Spectroscopic and laser properties of Er3+-doped monoclinic BaY2F8 single crystals

The luminescence and absorption properties of Ba(Y_1–x Er _x )₂F₈ (x=0.001, 0.01, 0.05, 0.1, 0.2 and 0.3) and the Er³⁺-ion decay kinetics of luminescent transitions from three initial laser states, the⁴S_3/2,⁴F._9/2 and⁴I_11/2 manifolds, were measured. The crystal-field splitting schemes for allJ-manifolds which are involved in (J J)-luminescence transitions and stimulated emission parameters of Er³⁺ -ions in BaY₂F₈ were determined. A comparison of laser powers and efficiencies of BaY₂F₈ and Y₃Al₅O₁₂, Lu₃Al₅O₁₂ and LiYF₄ single crystals doped with Er³⁺-ions shows the similar performance of these materials.     

Effect of different doped elements on visible light absorption and ultraviolet light emission on Er3+:Y3Al5O12

In this progress report, seven kinds of novel carefully designed and fabricated up-conversion luminescence agents, Er³⁺:Y₃Al₅O₁₂, Er³⁺:Yb_nY_3?nAl₅O₁₂, Er³⁺:Y₃B_aAl_5?aO₁₂, Er³⁺:Y₃Ga_bAl_5?bO₁₂, Er³⁺:Y₃Al₅N_xO_12?x, Er³⁺:Y₃Al₅F_yO_12?y and Er³⁺:Yb_nY_3?nB_aGa_bAl_5?a?bN_xF_yO_12?x?y, are successfully synthesized using sol–gel methods. After that, their corresponding photocatalysts, Er³⁺:Y₃Al₅O₁₂/TiO₂, Er³⁺:Yb_nY_3?nAl₅O₁₂/TiO₂, Er³⁺:Y₃B_aAl_5?aO₁₂/TiO₂, Er³⁺:Y₃Ga_bAl_5?bO₁₂/TiO₂, Er³⁺:Y₃Al₅N_xO_12?x/TiO₂, Er³⁺:Y₃Al₅F_yO_12?y/TiO₂ and Er³⁺:Yb_nY_3?nB_aGa_bAl_5?a?bN_xF_yO_12?x?y/TiO₂, are also prepared by sol–gel coating process. The obtained up-conversion luminescence agents and photocatalysts were characterized by using XRD, XPS, SEM, UV–vis and fluorescence spectrophotometer. Synchronously, several kinds of organic dyes are used to test their photocatalytic degradation using prepared photocatalysts. It indicates that the up-conversion luminescence ability of Er³⁺:Y₃Al₅O₁₂ can be improved obviously through doping of some elements. And then, the photocatalytic activity of TiO₂ is markedly enhanced by modified up-conversion luminescence agents which can transform much visible light into ultraviolet light.     

VUV luminescence of Er<Superscript>3+</Superscript> ions in LiYF<Subscript>4</Subscript> and BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals

Vacuum ultraviolet luminescence of Er³⁺ ions in LiYF4 and BaY₂F₈ crystals has been investigated. It is revealed that under excitation by 193 nm radiation from an ArF excimer laser the interconfigurational 5d–4f radiative transitions in Er³⁺ ions are observed. It is shown that from the LiYF₄:Er crystal only the spin-forbidden luminescence (λ = 165 nm) is detected, whereas both the spin-forbidden (λ = 169 nm) and spin-allowed (λ = 160.5 nm) components are observed from the BaY₂F₈:Er crystal.     

Improvement of sonocatalytic activity of TiO2 by using Yb,N and F-doped Er3+:Y3Al5O12 for degradation of organic dyes

