Growth and optical properties of Er,Yb:YAl3(BO3)4 crystal

Single crystal of erbium, ytterbium-codoped yttrium aluminum tetraborate Er,Yb:YAl₃(BO₃)₄(Er,Yb:YAB) has been grown by the flux method. The absorption spectrum in the visible and NIR regions of Er,Yb:YAl₃(BO₃)₄ crystal are measured at room temperature and fluorescence spectrum of Er,Yb:YAl₃(BO₃)₄ crystal are also measured at room temperature, excited by 976 nm laser. Not only the strong NIR emission peaks located at 1548 nm was observed, but also the visible up-conversion luminescence has been found. The specific heat of the Er/Yb:YAB crystal at room temperature is 0.81 J/g °C.     

Up-conversion emission in KGd(WO4)2 single crystals triply-doped with Er/Yb/Tm, Tb/Yb/Tm and Pr/Yb/Tm ions

Triply-doped single crystals KGd(WO₄)₂:Er³⁺/Yb³⁺/Tm³⁺, KGd(WO₄)₂:Tb³⁺/Yb³⁺/Tm³⁺ and KGd(WO₄)₂:Pr³⁺/Yb³⁺/Tm³⁺ were grown by the Top Seeded Solution Growth (TSSG) method, with an aim of getting efficient up-converted multicolored luminescence, which subsequently can be used for generation of white light. Such an aim determined the choice of the triply doped compounds: excitation of the Yb³⁺ ions in the infrared spectral region is followed by red, green and blue emission from other dopants. It was shown that all these systems exhibit multicolor up-conversion fluorescence under 980 nm laser irradiation. Detailed spectroscopic studies of their absorption and luminescence spectra were performed. From the analysis of the dependence of the intensity of fluorescence on the excitation power the conclusion was made about significant role played by the host’s conduction band and other possible defects of the KGd(WO₄)₂ crystal lattice in the up-conversion processes.     

Nanopowders of YAl3(BO3)4 doped by Nd, Yb and Cr obtained by sol-gel method: Synthesis, structure and luminescence properties

Structure, morphology and luminescence properties of nanocrystalline samples of YAl₃(BO₃)₄ (YAB) undoped and doped with neodymium, ytterbium and chromium obtained by the sol-gel method are presented. The best results of synthesis are obtained for mannitol as polymerizing agent. Single phase of nanopowder is obtained for pure YAB. Dopants destroy the compound structure; two other compounds, namely Al₁₈B₄O₃₃ and YBO₃, were revealed by X-ray investigation. Nanopowders show isometric and needles forms, the calculated size of crystallites is about 60 nm. Their optical properties are determined and results are compared to data obtained for single crystal counterparts. It is shown that the influence of rare earth ions incorporated into YBO₃ phase on luminescent spectra and excited state relaxation dynamics of the nanopowders is negligibly small when the YBO₃ content is of the order of several wt%. Residual impurity phases do not affect significantly spectroscopic properties of YAB nanopowders.     

Synthesis, structure and luminescent properties of Lu(PO3)3

A new structural type of rare earth metaphosphate, Lu(PO₃)₃, was prepared from high-temperature solution, of which the crystal structure was solved in S.G. of Cc (No.9) and Z = 4 with unit cell dimensions of a = 13.972(3) Å, b = 6.6710(13) Å, c = 9.958(2) Å and β = 127.36(3)°. In Lu(PO₃)₃, [LuO₆] octahedra connect with the non-bridging oxygens on (PO₃)_n infinite zigzag chains that extended along c-axis. The VUV and X-ray excited luminescent properties of undoped and Ln³⁺ (Ln = Ce, Eu, Tb) doped samples were examined, from which the optical band gap was estimated to be 8.3 eV. Besides, in the undoped sample a STE emission within 320–480 nm was observed, which probably be related to oxygen defects. However, in the Lu(PO₃)₃:Ce sample the Ce³⁺ emission was weak and STE emission was totally quenched under hard X-ray excitation.     

