EPR studies of linewidth anomalies at phase transitions in [N(C2H5)4]2MnCl4

We have studied [N(C₂H₅)₄]₂MnCl₄ crystal by X-band CW EPR spectra in the temperature range 170-300 K. The angular dependences of linewidth ΔH were measured and described in the light of a double-layer system (2D) with exchange interactions. Two temperature anomalies of linewidth ΔH were found at T₁=225 K and T₂=192 K on cooling. Different behaviors of ΔH anomalies recorded for an external magnetic field parallel and perpendicular to the ab crystallographic plane indicate ordering/disordering of MnCl₄ groups in this plane and their displacement along the c-axis which occurs in the temperature of about 225 K.     

EPR spectra of Fe centers in layered TlGaSe2 single crystal

A single-crystal TlGaSe₂ doped by paramagnetic Fe ions has been studied at room temperature by electron paramagnetic resonance (EPR) technique. The fine structure of EPR spectra of paramagnetic Fe³⁺ ions was observed. The spectra were interpreted to correspond to the transitions among spin multiplet (S=5/2, L=0) of Fe³⁺ ion, which are splitted by the local ligand crystal field (CF) of orthorhombic symmetry. Four equivalent Fe³⁺ centers have been observed in the EPR spectra and the local symmetry of crystal field at the Fe³⁺ site and CF parameters were determined. Experimental results indicate that the Fe ions substitute Ga at the center of GaSe₄ tetrahedrons, and the rhombic distortion of the CF is caused by the Tl ions located in the trigonal cavities between the tetrahedral complexes.     

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.     

Twinned EPR spectra of Fe centers in ternary layered TlGaS2 crystal

TlGaS₂ single crystal doped by paramagnetic Fe³⁺ ions has been studied by electron paramagnetic resonance (EPR) technique. The fine structure of EPR spectra of paramagnetic Fe³⁺ ions was observed. The spectra reveal a nearly orthorhombic symmetry of the crystal field (CF) on the Fe³⁺ ions. Two groups each consisting of four equivalent Fe³⁺ centers were observed in the EPR spectra. The local symmetry of the crystal field on the Fe³⁺ centers and CF parameters were determined. Experimental results indicate that the Fe ions substitute Ga at the center of the GaS₄ tetrahedrons. The rhombic distortion of the sulfur ligand CF is attributed to the effect of Tl ions located in the trigonal cavities between the tetrahedral complexes. The observed twinning of the resonance lines indicates a presence of two non-equivalent positions of Tl ions that confirms their zigzag alignment in the TlGaS₂ crystal structure.     

Magnetic resonance study of the two-dimensional spin diffusion in the Heisenberg paramaget (C18H37NH3)2MnCl4

¹H nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) techniques were employed to study the perovskite-type layered structure compound (C₁₈H₃₇NH₃)₂MnCl₄ undergoing structural phase transitions. The spin relaxation was found to sensitively reflect the two-dimensional electron spin diffusion.     

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.     

Growth and spectral properties of Nd:GdVO4 laser crystal

In this paper, the Czochralski growth, absorption spectra, and photoluminescence spectra of Nd:GdVO₄ crystals are studied. From its absorption spectra, Nd:GdVO₄ is found to exhibit an anisotropic optical absorption effect, and its effective Judd-Ofelt parameters are calculated: Ω₂=10.281×10⁻²⁰ cm², Ω₄=5.426×10⁻²⁰ cm² and Ω₆=9.943×10⁻²⁰ cm². By these parameters, the absorption oscillator strengths, emission oscillator strengths, transition probabilities, fluorescence branch ratios, energy lifetimes, and integrated emission cross-sections are also derived. The photoluminescence spectra of Nd:GdVO₄ crystal consist of a wide emission band of host and the characteristic emission bands of Nd³⁺. Based on the excitation spectrum, both the two evident peaks locating at 345 and 371 nm are ascribed to the characteristic excitation of Nd³⁺, and an energy transfer from the host to its doping Nd³⁺ ions is indicated.     

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.     

ESR investigation of the spin dynamics in (Gd1−xYx)2PdSi3

We report electron-spin resonance (ESR) measurements in polycrystalline samples of (Gd_1−xY_x)₂PdSi₃. We observe the onset of a broadening of the linewidth and of a decrease of the resonance field at approximately twice the Néel temperature in the paramagnetic state. This characteristic temperature coincides with the electrical resistivity minimum. The high-temperature behavior of the linewidth is governed by a strong bottleneck effect.     

ESR spectra of Eu centers in defect Ga2S3 single crystals

In this paper, the author presents the results of measurements of the low-temperature and angular dependences of the ESR spectra of Eu²⁺ centers in defect Ga₂S₃ single crystals in the temperature range 8–29 K and for 0–180° orientations of the static magnetic field. The electron structure of impurity ¹⁵¹Eu atoms in Ga₂S₃:Eu single crystals has been studied by using the ESR method at different doping proportions of Eu atoms. Ga₂S₃ single crystals were grown from the melt using the Bridgman method. The Eu concentration was determined by atomic absorption analysis and X–ray fluorescence analysis (XRFA). By investigation on the ESR spectra, the author has first determined the values of charge states for Eu, which have turned out to be a Eu²⁺(4f⁷) ion with spin S=7/2, g=4.18±0.02 and concentration of the states of Eu N=6.3×10¹⁴ cm⁻³.     

