Infrared and visible spectroscopic studies of the ytterbium doped borate Li6Y(BO3)3

The spectroscopic study of trivalent ytterbium doped Li₆Y(BO₃)₃ is conducted in the UV-visible and infrared range. An excitation in the charge transfer band of ytterbium has been selected in order to reduce the reabsorption effect on the IR emission intensity. The maximum of the emission is located at 972 nm for an excitation at 230 nm. The energy level assignment has been successfully conducted using vibrational spectroscopy to distinguish the pure electronic transitions from the phonon-assisted ones. The splitting of the ²F_5/2 and ²F_7/2 components is equal to 523 cm⁻¹ and 676 cm⁻¹, respectively. The decay time dependence as a function of the concentration is also reported. The calculated value τ_rad is about (1.03 ± 0.01) ms for the 1% doped material. For the highest concentration, an IR excitation gives rise to the observation of a blue-green luminescence caused by two mechanisms: an erbium emission at 550 nm after upconversion and a cooperative luminescence of ytterbium ions.     

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.     

Terahertz spectroscopy of multiferroic EuFe3(BO3)4

The terahertz spectra of a rare-earth iron borate with the huntite structure are obtained for the first time. We study the low-temperature (4.0–90 K) α-polarized transmittance spectra of the EuFe₃(BO₃)₄ single crystal in the region 0.9–6.0 THz. Pronounced shifts of phonon frequencies and appearance of new phonon modes at the temperature _TS=58 K$T_S=58\text{K}$ of the R32→P₃₁21$R32\to P{3}_{1}21$ structural phase transition are observed. Additional shifts of phonon frequencies occur at the temperature _TN=34 K$T_N=34\text{K}$ of the magnetic ordering of the Fe subsystem, thus evidencing the spin–phonon coupling in this multiferroic material.     

Luminescence properties of SrSi2O2N2 doped with divalent rare earth ions

The optical properties of SrSi₂O₂N₂ doped with divalent Eu²⁺ and Yb²⁺ are investigated. The Eu²⁺ doped material shows efficient green emission peaking at around 540 nm that is consistent with 4f⁷→4f⁶5d transitions of Eu²⁺. Due to the high quantum yield (90%) and high quenching temperature (>500 K) of luminescence, SrSi₂O₂N₂:Eu²⁺ is a promising material for application in phosphor conversion LEDs. The Yb²⁺ luminescence is markedly different from Eu²⁺ and is characterized by a larger Stokes shift and a lower quenching temperature. The anomalous luminescence properties are ascribed to impurity trapped exciton emission. Based on temperature and time dependent luminescence measurements, a schematic energy level diagram is derived for both Eu²⁺ and Yb²⁺ relative to the valence and conduction bands of the oxonitridosilicate host material.     

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.     

Luminescence properties of SrSi2AlO2N3 doped with divalent rare-earth ions

The optical properties of SrSi₂AlO₂N₃ doped with Eu²⁺ and Yb²⁺ are investigated towards their applicability in LEDs. The Eu²⁺-doped material shows emission in the green, peaking around 500 nm. The emission is ascribed to the 4f⁶5d¹–4f⁷ transition on Eu²⁺. In view of the too low quantum efficiency and the considerable thermal quenching of the emission at the operation temperature of high power LED (>1W/mm²) this phosphor is only suitable for application in low power LEDs. The Yb²⁺ emission shows an anomalously red-shifted emission compared to Eu²⁺, which is characterized by a larger FWHM, a larger Stokes shift and lower thermal quenching temperature. The emission is ascribed to self-trapped exciton emission. The Yb²⁺ activated phosphor is found to be unsuitable for the use in any phosphor-converted LEDs.     

Luminescent properties of Eu and Ce ions in strontium litho-silicate Li2SrSiO4

The luminescent properties of Eu²⁺ and Ce³⁺ ions in Li₂SrSiO₄ have been studied upon excitation in the 2-20 eV region. Based on the results of luminescent measurements, values of the crystal field splitting and the centroid shift of the Ce³⁺5d configuration in Li₂SrSiO₄ were found and compared with those of Ce³⁺ ions in some other inorganic compounds. The Eu²⁺ ions in Li₂SrSiO₄ exhibit a broad band emission with a maximum at 576 nm, which is due to the 4f⁶5d→4f⁷ transition. It was shown that the long-wavelength position of the Eu²⁺ emission in Li₂SrSiO₄ is caused by the large crystal-field splitting of the Eu²⁺ 4f⁶5d configuration and relatively high degree of covalency of the Eu-O bond. The stabilization of Eu²⁺ ions in Li₂SrSiO₄ during the synthesis process requires a strong reducing agent. Two phenomenological approaches to explain the low stability of Eu²⁺ in Li₂SrSiO₄ are also discussed.     

