中子探测晶体Li6Gd(BO3)3:Ce的光谱特性研究

文章用提拉法生长出Li₆Gd(BO₃)₃:Ce晶体,并对其光谱性能与发光过程进行了探索. 借助于真空紫外-紫外透过光谱测试,发现晶体的透过光谱中存在Ce³⁺离子和Gd³⁺的特征吸收峰,同时还存在与Ce⁴⁺离子相关的电荷迁移带. 对晶体的真空紫外-紫外激发发射光谱进行研究发现,在晶体存在着Ce³⁺离子的5d→4f辐射跃迁发光与Gd³⁺离子的4f→4f辐射跃迁发光,而且存在着Gd³⁺→Ce³⁺之间的能量传递. 对Li₆Gd(BO₃)₃:Ce晶体的X射线与γ射线激发发射光谱研究可知,晶体在高能射线激发下的闪烁光主要是Ce³⁺离子的发光. 关键词： 6Gd(BO₃)₃:Ce晶体')" href="#">Li₆Gd(BO₃)₃:Ce晶体 真空紫外-紫外透过光谱 真空紫外-紫外激发发射光谱 能量传递     

Luminescence properties of novel NaBa4(BO3)3:Ce, Eu phosphors

Novel Eu³⁺, Ce³⁺ activated NaBa₄(BO₃)₃ phosphors were synthesized by solid-state reactions. The excitation spectrum of NaBa₄(BO₃)₃:Ce³⁺ consists of an intense band peaking at 350 nm and a weak band in the higher energy side, and the emission spectrum exhibits a blue band with a maximum at about 420 nm. The Eu³⁺ emission in NaBa₄(BO₃)₃ consists of the transitions from ⁵D₀ to ⁷F_J, and the excitation spectrum consists of broad excitation band peaking at 270 nm and some intense narrow lines. The optimum doped concentration, the critical distance of the concentration quenching, and the fluorescence lifetime have also been investigated.     

Double emitting phosphor NaSr4(BO3)3:Ce, Tb for near-UV light-emitting diodes

Blue and green double emitting phosphor, Ce³⁺ and Tb³⁺ co-doped NaSr₄(BO₃)₃, was synthesized in a weak reducing atmosphere by a conventional high temperature solid-state reaction technique. For comparison, Ce³⁺ or Tb³⁺ singly doped NaSr₄(BO₃)₃ was also prepared. The emission and excitation spectra of all samples have been investigated. NaSr₄(BO₃)₃:Tb³⁺ excitation includes a strong absorption at about 240 nm and some weak sharp lines in near-ultraviolet (n-UV) spectral region. The excitation of Ce³⁺ and Tb³⁺ co-doped NaSr₄(BO₃)₃ shows a strong broad band absorption in the n-UV region from the contribution of Ce³⁺, which makes it suitable for excitation by a n-UV LED chip. The emission of NaSr₄(BO₃)₃:Ce³⁺,Tb³⁺ consists of a blue emission band from Ce³⁺ and a green emission from Tb³⁺ under the excitation of n-UV light. Energy transfer between Ce³⁺ and Tb³⁺ is also discussed, and the relative intensity of blue emission and green emission could be tuned by adjusting the concentration of Ce³⁺ and Tb³⁺. The phosphor NaSr₄(BO₃)₃:Ce³⁺,Tb³⁺ could be considered as a double emission phosphor for n-UV excited white light-emitting diodes.     

Energy levels and crystal-field analysis of Tm in YAl3(BO3)4 crystals

The electronic structure of the Tm³⁺ in YAl₃(BO₃)₄ crystals has been investigated by means of low temperature absorption and emission spectroscopy in the 5000-30,000 cm⁻¹ range. The assignment of the lines composing the observed manifolds to transitions between the Stark levels of Tm³⁺ is complicated by the presence of extra features having different origins. The energy levels scheme of the doping ion has been compiled after a careful analysis of the spectra by reproducing the observed transitions by means of theoretical calculations based on a Hamiltonian, including the free ion and the crystal field (CF) terms. The agreement between experimental and calculated energy values was reasonably good, the overall r.m.s. deviation being 16 cm⁻¹. The resulting CF parameters have been tabulated and compared with those reported in literature for other rare earth ions doped in YAB. The analysis of trends observed along the lanthanide series evidences some inconsistencies and the necessity of a systematic investigation of these systems.     