Growth and spectral properties of Tm/Er:NaGd(MoO4)2 single crystal

The Tm³⁺/Er³⁺:NaGd(MoO₄)₂ crystal with dimensions of Φ22×30 mm³ was grown by Czochralski method. Polarized spectra and fluorescence lifetime for the ⁴I_13/2(Er³⁺)→⁴I_15/2(Er³⁺) transition at room temperature were investigated. Based on the Judd-Ofelt theory, the spontaneous transition probabilities, the fluorescent branching ratios and the radiative lifetimes were calculated. The fluorescence lifetime was measured to be 1.81 ms. The detailed excited-transition mechanism with 800 nm radiation is also discussed.     

Synthesis and luminescence properties of Tb:NaGd(WO4)2 novel green phosphors

Tb³⁺:NaGd(WO₄)₂ (Tb:NGW) phosphors with different Tb³⁺ concentrations have been synthesized by a mild hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence excitation and emission spectra and decay curve were used to characterize the Tb:NGW phosphors. XRD analysis confirmed the formation of NGW with scheelite structure. SEM study showed that the obtained Tb:NGW phosphors appeared to be nearly spherical and their sizes ranged from 1 to 1.5 μm. The excitation spectra of these systems showed an intense broad band with maximum at 270 nm related to the O→W ligand-to-metal charge-transfer state. Photoluminescence spectra indicated the phosphors emitted strong green light centered at 545 nm under UV light excitation. Analysis of the photoluminescence spectra with different Tb³⁺ concentrations revealed that the optimum dopant concentration for Tb³⁺ is about 15 at% of Tb³⁺ ions in Tb:NGW phosphors.     

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     

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.     

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.     

Theoretical study of local lattice structure of Mn in perovskite fluorides A2MF4 (A=K, Rb; M=Mg, Zn, Cd) series

A theoretical method for investigating the inter-relation between the molecular structure and electronic structure has been established on the basis of the 252×252 complete energy matrices for a 3d⁵ configuration ion in a tetragonal ligand field. By means of this method, which is independent of the X-ray diffraction, the local structure of the paramagnetic Mn²⁺ ion in perovskite fluorides A₂MF₄ (A=K, Rb; M=Zn, Mg, Cd) are determined directly by analyzing the EPR spectrum of octahedral Mn²⁺ center in A₂MF₄ crystals and the optical absorption spectrum of the (MnF₆)⁴⁻ cluster. It is shown that, comparing with the octahedral cubic structure, the local micro-structure in the vicinity of Mn²⁺ displays an elongated distortion when and a compressed distortion when , and ΔR vs. as well as ΔR vs. in the distortion region is, respectively, approximately linear. Simultaneously, the theoretical zero-field-splitting parameters , and are in good agreement with the experimental values.     

Core level spectroscopy and RHEED analysis of KGd(WO4)2 surface

Structural and electronic characterisation of mechanically polished (010) KGd(WO₄)₂ (KGW) has been produced by reflection high-energy electron diffraction (RHEED) and X-ray photoelectron spectroscopy (XPS). With XPS analysis the original element binding energies, chemical composition and valence band structure of KGW have been determined.     

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.     

Spectroscopic characteristic and energy levels of Cr in Cr:KAl(MoO4)2 crystal

This paper reports polarized spectral properties and energy levels of Cr³⁺ in KAl(MoO₄)₂ crystal. The absorption and emission cross sections are estimated as 3.72×10^-20 cm² at 669 nm and 2.74×10^-20 cm^-2 at 823 nm for σ-polarization, respectively. The energy levels of Cr³⁺ ion in KAl(MoO₄)₂ crystal were calculated based on the Tanabe-Sugano theory. It is suggested that Cr³⁺ ions occupy at an intermediate crystal field site in Cr³⁺:KAl(MoO₄)₂.     

The domain structure of ferroelastic BiVO4 crystal studied by Gd EPR

The domain structure of ferroelastic BiVO₄ single crystal has been investigated using the electron paramagnetic resonance (EPR) of the Gd³⁺ ions existing as an impurity in the crystal. Two sets of Gd³⁺ EPR signals were obtained in the crystallographic ca-plane. These two sets of signals originated not from the two kinds of substitutional sites but from the twin-domain structure in the host crystal. It is found that the BiVO₄ crystal investigated with Gd³⁺ EPR has the prominent (W-plane) domain wall. The domain structure is stable in contrast with a previous report by Baran et al. From the observed W-plane of the domain wall, it is suggested that a ferroelastic transition in BiVO₄ is 4/mmm F 2/m instead of 4/m F 2/m. The model of twinning mechanism improved in a previous report by Mn²⁺ EPR is confirmed by Gd³⁺ EPR.