EPR and optical properties of KYb(WO4)2 and KTb0.2Yb0.8(WO4)2 single crystals

Well oriented KYb(WO₄)₂ and KTb_0.2Yb_0.8(WO₄)₂ single crystals have been investigated for their magnetic and optical properties using the Raman and EPR techniques. The registered EPR signal is dominated by three lines ascribed to ytterbium ions: one main and two satellites. Tb ions, although non-paramagnetic, distinctly modify magnetic properties of the KYb(WO₄)₂ single crystal. Basic parameters of the spin Hamiltonian, including Zeeman and hyperfine terms (g and A matrices) as well the spatial orientation between principal and crystallographic axes systems were determined for both crystals.     

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.     

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.     

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.     

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.     

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.     

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.     

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     

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.     

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.     

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.     

Optical holeburning in NaEu(WO4)2

Optical holeburning in the concentrated rare earth compound NaEu(WO₄)₂ is studied. The observation of narrow, 25 MHz, long lived holes and antiholes burned into the ⁷F₀ → ⁵D₀ transition of the Eu³⁺ ion are reported and discussed.     

Polarized fluorescence spectra analysis of Yb:KGd(WO4)2

The average fluorescence wavelength of the laser crystal is the most important factor in the radiation-balanced laser (RBL). Polarized fluorescence spectra measurements of the anisotropic laser material ytterbium-doped potassium gadolinium tungstate, Yb³⁺:KGd(WO₄)₂, are carried out along principal refractive index directions m, p, g in three configurations in order to achieve the best design for RBL. The average fluorescence wavelength of g polarization is the shortest, so g should be in the face of fluorescence emission; m polarization should be normal to that face to avoid its strong absorption to fluorescence photons. Fluorescence re-absorption causes the average fluorescence wavelength of the directly measured spectra red-shifted at least 9 nm. Methods for depressing radiation trapping are suggested accordingly, which are high power pumping, low doping concentration, small dimensions and fusing with undoped KGd(WO₄)₂.     

Short-wavelength luminescence in Ho-doped KGd(WO4)2 crystals

Emissions from the high-lying excited states, energy transfer and upconversion processes are investigated in Ho³⁺-activated KGd(WO₄)₂ crystal. The spectral assignment based on time-resolved emission spectra allowed to identify various near ultra-violet (UV), blue and green emissions starting from the excited ³H₅, ⁵G₄, ⁵G₅, ⁵F₃ and ⁵S₂ levels. The temporal behavior of these transitions after pulsed excitation was analyzed as a function of temperature and holmium ions concentration. The shortening and nonexponentiality of the decays, observed with increasing activator concentrations, indicated cross-relaxation (CR) among the Ho³⁺ ions. Cross-relaxation rates were experimentally determined as a function of activator concentration and used to evaluate the values of the nearest-neighbor trapping rates X₀₁ and to model the decays. It was observed that KGW, despite higher than in YAG maximum phonon energy of about 900 cm⁻¹, is more efficient short-wavelength emitter than YAG. Examples of the excited-state absorption (ESA) and energy transfer (ET) mechanisms responsible for the upconverted, short-wavelength emissions were identified by analyzing fluorescence dynamics and possible energy resonances.     

Synthesis process and the luminescence properties of rare earth doped NaLa(WO4)2 nanoparticles

Rare earth doped NaLa(WO₄)₂ nanoparticles have been prepared by a simply hydrothermal synthesis procedure. The X-ray diffraction (XRD) pattern shows that the Eu³⁺-doped NaLa(WO₄)₂ nanoparticles with an average size of 10-30 nm can be obtained via hydrothermal treatment for different time at 180 °C. The luminescence intensity of Eu³⁺-doped NaLa(WO₄)₂ nanoparticles depended on the size of the nanoparticles. The bright upconversion luminescence of the 2 mol% Er³⁺ and 20 mol% Yb³⁺ codoped NaLa(WO₄)₂ nanoparticles under 980 nm excitation could also be observed. The Yb³⁺-Er³⁺ codoped NaLa(WO₄)₂ nanoparticles prepared by the hydrothermal treatment at 180 °C and then heated at 600 °C shows a 20 times stronger upconversion luminescence than those prepared by hydrothermal treatment at 180 °C or by hydrothermal treatment at 180 °C and then heated at 400 °C.     

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.     

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.     

Spectral performance and intensive green upconversion luminescence in Er/Yb-codoped NaY(WO4)2 crystal

Using Czochralski (CZ) pulling method, an Er³⁺/Yb³⁺-codoped NaY(WO₄)₂ crystal was prepared. Absorption spectra, emission spectra and excitation spectra of this crystal were measured at room temperature. Some optical parameters, such as intensity parameters, spontaneous emission probabilities and lifetimes, were calculated from absorption spectra with Judd-Ofelt (J-O) theory. Upconversion luminescence excited by a 970 nm diode laser was studied. In this crystal, green upconversion luminescence is particularly intensive. Energy transfer mechanisms that play an important role in upconversion processes were analyzed. Two cross-relaxation processes: ⁴G_11/2 + ⁴I_9/2 → ²H_11/2 (or ⁴S_3/2) + ²H_11/2 (or ⁴S_3/2), and ⁴G_11/2 + ⁴I_15/2 → ²H_11/2 (or ⁴S_3/2) + ²I_13/2, which contribute to the intensive green luminescence under 378 nm excitation, were put forward. Background energy transfer ⁴G_11/2(Er³⁺) + ²F_7/2(Yb³⁺) → ⁴F_9/2(Er³⁺) + ²F_5/2(Yb³⁺) was also demonstrated.     

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.     

Synthesis and luminescence properties of red-emitting phosphors NaY0.87Eu0.13(WO4)1.2(MoO4)0.8

A series of NaY_1−yEu_y(WO₄)_2−x(MoO₄)_x (x=0−2 and y=0.06−0.15) phosphors have been prepared by a combustion route. X-ray powder diffraction, photoluminescence excitation and emission spectra were used to characterize the resulting samples. The excitation spectra of these phosphors show the strongest absorption at about 396 nm, which matches well with the commercially available n-UV-emitting GaN-based LED chip. Their emission spectra show an intense red emission at 616 nm due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. As the Mo content increases, the intensity of the ⁵D₀→⁷F₂ emission of Eu³⁺ activated at wavelength of 396 nm increases and reaches a maximum when the relative ratio of Mo/W is 2:3. The intense red-emission of the tungstomolybdate phosphors at near-UV excitation suggests that the material is a potential candidate for white light emitting diode (WLEDs).