Shaped single crystal growth and scintillating application of Yb:(Gd,Lu)3(Ga,Al)5O12 solid solutions

Shaped single crystals of (Yb_0.05Lu_xGd_0.95−x)Ga₅O₁₂ (0.0x0.9) and Yb_0.15Gd_0.15Lu_2.7(Al_xGa_1−x)O₁₂ (0.0x1.0) were grown by the modified micro-pulling-down method. Continuous solid solutions with garnet structure and a linear compositional dependency of crystal lattice parameter in the system Yb:(Gd,Lu)₃(Ga,Al)₅O₁₂ are formed. Measured optical absorption spectra of the samples show 4f–4f transitions related to Gd³⁺ ion at 275 and 310 nm, and also an onset of charge transfer transitions from oxygen ligands to Gd³⁺ or Yb³⁺ cations below 240 nm. A complete absence of Yb³⁺ charge transfer luminescence under X-ray excitation in any of the investigated samples was explained by the overlapping of charge transfer absorption of Yb³⁺ by that of Gd³⁺ ions. For specific composition of Lu_1.5Gd_1.5Ga₅O₁₂ an intense defect––host lattice-related emission, which achieve of about 40% integrated intensity compared with Bi₄Ge₃O₁₂, was found.     

Crystal growth and spectral properties of Pr:La2(WO4)3

Pr³⁺-doped La₂(WO₄)₃ single crystal with dimensions up to Ø 20 mm × 35 mm has been grown by the Czochralski method. The structure of the Pr³⁺:La₂(WO₄)₃ crystal was determined by the X-ray powder diffraction and the Pr³⁺ concentration in this crystal was determined. The absorption and fluorescence spectra of Pr³⁺:La₂(WO₄)₃ crystal were measured at room temperature, and the fluorescence lifetime of main emission multiplets were estimated from the recorded decay curves. The spectral properties related to laser performance of the crystal were evaluated.     

Photoluminescence investigation of rare-earth activated GdCa3(GaO)3(BO3)4 phosphors under UV excitation

A borate compound was adopted as a new host material of Eu³⁺ and Tb³⁺ activators to fabricate efficient luminescence materials. The phosphor compositions, Gd_1−xEu_xCa₃(GaO)₃(BO₃)₄ and Gd_1−xTb_xCa₃(GaO)₃(BO₃)₄, were synthesized by conventional solid-state reactions. The crystalline phases of the resulting powders were identified using an X-ray diffraction system. Their photoluminescence properties were investigated under long-wavelength UV excitation. The Eu³⁺-doped and Tb³⁺-doped GdCa₃(GaO)₃(BO₃)₄ phosphors efficiently emitted red and green light, respectively. The temperature dependency of emission intensity was measured in a range from room temperature to 150 °C. The emission intensities of the red and green phosphors at 150 °C are 87% and 91% of those at room temperature, respectively. In addition, the decay times of both the red and green phosphors are shorter than 3 ms.     

Growth, thermal and optical properties of Yb:GdYAl3(BO3)4 crystal

Single crystal of Yb:GdYAl₃(BO₃)₄(Yb:GdYAB) has been grown by the flux method. The structure of Yb:GdYAB crystal has been determined by X-ray diffraction analysis. The experiment show that the crystal has the same structure as that of YAl₃(BO₃)₄ crystal and its unit cell constants have been measured to be a = 9.30146 Å, c = 7.24164 Å, Vol = 542.59 Å³. The absorption and fluorescence spectrum of Yb:GdYAl₃(BO₃)₄ crystal have also been measured at room temperature. In the absorption spectra, there are two absorption bands at 938 nm and 974 nm, respectively, which is suitable for InGaAs diode laser pumping. In the fluorescence spectra, there are two fluorescence peaks at 992 and 1040 nm. The thermal properties of Yb:GdYAl₃(BO₃)₄ crystal have been studied for the first time. The thermal expansion coefficient along c-axis is almost 5.4 times larger than that along a-axis. The specific heat of the crystal has been measured to be 0.77 J/g °C at room temperature. The calculated thermal conductivity is 5.26 Wm⁻¹ K⁻¹ along a-direction.     

Growth and characterization of Ca5(BO3)3F fiber crystals, a new nonlinear optical material for UV light generation

For the first time, Ca₅(BO₃)₃F (CBF) fiber crystals were grown by the micro-pulling down technique from LiF-based flux. Regular and transparent fibers were obtained with good optical quality. Characterization by Raman spectroscopy and EDX microprobe showed fibers compositionally homogeneous. The specific heat capacity of the fibers was measured indicating a laser damage threshold slightly lower, at room temperature, than for crystals belonging to the related rare earth calcium oxoborate family.     

