Dielectric properties and temperature stability of BaTiO3 co-doped La2O3 and Tm2O3

The influence of La₂O₃ and Tm₂O₃ co-doping on the dielectric properties and the temperature stability of BaTiO₃ was investigated. BaTiO₃ ceramics were prepared with the compositional formula of (Ba_1−xLa_x)(Ti_1-x/4−yTm_y)O₃. La₂O₃ and Tm₂O₃ co-doping in BaTiO₃ mainly had effects on an increase in the dielectric constant and the temperature stability, respectively. The increase of La₂O₃ concentration and the decrease of Tm₂O₃ concentration in BaTiO₃ resulted in a decrease of lattice parameter and tetragonality because La³⁺ ion substituting for Ba site is smaller than Ba²⁺ ion and Tm³⁺ ion substituting for Ti site is larger than Ti⁴⁺ ion. With the increase of La₂O₃ and the decrease of Tm₂O₃, the dielectric constant of BaTiO₃ was enhanced in spite of the reduction of tetragonality. P-E hysteresis measurements revealed that this phenomenon was based on the improvement of remanent polarization with the increase of La₂O₃ concentration. The introduction of excess Tm₂O₃ in BaTiO₃ suppressed the grain growth and BaTiO₃ ceramics showed higher temperature stability due to the stable tetragonal structure and the small grain size with the increase of Tm₂O₃ concentration.     

Temperature-dependent photoluminescence spectra of Er-Tm-codoped Al2O3 thin film

Er-Tm-codoped Al₂O₃ thin films with different Tm to Er concentration ratios were synthesized by cosputtering from separated Er, Tm, Si, and Al₂O₃ targets. The temperature dependence of photoluminescence (PL) spectra was studied. A flat and broad emission band was achieved in the 1.4-1.7 μm and the observed 1470, 1533 and 1800 nm emission bands were attributed to the transitions of Tm³⁺: ³H₄ → ³F₄, Er³⁺: ⁴I_13/2 → ⁴I_15/2 and Tm³⁺: ³F₄ → ³H₆, respectively. The temperature dependence is rather complicated. With increasing measuring temperature, the peak intensity related to Er³⁺ ions increases by a factor of five, while the Tm³⁺ PL intensity at 1800 nm decreases by one order of magnitude. This phenomenon is attributed to a complicated energy transfer (ET) processes involving both Er³⁺ and Tm³⁺ and increase of phonon-assisted ET rate with temperature as well. It should be helpful to fully understand ET processes between Er and Tm and achieve flat and broad emission band at different operating temperatures.     

Crystal field and microscopic spin Hamiltonians approach including spin-spin and spin-other-orbit interactions for d and d ions at low symmetry C3 symmetry sites: V in Al2O3

A new module has been developed within the CFA/MSH computer package, which is applicable for d² and d⁸ ions at sites of trigonal symmetry type I (C_3v,D₃,D_3d) and type II (C₃,C_3i), including the ‘imaginary’ CF term. For the first time the spin-spin (SS) and spin-other-orbit (SOO) interactions have also been included in the Hamiltonian. This module enables to study the contributions to the energy levels and the spin Hamiltonian parameters, i.e. zero-field splitting D and g-factors: g_∥ and g_⊥. The contributions arising from the spin-orbit (SO), SS, and SOO interaction as well as those due to the low symmetry CF effects induced by the distortion angle ?, which describes the difference between C₃ and C_3v symmetry, can be studied. As an application of the new module, calculations have been carried out for V³⁺(3d²) ions in α-Al₂O₃ crystal, taking into account for the first time the SS and SOO interactions, and the low symmetry CF effects. The results show that (i) the contributions from the SS and SOO interactions to the energy levels are larger for free V³⁺ ions than those for V³⁺ ions in α-Al₂O₃ crystal, (ii) both the contributions to the SH parameters and the energy levels arising from the SOO interaction are larger than those arising from the SS interaction, (iii) the contributions due to the low symmetry CF effects induced by the distortion angle ? are in general significant, (iv) D and g_⊥ are sensitive to the distortion angle ?, whereas g_∥ is insensitive to ?, and (v) the influence of the lattice distortions on the spectroscopic properties of V³⁺ ion in α-Al₂O₃ is pronounced. It appears important for similar ion-crystal cases to consider the lattice distortions in detailed calculations, which take into account the relevant contributions from the SO, SS and SOO interactions. A good agreement between the theoretical and experimental results has been obtained.     