Characterization of the VUV excitation spectrum of BaZr(BO3)2:Eu

The excitation spectra of M (M=Si⁴⁺, Ti⁴⁺) and Eu³⁺ co-doped BaZr(BO₃)₂, BaZrO₃:Eu and La₂Zr₂O₇:Eu in the vacuum ultraviolet (VUV) regions of 110-300 nm are investigated and the host-lattice absorption are characterized. The result indicated that BaZr(BO₃)₂:Eu³⁺ phosphor has a strong absorption under the VUV excitation, and in the host-lattice excitation, the strong band at 130-160 nm could be due to the BO₃ atomic groups; the band at 160-180 nm is related to the excitation of Ba-O; 180-200 nm corresponds to the charge transfer (CT) transition of Zr-O. The band at 200-235 nm due to the CT band of Eu³⁺-O²⁻ and a bond valence study explained the observed weak CT band of Eu³⁺-O²⁻ in the excitation spectra of BaZr(BO₃)₂:Eu³⁺. The emission results show that Si⁴⁺ can sensitize luminescence in the host of BaZr(BO₃)₂:Eu but Ti⁴⁺ has no improvement effect on luminescence.     

New red phosphors BaZr(BO3)2 and SrAl2B2O7 doped with Eu for PDP applications

Vacuum ultraviolet (VUV) excitation and photoluminescence (PL) characteristics of Eu³⁺ ion doped borate phosphors; BaZr(BO₃)₂:Eu³⁺ and SrAl₂B₂O₇:Eu³⁺ are studied. The excitation spectra show strong absorption in the VUV region with the absorption band edge at ca. 200 nm for BaZr(BO₃)₂:Eu³⁺ and 183 nm for SrAl₂B₂O₇:Eu³⁺, respectively, which ensures the efficient absorption of the Xe plasma emission lines. In BaZr(BO₃)₂:Eu³⁺, the charge transfer band of Eu³⁺ does not appear strongly in the excitation spectrum, which can be enhanced by co-doping Al³⁺ ion into the BaZr(BO₃)₂ lattices. The luminescence intensity of BaZr(BO₃)₂:Eu³⁺ is also increased by Al³⁺ incorporation into the lattices. The PL spectra show the strongest emission at 615 nm corresponding to the electric dipole ⁵D₀→⁷F₂ transition of Eu³⁺ in both BaZr(BO₃)₂ and SrAl₂B₂O₇, similar to that in YAl₃(BO₃)₄, which results in a good color purity for display applications.     

Investigation of the iron borates DyFe3(BO3)4 and HoFe3(BO3)4 by the method of Er spectroscopic probe

Temperature-dependent high-resolution optical spectra of the Er³⁺ probe ion in DyFe₃(BO₃)₄ and HoFe₃(BO₃)₄ are reported. The data provide the temperature of magnetic ordering and direction of the Fe³⁺ magnetic moments. Both compounds order magnetically at TN=39±1 K$T_{\mathrm{N}}=39\pm 1\text{ K}$. The magnetic structure of DyFe₃(BO₃)₄ is of the easy-axis type, while that of HoFe₃(BO₃)₄ is of the easy-plane type. The role of anisotropic interactions between the iron and the rare-earth subsystems is discussed.     

Optical properties and electronic structure of rare-earth ferroborates

The optical absorption spectra of single-crystal ferroborate GdFe₃(BO₃)₄ and GdFe_2.1Ga_0.9(BO₃)₄ are measured and interpreted. It is found that the absorption edge and the absorption bands A, B, and C observed below the edge are close to those for FeBO₃. A many-electron model of the band structure of GdFe₃(BO₃)₄ is suggested including strong electron correlations between the iron d states. It is shown that GdFe₃(BO₃)₄ has a charge-transfer dielectric gap. A rise in pressure is predicted to result in a crossover between the high-spin and low-spin states of the Fe³⁺ ion, collapse of the magnetic moment, a weakening of Coulomb correlations, an abrupt reduction in the energy gap, and an insulator-semiconductor transition.     

Time-resolved site-selection spectroscopy studies of NdAl3(BO3)4 crystals

A pulsed, tunable dye laser was used to selectively excite Nd³⁺ ions in nonequivalent crystal field sites in NdAl₃(BO₃)₄ crystals and energy transfer between ions in different types of sites was studied by monitoring the time evolution of the fluorescence spectrum. The results show that the energy transfer rate varies as t^{$\text{-1}\text{2}$} and increases with temperature. The predictions of various models of phonon-assisted energy transfer are compared to the results.     