In this study, several up-conversion luminescence agents (Er³⁺:Y₃Al₅O₁₂, Er³⁺:Yb_0.2Y_2.79Al₅O₁₂, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01O_11.99, Er³⁺:Yb_0.2Y_2.79Al₅F_0.01O_11.99 and Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98) were synthesized using sol–gel method. And then, the corresponding sonocatalyst (Er³⁺:Y₃Al₅O₁₂/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅O₁₂/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01O_11.99/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅F_0.01O_11.99/TiO₂ and Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites) were prepared by sol–gel coating process. The synthesized up-conversion luminescence agents and their coated composites were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). And that, the sonocatalytic activities were detected through the degradation of Azo Fuchsine (AF) dye in aqueous solution by UV–vis spectroscopy. Some key influences such as heat-treated temperature and heat-treated time on the sonocatalytic activity of Er³⁺:Yb_aY_2.99−aN_xF_yAl₅O_12−x−y/TiO₂ coated composite, as well as ultrasonic irradiation time and initial dye concentration on the sonocatalytic degradation were studied. The results showed that the doping of Yb, N and F into Er³⁺:Y₃Al₅O₁₂/TiO₂ significantly enhanced the sonocatalytic activity of Er³⁺:Y₃Al₅O₁₂/TiO₂ coated composite in the degradation of organic dyes. Particularly, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites with 3:7 M ratio heat-treated at 550 °C for 60 min showed the highest sonocatalytic activity. At last, the experiments also indicated that the Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites has a good sonocatalytic activity to degrade other organic dyes under ultrasonic irradiation.     

Efficiency of the generation and self-addition of laser line frequencies upon the diode pumping of Er:BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals

Features of the generation of laser lines upon the diode pumping of Er:BaY₂F₈ crystals are studied. Blue, violet, and UV laser lines are most efficiently generated via the nonlinear frequency self-addition of 541 and 553 nm lines of Er³⁺ radiation with the corresponding IR line of Er³⁺ for Er:BaY₂F₈ crystals pumped by a laser diode with a wavelength of 972 nm.     

Excited-state absorption in Er: BaY2F8 and Cs3Er2Br9 and comparison with Er: LiYF4

The influence of Excited-State Absorption (ESA) on the green laser transition and the overlap of Ground-State Absorption (GSA) and ESA for 970 nm upconversion pumping in erbium is investigated in Er³⁺ : BaY₂F₈ and Cs₃Er₂Br₉. Results are compared to Er³⁺ : LiYF₄. In Er³⁺: BaY₂F₈, a good overlap between GSA and ESA is found at 969 nm in one polarization direction. The emission cross section at 550 nm is a factor of two smaller than in LiYF₄. In Cs₃Er₂Br₉, the smaller Stark splitting of the levels shifts the wavelengths of the green emission and ESA from⁴ I _{1 3/2} off resonance. It enhances, however, ground-state reabsorption. The emission cross section at 550 nm is comparable to LiYF₄. Upconversion leads to significant green fluorescence from² H _9/2. A significant population of the⁴ I _11/2 level and ESA at 970 nm are not present under 800 nm pumping.     

共沉淀法制备Y2SiO5∶Er3+ ,Yb3+ ,Tm3+及其上转换发光性能研究

采用化学共沉淀法制备了系列Y_1.98-2xYb_2x Er_0.02SiO₅(0.00≤x≤0.15)以及Y_1.736Yb_0.24Er_0.02Tm_0.004SiO₅上转换发光材料,比较了室温下Y_1.98-2xYb_2x Er_0.02 SiO₅ (x=0.00,0.08)样品在400—1600 nm范围内的吸收光谱,测量了所有样品在976 nm OPO激光器激发下的上转换发射光谱,以及Er³⁺离子⁴S_3/2(⁴F_9/2)→⁴I_15/2,Tm³⁺离子¹G₄→³H₆荧光衰减曲线和不同激发功率下的上转换蓝光发射强度,从而分析讨论了Er³⁺,Tm³⁺在Y₂SiO₅中的上转换发光机理.研究结果表明:在1250 ℃相对较低的温度下合成了X2型单斜晶系Y₂SiO₅ ∶Ln³⁺(Ln³⁺=Er³⁺,Yb³⁺,Tm³⁺),Yb³⁺的敏化显著增强了样品在976 nm附近的吸收能力,并大幅度加宽了该处的吸收带.分析上转换发射光谱发现:上转换绿光和红光强度都随着Yb³⁺浓度的增加先增强后减弱,但红光的猝灭浓度较高,归因于Er³⁺→Yb³⁺反向能量传递ETU4和Yb³⁺→Er³⁺正向能量传递ETU3过程的发生;上转换蓝光发射是三光子吸收过程,是通过Yb³⁺,Tm³⁺之间三次声子辅助的能量转移方式实现的. 关键词： 上转换 共沉淀 2SiO₅∶Er³⁺')" href="#">Y₂SiO₅∶Er³⁺ 3+')" href="#">Yb³⁺ 3+')" href="#">Tm³⁺     