Preparation and luminescent properties of phosphor MGd2(MoO4)4: Eu (M=Ca, Sr and Ba)

Intense red emitting phosphors MGd₂(MoO₄)₄: Eu³⁺ (M=Ca, Sr and Ba) have been synthesized by the simple sol-gel technique. The formation processes and the phase impurity of phosphors are characterized by thermogravimetry-differential thermal analysis (TG-DTA) and power X-ray diffraction (XRD). The narrower size distribution and the regular shape of the phosphor particles are also measured by Field emission scanning electronic microscopy (FE-SEM). Photo-luminescent properties of the phosphors are performed at room temperature. Their excitation spectra present strong absorption at 395 nm near-UV light and 465 nm blue light, which match well with commercial LED chips. The phosphors exhibit satisfactory and excellent red light dominated by 616 nm and their photoluminescence intensity is about 3-4 times stronger than that of phosphor YAG under the 465 nm excitation. In addition, the optimal concentrations of Eu³⁺ for phosphors MGd₂(MoO₄)₄ (M=Ca, Sr and Ba) have also been determined.     

Formation of luminescent (NH4)2SiF6 phase from vapour etching-based porous silicon

In this paper we describe the formation of a luminescent (NH₄)₂SiF₆ via porous silicon (PS) obtained from HNO₃/HF vapour etching (VE) silicon (Si) substrates. It was found that at specific conditions, PS transforms in a luminescent thick white powder (WP) layer. Scanning electron microscopy (SEM) revealed that the WP has a coral-like structure. It was also found that PS persists as an intermediate layer between the Si substrate and the WP, and seems to be the seed that transforms into the WP. SEM microanalysis show that the WP is essentially composed of silicon (Si), nitrogen (N) and fluorine (F). Fourier transform infrared (FTIR) spectroscopy investigations show that this WP contains SiF₆²⁻ and NH₄⁺ ions and N---H chemical bonds. X-ray diffraction (XRD) patterns of the WP confirm that a (NH₄)₂SiF₆ cubic phase is concerned. SEM microanalyses show an excess of Si in the WP matrix. FTIR spectroscopy and XRD analysis reveal the presence of crystalline Si particles and SiO_x, both originating from the excess of Si. The (NH₄)₂SiF₆ WP phase emits an intense photoluminescence (PL) band, shifted towards higher energies as compared to the starting PS layer. The possible origin and mechanism of the luminescence emission was discussed taking into account the ability of small SiO_x-surrounded Si particles to emit PL at rather high energy. The wide range variation of the thickness of the (NH₄)₂SiF₆ WP may be easily used for the grooving of Si wafers.     

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.     

Synthesis and properties of magnetic and luminescent Fe3O4/SiO2/Dye/SiO2 nanoparticles

A simple and reproducible method was developed to synthesize a novel class of Fe₃O₄/SiO₂/dye/SiO₂ composite nanoparticles. As promising candidates for use in bioassays, the obtained nanoparticles have an average diameter of 30 nm, and the thickness of the outer shell of silica could be tuned by changing the concentration of the silicon precursor tetraethyl orthosilicate during the synthesis. These multifunctional nanoparticles were found to be highly luminescent, photostable and superparamagnetic. The luminescence intensity of the nanoparticles was increased as the dye concentration was increased in the preparation process. The color of the luminescence was successfully tuned by incorporating different dyes into the nanoparticles. The measurements of the emission spectra indicated that relative to the dye molecules dissolved in ethanol, the emission of the dye-doped nanoparticles exhibited either a red shift or a blue shift, to which a tentative explanation was given.     

Influence of different annealing conditions on the luminescent properties of Li2B4O7:Mn single crystals

The influence of reducing annealing and repeated oxidizing annealing of the Li₂B₄O₇:Mn single crystals on their thermostimulated luminescence (TSL) and X-ray luminescence (XL) has been studied. Because of the oxygen vacancies formation and the dopant ions reduction, the reducing annealing results in a drastic decrease of the luminescence intensity along with the simultaneous shift of a part of the maxima and redistribution of the peak intensities. The repeated annealing in the oxidizing environment leads only to the partial reduction of the luminescent properties of the Li₂B₄O₇:Mn crystals.     