Absorption spectrum of VO2+ in Na2Zn(SO4)2 · 4H2O single crystals

Optical absorption spectrum of VO²⁺ ion in sodium zinc sulphate tetrahydrate single crystal has been reported at room and liquid nitrogen temperatures. From the nature and position of the observed bands, they have been attributed to VO²⁺ ion in C_4v symmetry. The crystal field and molecular orbital coefficients have been evaluated.     

Electron spin resonance of diluted solid solutions of MnO2 in Y2O3

Electron spin resonance spectra of Mn²⁺ in diluted solid solutions of MnO₂ in Y₂O₃ have been studied at room temperature for Mn concentrations between 0.20 and 2.00 mol%. Isolated Mn²⁺ ions in sites with two different symmetries were observed, as well as Mn²⁺ ions coupled by the exchange interaction. The relative concentration of isolated to coupled Mn²⁺ ions decreases with increasing manganese concentration. The results are consistent with the assumption that the manganese ions occupy preferentially the C₂ symmetry sites. A theoretical calculation based on this model yields an effective range of the exchange interaction between Mn²⁺ ions of 0.53 nm, of the same order as that of Mn²⁺ ions in CaO.     

Van Vleck paramagnetism of the thulium garnet Tm3Al5O12

The magnetic susceptibility of the garnet-type single crystal Tm₃Al₅O₁₂ exhibits the typical Van Vleck temperature independent paramagnetism below ≈8 K. The temperature dependence of the susceptibility over the range 2.0-300 K has been analyzed on the assumption that the cubic crystal-electric-field dominates the energy level on ³H₆ (J=6) ground multiplet for Tm³⁺ ion having 12-electrons in 4f shell. The ground state of the ³H₆ is nonmagnetic with Γ₂ singlet, avoiding the Kramers doublet. The energy separation between Γ₂ and the first excited state Γ⁽²⁾₅ triplet is evaluated to be 68.0 K. The whole energy interval Δ between Γ₂ and the highest state Γ₁ in ³H₆ is estimated to be 339.5 K.     

Er3+，Tm3+共掺的NaY(WO4)2晶体的光谱分析和上转换发光

在室温下，测量了Er:Tm:NaY(WO₄)₂晶体的吸收光谱、激发光谱、发射光谱以及上转换发光，并运用J-O理论对测量的结果进行了计算，得出了Er:Tm:NaY(WO₄)₂晶体的强度参数.报道了Tm，Er离子间特殊的能量传递和相关上转换，解释了离子间的能级跃迁过程.同时，对于Er增强Tm离子近红外发光的特性也作了充分研究. 关键词： 4)₂晶体')" href="#">Er:Tm:NaY(WO₄)₂晶体 吸收光谱 发射光谱 激发光谱 上转换     

Excitation power controlled luminescence switching in Yb-Tm co-doped hexagonal NaYF4 nanorods

Intense infrared-to-visible up-conversion (UC) emissions were obtained in hexagonal Yb³⁺-Tm³⁺ co-doped NaYF₄ nanorods under excitation at 980 nm. Especially, luminescent switching between different UC emission wavelengths at 800, 480 and 450 nm were observed by adjusting excitation powers. Based on power-dependent spectral analyses, it was found that the cooperative energy transfer between Yb³⁺-Yb³⁺ pairs and Tm³⁺ ions play a key role on the luminescent switching besides the saturation effect of Yb³⁺²F_5/2 and Tm³⁺¹G₄ excited states. Our results indicate that hexagonal NaYF₄ nanostructures have potential applications in miniaturized solid-state laser, optical processing sensors and fluorescent biolabels.     

Theoretical studies of the optical and EPR spectra for V in Y2O3 crystal

In this paper, we give an alternative suggestion that both the observed optical and electron paramagnetic resonance (EPR) spectra of Yttrium oxide (Y₂O₃):V³⁺ are attributed to V³⁺ ions at the S₆ site of Y₂O₃. This suggestion is different from the opinion in the previous paper that the optical and EPR spectra are attributed to V³⁺ ions at the C₂ and S₆ sites, respectively. From the suggestion, the optical band positions and spin-Hamiltonian parameters are calculated by diagonalizing the complete energy matrix for 3d² ions in trigonal symmetry. The results are in good agreement with the experimental values, suggesting that both the observed optical and EPR spectra in Y₂O₃:V³⁺ may be due to V³⁺ at S₆ site of Y₂O₃ crystal.     

Absorption spectra and Zeeman effects of Tm3+ in CaF2

The absorption spectra of Tm³⁺ in CaF₂ were analyzed by the concentration series method at 4·2^°K. Systems of lines, belonging to Tm³⁺ion centers of different structure, are isolated from the general spectra. Some of structures of Tm³⁺ ion centers were made clear by studying optical Zeeman effects and a change of absorption lines during thermal treatment. The tetragonal crystal field parameters and g-value of the upper state are also discussed.     