Scintillation properties of Er-doped Y3Al5O12 single crystals

Er-doped Y₃Al₅O₁₂ single crystals with different Er concentrations of 0.1, 1.0, 10, 30, and 50% were grown by the micro-pulling down method. There were several absorption lines due to the Er³⁺ 4f-4f transitions in the transmittance spectra and these lines correspond to the transitions from the ground state of ⁴I_15/2 to the excited states. The photo- and radio-luminescence spectra showed Er³⁺ 4f-4f emissions. Relative light yield under 5.5 MeV alpha-ray irradiation of Er 0.1%:Y₃Al₅O₁₂ was estimated to be 63% of that of Bi₄Ge₃O₁₂.     

Effect of composition disorder on the electron paramagnetic resonance spectrum of the thermally populated excited state of Er<Superscript>3+</Superscript> ions in YLuAG mixed garnets

The results of investigation of electron paramagnetic resonance of Er³⁺ ions in the thermally populated first excited state in (Y_{1 − x} Lu _x )₃Al₅O₁₂ (YLuAG) mixed yttrium-lutetium garnet single crystals (0 ≤ x ≤ 1) are considered. In composition-disordered YLuAG, a number of new (as compared to Y₃Al₅O₁₂ (YAG)) Er³⁺ paramagnetic centers are detected; these centers appear due to a change in the crystal field symmetry and magnitude upon isomorphic substitution of Lu³⁺ for Y³⁺ in the yttrium sublattice of garnets. The origin of new paramagnetic centers is established and their formation probability is calculated.     

Doubly doped BaY2F8:Er,Nd VUV scintillator

Doubly doped BaY₂F₈:Er,Nd scintillation crystals were grown by modified micro-pulling-down method. The Er co-doping was chosen to enhance the energy transfer from the host lattice to the Nd³⁺ luminescence center via the 5d-levels of Er³⁺, which can be enabled by the overlap of Er³⁺ 5d-4f emission spectrum with the Nd³⁺ 4f-5d absorption. The energy transfer was clearly evidenced in the BaY₂F₈:Er,Nd. The processes are complicated by energy migration to killer centres and/or cross-relaxation processes. The luminescence and energy transfer mechanism are discussed.     

Enhanced optical activation of Er in Er-doped Al2O3 powders by Y codoping in a sol-gel method

Enhanced photoluminescence (PL) mechanism of Er³⁺-doped Al₂O₃ powders by Y³⁺ codoping at wavelength 1.53 μm has been investigated through PL measurements of 0.1 mol% Er³⁺- and 0-20 mol% Y³⁺-codoped Al₂O₃ powders prepared at a sintering temperature of 900 °C in a non-aqueous sol-gel method. PL intensity and lifetime of Er³⁺-Y³⁺-codoped Al₂O₃ powders composed of γ-(Al,Er,Y)₂O₃ and θ-(Al,Er,Y)₂O₃ phases increased with increasing Y³⁺-codoping concentration. The 10-20 mol% Y³⁺ codoping in 0.1 mol% Er³⁺-doped Al₂O₃ powders intensified the PL intensity by about 20 times, with a PL lifetime prolonged from 3.5 to 5.8 ms. A maximal increase of the optical activity of Er³⁺ in 0.1 mol% Er³⁺-Y³⁺-codoped Al₂O₃ powders about one order was achieved by 10-20 mol% Y³⁺ codoping. It is found that the improved PL properties for Er³⁺-Y³⁺-codoped Al₂O₃ powders are mainly attributed to enhanced optical activation of Er³⁺ in the Al₂O₃ by Y³⁺ codoping, and to the slightly increased radiative quantum efficiency of Er³⁺ in the Al₂O₃.     