Growth and characterization of Nd-doped disordered Ca3Gd2(BO3)4 crystal

A high-quality disordered Nd³⁺:Ca₃Gd₂(BO₃)₄ (Nd³⁺:CGB) laser crystal was grown by the Czochralski method. The space group and effective segregation coefficient of Nd³⁺ were determined to be Pnma and 1.06, respectively. The thermal properties, including the average linear thermal expansion coefficient, thermal diffusivity, specific heat, and thermal conductivity were systematically measured for the first time. It was found that the thermal conductivity increases with increasing temperature, indicating glasslike behavior. The polarized spectral properties of the crystal were investigated, including the polarized absorption spectra, polarized fluorescence spectra, and fluorescence decay. The spectroscopic parameters of Nd³⁺ ions in Nd³⁺:CGB crystal have been obtained based on Judd–Ofelt theory. The anisotropy of the spectral properties for different polarized directions was discussed. Additionally, the continuous-wave (CW) laser performance at 1.06 μm was demonstrated for the first time. The maximum output power of 603 mW was achieved with corresponding optical conversion efficiency of 8.33% and slope efficiency of 9.95%.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

Synthesis, photoluminescence, thermoluminescence and dosimetry properties of novel phosphor Zn(BO2)2:Tb

Polycrystalline powder samples of terbium doped Zn(BO₂)₂ phosphors were prepared by solid state reaction in the thermal carbon reducing atmosphere at high temperature. The photoluminescence (PL), three-dimensional (3D) TL emission spectrum and dosimetric characteristics following ⁶⁰Co gamma-rays irradiation were studied. Characteristic emission bands of Tb³⁺ at about 490, 543, 584 and 620 nm, attributed to the ⁵D₄→⁷F_J (J=3, 4, 5, 6) transitions of Tb³⁺ ions, were observed in the TL and PL emission spectrum. No emission from Tb⁴⁺ ions was observed in the TL emission spectrum. The TL-dose response of the powder samples Zn(BO₂)₂:Tb to ⁶⁰Co gamma-rays radiation in the dose range from 1 to 100 Gy for clinical dose levels was almost linear. The experiment results showed that Zn(BO₂)₂:Tb has potential use as the materials of gamma-rays thermoluminescence dosimeter (TLD) for clinical dosimetry.     

Specific heat of YFe3(BO3)4, Y0.5Gd0.5Fe3(BO3)4, and GdFe3(BO3)4

The specific heat was measured in the range 0.4–300 K in YFe₃(BO₃)₄, Y_0.5Gd_0.5Fe₃(BO₃)₄, and GdFe₃(BO₃)₄ single crystals. Sharp anomalies were found at temperatures of first-order structural, second-order antiferromagnetic, and first-order spin-reorientational transitions. A Néel temperature of about 37 K was found to be virtually independent of presence of rare-earth ions, indicating rather weak coupling of Gd and Fe subsystems. The contribution of the magnetic system to specific heat was separated through the scaling procedure allowing determination of the magnetic entropy of Fe and Gd subsystems. At the lowest temperatures, the specific heat in GdFe₃(BO₃)₄ exhibits a Schottky-type anomaly, which is due to Gd³⁺ eightfold degenerate ground-level splitting by the internal magnetic field of the Fe subsystem of about 7 T. The text was submitted by the authors in English.     

A new sodium samarium borate Na3Sm2(BO3)3

A new sodium samarium borate with composition Na₃Sm₂(BO₃)₃ (NSBO) has been synthesized by high temperature solid state reaction. The yellowish transparent single crystals of Na₃Sm₂(BO₃)₃ have been grown from the Na₂CO₃-H₃BO₃ flux system using the top-seeded solution growth (TSSG) method. X-ray diffraction analysis demonstrated that the NSBO crystals belong to orthorhombic systems and lattice parameters are a=5.0585 Å, b=11.0421 Å, c=7.0316 Å. The measurement of the infrared spectrum indicated that the basic anionic groups are the BO³⁻₃ groups. Furthermore, Na₃Sm₂(BO₃)₃ exhibits an optical second harmonic generation effect which is close to that of KDP (KH₂PO₄).     