Dosimetric properties of rare earth doped LiCaBO3 thermoluminescence phosphors

Lithium Calcium borate (LiCaBO₃) polycrystalline thermoluminescence (TL) phosphor doped with rare earth (RE³⁺) elements has been synthesized by high temperature solid state diffusion reaction. The reaction has produced a very stable crystalline LiCaBO₃:RE³⁺ phosphors. Among these RE³⁺ doped phosphors thulium doped material showed maximum TL sensitivity with favorable glow curve shape. TL glow curve of gamma irradiated LiCaBO₃:Tm³⁺ samples had shown two major well-separated glow peaks at 230 and 430 °C. The glow peak at 430 °C is almost thrice the intensity of the glow peak at 230 °C. The TL sensitivity of the phosphor to gamma radiation was about eight times that of TLD-100 (LiF). Photoluminescence and TL emission spectra showed the characteristic Tm³⁺ peaks. TL response to gamma radiation dose was linear up to 10³ Gy. Post-irradiation TL fading on storage in room temperature and elevated temperatures was studied in LiCaBO₃:Tm³⁺ phosphor.     

Upconversion emission enhancement of TiO2 coated lanthanide-doped Y2O3 nanoparticles

To investigate the upconversion emission,this paper synthesizes Tm3+ and Yb3+ codoped Y2O3 nanoparticles,and then coats them with TiO2 shells for different coating times.The spectral results of TiO2 coated nanoparticles indicate that upconversion emission intensities have respectively been enhanced 3.2,5.4,and 2.2 times for coating times of 30,60 and 90 min at an excitation power density of 3.21×102 W.cm 2,in comparison with the emission intensity of non-coated nanoparticles.Therefore it can be concluded that the intense upconversion emission of Y2O3:Tm3+,Yb3+ nanoparticles can be achieved by coating the particle surfaces with a shell of specific thickness.     

Room temperature magnetoresistance in Ln2/3A1/3MnO3 manganites

The investigation of the manganites La_2/3−xPr_xSr_1/3MnO₃, La_2/3Sr_1/3−xCa_xMnO₃ and La_2/3+xCa_1/3−2xAg_xMnO₃, which all exhibit Mn³⁺:Mn⁴⁺=2, shows that it is possible to reach high magnetoresistance at room temperature, up to 21% under 1.2 T. These materials are compared to La_5/6Ag_1/6MnO₃ which corresponds to the same Mn³⁺:Mn⁴⁺ ratio and exhibits a magnetoresistance of 25% in this field. An interesting feature deals with the value of the insulator-metal transition temperature T_IM, often higher than T_C, especially for Ag-based compounds. It is suggested that the latter results either from a better oxygenation of the surface of the grains or from a migration of silver toward the surface.     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

Tm3+/Ho3+共掺镓铋酸盐玻璃1.47μm发光特性和能量传递的研究

报道了Tm³⁺/Ho³⁺共掺的镓铋酸盐玻璃14Ga₂O₃-25Bi₂O₃-20GeO₂-31PbO-10PbF₂玻璃1.47μm(S波段)发光和能量传递特征，应用Judd-Ofelt理论计算了玻璃的强度参数Ω_t(t=2，4，6)，自发辐射概率A、荧光分支比β，荧光辐射寿命τ等各项光谱参数以及有效荧光线宽Δλ_eff和峰值发射截面σ^peak_e.通过测量荧光光谱和荧光寿命研究了Ho³⁺离子掺杂浓度对Tm³⁺离子1.47μm波段发光性能的影响，分析了Tm³⁺和Ho³⁺之间的能量传递过程.结果表明一定浓度内Ho³⁺的共掺迅速降低了Tm³⁺：³F₄能级的粒子数，而对³H₄能级粒子数影响不大，从而降低了³F₄和³H₄能级间布居数反转的难度，极大地提高了1.47μm发光效率.研究表明镓铋酸盐玻璃是适用于S波段光纤放大器的一种潜在基质材料，而掺杂一定浓度的Ho³⁺离子有利于提高Tm³⁺离子在1.47μm波段的发光效率. 关键词： 重金属氧化物玻璃 光谱性质 3+/Ho³⁺离子')" href="#">Tm³⁺/Ho³⁺离子 能量传递     