Optical and EPR study of BaY2F8 single crystals doped with Yb

Optical and electron paramagnetic resonance study have been carried out on BaY₂F₈ single crystals doped with Yb ions at 0.5 and 10 mol%. The crystals have been obtained using the Czochralski method modified for fluoride crystal growth. Optical transmission measurements in the range of 190-3200 nm and photoluminescence measurements were carried out at room temperature. Absorption spectra of BaY₂F₈ single crystals doped with Yb due to the ²F_7/2→²F_5/2 transitions have been observed in the 930-980 nm range. To analyze the possible presence of Yb²⁺ ions in the investigated crystals, irradiation with γ-quanta with a dose of 10⁵ Gy have been performed. The observed photoluminescence bands show usual emission in IR and other one in VIS, being an effect of cooperative emission of Yb³⁺ ions and energy up-conversion transitions of photons from IR to UV-vis(visible) due to hoping process between energy levels of paired Yb³⁺ and Er³⁺, where Er³⁺ ions are unintentional dopants. The EPR spectra of BaY₂F₈:Yb 10 mol% consist of many overlapping lines. They have been analyzed in terms of spin monomers, pairs, and clusters. The angular dependence of the resonance lines positions have been studied also to find the location of coupled ytterbium ions in the crystal structure.     

Infrared-to-visible up-conversion emissions and thermometric applications of Er 3+-doped Al 2 O 3

Er³⁺-doped Al₂O₃ has been prepared by a sol–gel method, using aluminium isopropoxide [Al(OC₃H₇)₃]-derived Al₂O₃ sols with addition of erbium nitrate [Er(NO₃)₃·5H₂O]. The phase structure of θ-(Al,Er)₂O₃ phase was obtained for the 0.1 mol. % Er³⁺-doped Al₂O₃ at the sintering temperature of 1273 K. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the ² H _11/2, ⁴ S _3/2→⁴ I _15/2 and ⁴ F _9/2→⁴ I _15/2 transitions of Er³⁺, were detected by a 978-nm semiconductor laser diode excitation. The temperature dependence of green up-conversion emissions was studied over a wide temperature range of 295–725 K, and reasonable agreement between the calculated temperatures obtained by the fluorescence intensity ratio theory and the measured temperature was obtained, which proved that Er³⁺-doped Al₂O₃ has a good potential for the development of high-temperature sensors. It has some advantages compared to glasses due to its higher thermal and mechanical resistance and allows measurements in a large temperature range. PACS 78.55.Hx; 81.40.Tv     

Up-conversion multiwave (White) luminescence in the visible spectral range under excitation by IR laser diodes in the active BaY2F8:Yb3+,Pr3+ medium

The possibilities of occupying high-lying 4f states of Pr³⁺ ions in the active BaY₂F₈:Yb³⁺,Pr³⁺ medium according to the photon avalanche and step-by-step sensitization mechanisms are compared. It is shown that the photon avalanche is unlikely to occur in the BaY₂F₈:Yb³⁺,Pr³⁺ crystal. The multiband luminescence spectra in the visible spectral range (white emission) under single- and multiwave pumping of BaY₂F₈:Yb³⁺,Pr³⁺ crystal by IR laser diodes are reported.     

Excited state absorption and stimulated emission of Nd3+ in crystals. Part I: Y3Al5O12, YAlO3, and Y2O3

4 F_3/2 excited state of the Nd³⁺ ion in Y₃Al₅O₁₂, YAlO₃, and Y₂O₃ were measured in a continuous wave pump- and probe experiment in a wide spectral range from 850 nm (780 nm for Y₃Al₅O₁₂) to 1500 nm. The cross sections were determined from a comparison with the emission spectra and the simultaneously measured ground state absorption bleaching. The strongest excited state absorption transitions were found in the 1220–1400 nm spectral region due to transitions to the ²G_9/2 and ⁴G_7/2 levels. The spectral positions of the measured transitions are in good agreement with the theoretically expected transitions calculated from the known Stark-level splittings. Received: 4 December 1997/Revised version: 8 May 1998     

Control of luminescence and conductivity of delafossite-type CuYO2 by substitution of rare earth cation (Eu, Tb) and/or Ca cation for Y cation