Thermally stable luminescence and energy transfer in Ce, Mn doped Sr2Mg(BO3)2 phosphor

Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺ and Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ phosphors have been synthesized by conventional solid state reaction technology at 900 °C for 12 h in reducing atmosphere. The phase purity, photoluminescence (PL) properties, thermal stability, energy transfer and luminescent decay curves have been investigated. Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ phosphors show blue and deep-red¹ emission bands. The deep-red emission band is attributed to the energy transfer from Ce³⁺ to Mn²⁺. The fluorescence lifetimes of Ce³⁺ in co-doped sample are shorter than that in single doped one, which confirms that the energy transfer takes place. The phosphors have weak thermal quenching. The luminescence properties of Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ make the phosphor a new bicolor emitting material.     

Sol-gel synthesis and green upconversion luminescence in BaGd2(MoO4)4:Yb,Er phosphors

Yb³⁺/Er³⁺ codoped BaGd₂(MoO₄)₄ phosphor powders were prepared by the Sol-gel method and the upconversion luminescence properties were investigated in detail. Under 980 nm semiconductor laser excitation, BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor exhibits green upconversion luminescence with peaks at 530 and 550 nm, which are due to the transitions of Er³⁺ (²H_11/2) → Er³⁺ (⁴I_15/2) and Er³⁺ (⁴S_3/2) → Er³⁺ (⁴I_15/2), respectively. Both of the two green emission lines are produced by populating Er³⁺ ions to the excited state through a two-photon process. By monitoring the intensities of the green upconversion luminescence, the optimum conditions for the Sol-gel synthesis were determined when the molar ratio of citric acid to total chelate metal cations was 2:1 and the sintering temperature was at 1073 K. The concentration quenching effect for Er³⁺ was found at the optimum doping concentration of 6 mol%, and the critical distance for the neighboring Er³⁺ was determined to be about 21.5 Å.     

Study of the pumping regimes in Ti-sapphire and Nd0.5La0.5Al3(BO3)4 powders

Stimulated emission without a cavity was obtained (at λ=800 nm) in powders of Ti-sapphire laser crystal and compared to that in Nd_0.5La_0.5Al₃(BO₃)₄. The formation of a narrow channel in a powder sample by a pumping laser beam was found to be advantageous for stimulated emission in Ti-sapphire and disadvantageous in Nd_0.5La_0.5Al₃(BO₃)₄. The effect of the material volume density on stimulated emission in scattering Nd_0.5La_0.5Al₃(BO₃)₄ was experimentally studied. The experimental results are explained in terms of absorption of pumping light in scattering materials, penetration depth for pumping, and residence time for emission photon in the pumped volume.     

Multi-wavelength continuous-wave laser operation of Yb:Ca3Gd2(BO3)4 disordered crystal

The diode-pumped multi-wavelength continuous-wave laser operation of the disordered Yb:Ca₃Gd₂(BO₃)₄ crystal was firstly investigated in this paper. The simultaneous emission wavelengths varied from 2 to 5 in the range from 1045.4 to 1063.6 nm with the change of the absorbed pump power and crystal length. An output power of 1.4 W was obtained with four-wavelength emission, corresponding to an optical-optical slope efficiency of 23.7%. Five-wavelength emission at 1049.4, 1051.3, 1053.4, 1055.6 and 1057.4 nm was realized under the output power of 1.0 W. The absorption behavior of Yb:Ca₃Gd₂(BO₃)₄ have also been measured.     

Er:YAl3(BO3)4 glassy thin films from polymeric precursor and sol-gel methods: Waveguides for integrated optics

This paper presents the characterization of single-mode waveguides for 980 and 1550 nm wavelengths. High quality planar waveguide structure was fabricated from Y_1 − xEr_xAl₃(BO₃)₄ multilayer thin films with x = 0.02, 0.05, 0.1, 0.3, and 0.5, prepared through the polymeric precursor and sol-gel methods using spin-coating. The propagation losses of the planar waveguides varying from 0.63 to 0.88 dB/cm were measured at 632.8 and 1550 nm. The photoluminescence spectra and radiative lifetimes of the Er^{3+ 4}I_13/2 energy level were measured in waveguiding geometry. For most samples the photoluminescence decay was single exponential with lifetimes in between 640 μs and 200 μs, depending on the erbium concentration and synthesis method. These results indicate that Er doped YAl₃(BO₃)₄ compounds are promising for low loss waveguides.     

