO₄)₂ phosphor synthesized by the combustion method at 1100 °C exhibits the strongest red emission under 394 nm excitation and appropriate CIE chromaticity coordinates (x=0.64, y=0.33) close to the NTSC standard value. Thus, its excellent luminescence properties make it a promising phosphor for near UV InGaN chip-based red-emitting LED application.     

On spectroscopic properties of the KYb(WO4)2:Pr3+ crystal

Spectroscopic properties of Pr³⁺ doped KYb(WO₄)₂ single crystals were investigated. The crystal lattice parameters were determined. Energy levels of Pr³⁺ in KYb(WO₄)₂ were assigned. The absorption, emission, excitation, time-resolved emission and excitation spectra were measured at low (10 K) and at room temperature. Decay times of the praseodymium emissions are non-exponential and unusually short. Site selection spectroscopy evidences several different Pr³⁺ sites. The Judd-Ofelt intensity model was used to analyse the experimental data. The Ω λ parameters, branching ratio and electric dipole transition probabilities were determined.