Delafossite-type oxides of CuTb_yY_1−yO₂, CuEu_yY_1−yO₂, CuCa_xTb_yY_1−x−yO₂ and CuCa_xEu_yY_1−x−yO₂ have been prepared by solid state reactions. The lattice-parameter dependence on the composition implies substitution of the Tb³⁺, Eu³⁺ and Ca²⁺ cations for the Y³⁺ site. Noticeable sharp emission lines due to the f-f transitions (⁵D₄→⁷F_J, J=3-6) of Tb³⁺ or due to the f-f transitions (⁵D₀→⁷F_J, J=0-4) of Eu³⁺ are observed at room temperature. Electrical conductivities of CuCa_xTb_yY_1−x−yO₂ and CuCa_xEu_yY_1−x−yO₂ are larger than those of CuTb_yY_1−yO₂ and CuEu_yY_1−yO₂, indicating the increase of the hole concentration caused by the substitution of Ca²⁺ for the Y³⁺ site. These results indicate the controllability of the luminescence and conductivity in CuCa_xTb_yY_1−x−yO₂ and CuCa_xEu_yY_1−x−yO₂ delafossite-type oxides by simultaneous substitution of the rare earth Tb³⁺ or Eu³⁺ cation and the Ca²⁺ cation for the Y³⁺ site.     

Synthesis and Characterization of Monodispersed SiO2@Y3Al5O12:Er3+ Core-Shell Particles

Submicron core-shell structure particles SiO₂@Y₃Al₅O₁₂:Er³⁺, which silica spherical particles was coated with an yttrium aluminum garnet (Y₃Al₅O₁₂) layer doped with Er³⁺, were prepared by the modified Pechini-Type sol-gel method for the first time. The structure and morphology of samples were detected by the X-ray powder diffraction (XRD) measurement, field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM), respectively. The results indicate that well-crystallized garnet nanocrystallines were formed on the surface of the silica particles. The luminescent spectra in near infrared and visible region of the core-shell structured SiO₂@Y₃Al₅O₁₂:Er³⁺ powders were also investigated and compared with those of the pure Y₃Al₅O₁₂:Er³⁺ and the Er³⁺ doped silicate glass. The results show that mono-dispersed SiO₂@Y₃Al₅O₁₂:Er³⁺ core-shell spherical particles with the near infrared, red and green luminescent emissions under the excitation of 980 nm laser diode have been successfully synthesized.     

Crystal-field and superposition model analysis of :BaY F ( = Er, Dy, Nd)

The experimental values of the energy levels of Er³⁺, Dy³⁺, and Nd³⁺ in BaY₂F₈ were fitted to a single-ion Hamiltonian containing free-ion and crystal-field interactions. The crystal-field parameters so evaluated were then analyzed by using Newman's Superposition Model. The agreement between the two sets of parameters is good, provided a possible distortion of the F^- polyhedron around the rare-earth site is taken into account. The effects of a possible displacement of the rare-earth ion substituting for Y³⁺ are also evaluated. Received 14 May 2002 / Received in final form 12 July 2002 Published online 17 September 2002     

The laser-diode-excited 5d-4f luminescence of Ce3+ and Pr3+ ions embedded into a BaR2F8 matrix

We show the possibility of obtaining UV luminescence from 5d-4f transitions of rare-earth ions in the BaY₂F₈: (Yb³⁺, Pr³⁺, Ce³⁺) crystal under upconversion excitation by standard laser diodes with lasing wavelengths of 960, 808, and 840 nm. Various upconversion mechanisms of pumping for populating the higher-lying energy levels of the active ions, as well as methods of adaptation of the active medium BaY₂F₈: (Yb³⁺, Pr³⁺, Ce³⁺) to these mechanisms, are considered.     

Vibronic Transitions of Trivalent Er and Ce in BaY2F8 Single Crystals

High resolution (0.02 cm^?1) Fourier transform spectroscopy was applied in the 9–300 K and 100–24,000cm^?1 ranges, respectively, to detect in Er^3? and Ce^3? doped BaY₂F₈ single crystals (1) the narrow line spectra due to the intraconfigurational 4f→4f transitions of the rare earths (RE) and (2) the possible vibronic tails accompanying the zero-phonon lines. The ²F_5/2→²F_7/2 transition was monitored for the Ce^3?-doping and the crystal field splitting of the initial and final manifold was determined. Weak vibronic spectra accompanying six among the nine investigated 4f→4f transitions of Er^3? and the ²F_5/2→²F_7/2 transition of Ce^3? were detected. The vibronic spectra amplitude was found to scale with the RE contents. On the basis of the IR- and Raman-active vibrational modes, either measured or quoted in the literature, most of the vibronic lines could be successfully assigned to the lattice modes. Violations of the selection rules were envisaged and discussed.