Crystal growth and spectroscopic studies of novel Yb-doped K5Nd(MoO4)4 single crystals

K₅Nd(MoO₄)₄ crystals with different Yb³⁺ concentrations were grown using Czochralski technique. Room-temperature absorption spectra were recorded and assigned on the basis of Dieke's diagram for Nd³⁺ ion; the standard Judd-Ofelt theory has been used to analyze the spectra. Increase of Yb³⁺ concentration leads to variation of the corresponding Judd-Ofelt intensity parameters. Significant contribution of the Yb↔Nd energy transfer into the formation of the Nd³⁺ absorption spectra causes the observed changes. After illumination of the crystals with CW Nd:YAG laser changes of the birefringence for the laser line of CW He-Ne laser at 633 nm were studied. Birefringence changes show good correlation with the content of Yb ions.     

Thermoluminescence properties of Ce-doped LiSr4(BO3)3 phosphor

Borates LiSr₄(BO₃)₃ were synthesized by high-temperature solid-state reaction. The thermoluminescence (TL) and some of the dosimetric characteristics of Ce³⁺-activated LiSr₄(BO₃)₃ were reported. The TL glow curve is composed of only one peak located at about 209 °C between room temperature and 500 °C. The optimum Ce³⁺ concentration is 1 mol% to obtain the highest TL intensity. The TL kinetic parameters of LiSr₄(BO₃)₃:0.01Ce³⁺ were studied by the peak shape method. The TL dose response is linear in the protection dose ranging from 1 mGy to 1 Gy. The three-dimensional thermoluminescence emission spectra were also studied, peaking at 441 and 474 nm due to the characteristic transition of Ce³⁺.     

Crystal structure and spectroscopic studies of NaGd(PO3)4

Single crystals of gadolinium–sodium polyphosphate NaGd(PO₃)₄ were grown for the first time using a flux method and characterized by X-ray diffraction. This phosphate crystallizes in a monoclinic system with P2₁/n space group and with the following unit-cell dimensions: a = 9.767(3) Å, b = 13.017(1) Å, c = 7.160(2) Å, β = 90.564(5)°, V = 910.3(4) Å³ and Z = 4. The crystal structure was solved from 3451 X-ray independent reflections with final R(F²) = 0.0219 and R_w(F²) = 0.056 refined with 164 parameters (). The atomic arrangement can be described as a long chain polyphosphate organization. Two infinite (PO₃)∝ chains with a period of eight tetrahedra run along the [0 1 1] direction. The structure of NaGd(PO₃)₄ consists of GdO₈ polyhedra sharing oxygen atoms with phosphoric group PO₄. Each Na⁺ ion is bonded to eight oxygen atoms.     

Crystal growth and Judd-Ofelt analysis of novel Yb-doped RbNd(WO4)2 single crystals

RbNd(WO₄)₂ single crystals with different concentrations of Yb³⁺ have been grown using the top seeded solution growth. Room-temperature absorption spectra were assigned on the basis of the Dieke's diagram for Nd³⁺ ion and analyzed by means of the standard Judd-Ofelt theory. It was shown that the increase of the Yb³⁺ concentration and corresponding decrease of the Nd³⁺ concentration leads to the increase of the corresponding Judd-Ofelt intensity parameters, which suggests significant contribution of the Yb-Nd energy transfer in the formation of the absorption spectra.     

Preparation and some properties of rare earth iron borates,RFe3 (BO3)4

A new series of rare earth iron borates having the general formula RFe₃(BO₃)₄ (R=Y, Nd, Sm, Gd, Dy or Ho) was synthesized. The compounds were isostructural with huntite, CaMg₃(CO₃)₄, like other rare earth double borates, RM₃(BO₃)₄, M=A1 or Ga. Single crystals of Y and Gd compounds were grown by the flux method. Thermomagnetic measurements indicated that all the compounds are paramagnetic and have no spontaneous magnetization between 78°K and 730°K.     

Spectroscopic evaluation of CaYA1O4 doped with trivalent Er, Tm, Yb and Ho for eyesafe laser applications

Spectroscopic properties of relevance for laser applications have been studied for rare earths in CaYA1O₄. Fitting of a theoretical model to observed energy levels yields crystal field parameters and unobserved levels. Structural disorder leads to broad linewidths,but cross sections are larger than in many common hosts. Tm-Tm cross relaxation rates are comparable to those in Tm: YAG, and Yb-Er transfer rates are comparable to those in Yb, Er:phosphate glass. Room temperature Yb-Er upconversion is stronger than in YAG, but modeling shows that neither unconversion nor population of Er⁴I_13/2 is very efficient upon pumping Yb. The host's yellow color intensifies upon annealing in air, a potential problem for visible laser operation. Tm or Ho 2 μm laser operation, or Er 1.5 μ operation upon direct excitation of Er⁴I_13/2, are more promising.