Yb and Yb-Eu luminescent properties of the Li2Lu5O4(BO3)3 phase

The luminescence of Yb³⁺ in the oxyborate Li₂Lu₅O₄(BO₃)₃ is reported. At low temperature, in addition to the usual ytterbium infrared emission, this phosphor presents an emission in the ultraviolet () which corresponds to the transition from the charge transfer state (O-Yb) to the 4f levels of Yb³⁺. The temperature quenching Tq50% is equal to 120 K. The infrared emission studied at room temperature is located between 950 and 1100 nm.Europium emission quenching in the Li₂Yb₅O₄(BO₃)₃ phase is related to Eu→Yb transfer by cross-relaxation. The reverse Yb→Eu transfer by cooperative sensitization is highlighted in the codoped Li₂Lu₅O₄(BO₃)₃ compound.     

Optical absorption spectrum and local symmetry of Tm ion in TmAl3(BO3)4 crystal

With the help of group theory analysis of absorption spectra of the transition ³H₆ → ³F₃ of Tm³⁺ ion in TmAl₃(BO₃)₄ crystal, measured at several temperatures from 1.8 till 293 K, it has been shown, that the local symmetry of the Tm³⁺ environment is C₃ and it decreases to C₁ at a low temperature. Effective selection rules and polarizations of lines at high enough temperatures (when the line-width is larger than the splitting in C₃ symmetry) have been obtained.     

Growth and spectroscopic properties of Yb-doped Li6Y(BO3)3 single crystal

The spectroscopic properties of high-quality Czochralski grown 20% Yb³⁺-doped Li₆Y(BO₃)₃ single crystal as new promising laser material are presented. The crystal was seeded-grown in the 〈0 1 0〉 direction and its crystallinity was measured using X-ray rocking curve analysis. Low temperature transmission spectrum exhibits broad bands in a short range of wavelengths and two sharp lines at 972.5 and 978 nm, interpreted as two zero-lines of two nonequivalent Yb³⁺ centers inside the lattice. The fluorescence lifetimes associated to these two intense lines are different: 0.867 and 1.33 ms. An attempt of determination of the Stark sublevels energies of the ⁴F_5/2 and ⁴F_7/2 manifolds of the two Yb³⁺ nonequivalent ions is given. The polarized absorption and emission spectra were also recorded at room temperature and we conclude that the most favorable emission line for laser application could be around 1042 nm in n_g polarization.     

Spectroscopy of Ca3(BO3)2: Dy crystal

Dy³⁺: Ca₃(BO₃)₂ crystal was grown successfully by the Czochraski technique. The absorption spectrum was measured and its absorption peaks were assigned. The Judd-Ofelt intensity parameters were found to be Ω₂=5.216×10⁻²⁰, Ω₄=1.858×10⁻²⁰, Ω₆=0.623×10⁻²⁰ cm². The spectroscopic parameters of this crystal such as the oscillator strengths, radiative transition probabilities, radiative lifetime as well as the branching ratios were calculated. Also, room temperature luminescence decay curve in correspondence with the emission line ⁴F_9/2→⁶H_13/2 centered at 575 nm was measured.     

Energy transfer in Li6Gd(BO3)3

The synthesis and structure of the new one-dimensional material Li₆Gd(BO₃)₃ are described. The Gd³⁺ fluorescence is studied from 300 to 1.5 K after selective pulsed excitation into the ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ manifold. Above 40 K the fluorescence decays indicate fast diffusion of the energy among intrinsic and perturbed Gd³⁺ ions, and trapping by impurities. Below 40 K the energy transfer takes place dominantly towards perturbed Gd³⁺ ions and is diffusion limited. This behaviour is discussed in relation with the quasi one-dimensional crystal structure.     

Optical amplification properties of Dy3+-doped Gd2SiO4, Lu2SiO5 and YAl3(BO3)4 single crystals

Comparative investigation of the optical amplification properties of dysprosium doped Gd₂SiO₅, Lu₂SiO₅ and YAl₃(BO₃)₄ single crystals was performed in a pump-and-probe experiment. High power laser pulses at 475 nm were used as the pump source in order to strongly populate the ⁴F_9/2 level of the Dy³⁺ ions due to ground state absorption. Low signal beam cw radiation at 574 nm was used as the probe beam to stimulate the emission associated with the ⁴F_9/2→⁶H_13/2 electronic transition of the Dy³⁺ ions. The process was modelled as a three levels system, and their populations were analysed and simulated in order to study the gain dynamics. Positive optical gain was observed and compared in these crystals. These results confirmed that among the systems studied the Dy³⁺-doped YAl₃(BO₃)₄ single crystal can be considered as a good candidate to develop an optical amplifier employing the ⁴F_9/2→⁶H_13/2 transition at around 574 nm which is the first step to consider as laser active media.