Cr3+/Tm3+/Ho3+共掺氟磷酸盐玻璃的制备及性能表征

制备了不同 Al(PO₃)₃含量的掺铥系列氟磷酸盐玻璃,研究了其结构、热稳定性和光谱性质. 研究了不同摩尔百分数 Al(PO₃)₃掺杂下 Cr³⁺/Tm³⁺/Ho³⁺共掺氟磷酸盐玻璃在 2.0μm 处的发光特性. 并且用Judd-Ofelt理论计算了强度参量,并由此计算了激发能级的自发辐射跃迁速率、辐射寿命、荧光分支比等光谱参量. 结果表明,随着 Tm³⁺浓度增加,2.0μm 处发光的强度逐渐增强. 证明了Tm³⁺(³F₄) →Ho³⁺(⁵I₇)能量转移是非常有效的,并与掺杂浓度有关. 关键词： 氟磷酸盐玻璃 能量传递 荧光光谱 吸收光谱     

Tm3+ 掺杂ZrF4 -BaF2 -LaF3 -AlF3 -NaF-PbF2玻璃激光制冷中荧光再吸收效应的理论分析

固体材料的激光制冷是近年来发展起来的一个新的研究领域. 掺Tm³⁺的ZrF₄-BaF₂-LaF₃-AlF₃-NaF-PbF₂(ZBLANP)玻璃材料是激光冷却的典型材料之一. 与另一种制冷掺杂离子Yb³⁺相比,Tm³⁺具有更好的制冷潜力. 目前制约材料制冷的一个主要机理就是荧光再吸收. 首先根据Tm³⁺:ZBLANP的光谱参数,利用半经典的随机行走模型得到了不同情况下的平均荧光再吸收次数,随后分析了荧光光子界面出射的全反射效应,并对所得结果进行了修正. 计算结果表明,荧光再吸收会导致量子效率降低0.5%-1%,出射荧光波长红移达到2-10 nm,激光制冷的效率和功率降低. 为了有利于荧光出射和净制冷的实现, 宜采用小体积细长棒的制冷元. 关键词： 激光制冷 稀土离子 荧光再吸收     

Study on up-conversion emissions of Yb/Tm co-doped GdF3 and NaGdF4

The Yb³⁺/Tm³⁺ co-doped GdF₃ and NaGdF₄ samples were synthesized through a combination method of a co-precipitation and an argon atmosphere annealing procedures. X-ray diffraction analysis indicated that the Yb³⁺/Tm³⁺ co-doped GdF₃ sample crystallized well and was orthorhombic phase, and the Yb³⁺/Tm³⁺ co-doped NaGdF₄ sample was hexagonal phase. With a 980-nm semiconductor continuous wave laser diode as the excitation source, the up-conversion emission spectra of the two samples in the wavelength range of 240-510 nm were recorded. In the up-conversion emissions of the samples, Yb³⁺ transferred energies to Tm³⁺ resulting in their ultraviolet, violet, and blue up-conversion emissions. And, Tm³⁺ simultaneously transferred energies to Gd³⁺, which finally resulted in ultraviolet up-conversion emissions of Gd³⁺. The study on the excitation power dependence of up-conversion fluorescence intensity indicated that there were multi-photon (three-, four-, five-, and six-) processes in the up-conversion emissions of the samples. And the up-conversion emissions of Gd³⁺ and Tm³⁺ in the Yb³⁺/Tm³⁺ co-doped GdF₃ and NaGdF₄ samples were compared studied, too.     

NIR luminescence from Er/Yb, Tm/Yb, Er/Tm and Nd ions-doped zincborotellurite glasses for optical amplification

In this paper, we report the near-infrared luminescence from the Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Er³⁺/Tm³⁺ and Nd³⁺ ions-doped TeO₂-ZnO-B₂O₃-Li₂O-Na₂O glasses for optical amplification. The X-ray diffraction (XRD) and differential scanning calorimetry (DSC) profiles of the host glass matrix have been carried out. From the DSC thermogram, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The near-infrared spectra of Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Er³⁺/Tm³⁺ and Nd³⁺ ions-doped glasses have shown full-width at half-maxima (FWHM) around 58, 127, 87 and 35 nm, respectively. These glasses with better thermal stability and broad near-infrared emissions should have potential applications in broadly tunable laser sources and broadband optical amplification at low-loss telecommunication windows.     

Tm3+/Yb3+共掺氧卤碲酸盐玻璃上转换发光研究

研究了Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光光谱，分析了Tm₂O₃含量对Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃上转换发光的影响机理.结果表明：在Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光中，Tm³⁺存在较强的浓度猝灭效应.随Tm₂O₃含量增加，Tm³⁺的上转换蓝光和红光强度先增加，后降低，在0.1mol% Tm₂O₃达到最大.该结果有助于进一步提高Tm³⁺的上转换发光效率.