Preparation and luminescent properties of BaCa2Si3O9:Eu

A blue emitting phosphor of the triclinic BaCa₂Si₃O₉:Eu²⁺ was prepared by the combustion-assisted synthesis method and an efficient blue emission ranging from the ultraviolet to visible was observed. The luminescence and crystallinity were investigated using luminescence spectrometry and X-ray diffractometry (XRD), respectively. The emission spectrum shows a single intensive band centered at 445 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. The excitation spectrum is a broad extending from 260 to 450 nm, which matches the emission of ultraviolet light-emitting diodes (UV-LEDs). The critical quenching concentration of Eu²⁺ in BaCa₂Si₃O₉:Eu²⁺ phosphor is about 0.05 mol. The corresponding concentration quenching mechanism is verified to be a dipole-dipole interaction. The CIE of the optimized sample Ba_0.95Ca₂Si₃O₉:Eu_0.05²⁺ was (x, y)=(0.164, 0.111). The result indicates that BaCa₂Si₃O₉:Eu²⁺ can be potentially useful as a UV radiation-converting phosphor for white light-emitting diodes (LEDs).     

VUV-UV excited luminescent properties of LnCa4O(BO3)3:RE (Ln=Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa₄O(BO₃)₃:RE³⁺ (LnCOB:RE, Ln=Y, La, Gd, RE=Eu, Tb, Dy, Ce) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos’ and Jφrgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. Jφrgensen, Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E_ct were calculated and compared with their excitation spectra.Eu³⁺ and Tb³⁺ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce³⁺ ions do not show efficient luminescence and quench the luminescence of Tb³⁺ ions when Tb³⁺ and Ce³⁺ ions are co-doped into LnCOB. GdCOB doped with Dy³⁺ shows yellowish white light under irradiation of 254 nm light for the reason that Gd³⁺ ions transfer the energy from itself to Dy³⁺. Because of the existence of Gd³⁺, the samples of GdCOB:RE³⁺ show higher excitation efficiency than LaCOB:RE³⁺ and YCOB:RE³⁺, around 188 nm, which indicates that the Gd³⁺ ions have an effect on the host absorption and can transfer the excitation energy to the luminescent center such as Tb³⁺, Dy³⁺ and Eu³⁺.     

Fluorescence emission spectrum and energy transfer in Eu and Mn co-doped Ba2Ca(BO3)2 phosphors

Eu²⁺ and Mn²⁺ co-doped Ba₂Ca(BO₃)₂ phosphors yield two emission bands consisting of green and red components under the excitation of 360 nm, which shows a great potential for white LEDs. Effective energy transfer occurs in Eu²⁺/Mn²⁺ co-doped Ba₂Ca(BO₃)₂ host due to the large spectral overlap between the emission of Eu²⁺ and the excitation of Mn²⁺. The energy transfer from Eu²⁺ to Mn²⁺ is thoroughly investigated by their excitation, emission and photoluminescence decay behaviors, and is demonstrated to be via the dipole–quadrupole interaction.     

Continuous-wave diode-pumped operation of an Yb:NaLa(WO4)2 laser at room temperature

Room-temperature continuous-wave (cw) laser operation is demonstrated with the newly developed Yb:NaLa(WO₄)₂ disordered crystal by end-pumping with a fiber-coupled diode laser. A maximum output power of 330 mW is obtained with an optical efficiency of 4.9% and a slope efficiency of 6.3% with respect to the incident pump power. The efficiencies in terms of the absorbed pump power are roughly three times higher. Sellmeier dispersion curves for the ordinary and extraordinary refractive indices of the NaLa(WO₄)₂ host are reported along with crystallographic and spectroscopic properties related to the Yb³⁺-doping.     

Nature of optical properties of GdFe3(BO3)4 and GdFe2.1Ga0.9(BO3)4 crystals and other 3d5 antiferromagnets

Influence of the partial substitution of paramagnetic Fe³⁺ ions by diamagnetic Ga³⁺ ions in the trigonal crystal GdFe₃ (BO₃)₄ on its optical and magnetic properties is studied and discussed in connection with problems common for all antiferromagnets containing 3d ⁵ ions. Polarized optical absorption spectra and linear birefringence of GdFe₃ (BO₃)₄ and GdFe_2.1Ga_0.9 (BO₃)₄ single crystals have been measured in the temperature range 85–293 K. Specific heat temperature dependence (2–300 K) and structure of GdFe_2.1Ga_0.9 (BO₃)₄ crystal have been also studied. As a result of substitution of 30% Fe to Ga the Neel temperature diminishes from 38 till 16 K, the strong absorption band edge shifts on 860 cm^-1 (0.11 eV) to higher energy and the d-d transitions intensity decreases substantially larger than the Fe concentration does. Strong absorption band edge is shown to be due to Mott-Hubbard transitions. Correlation between position of the strong absorption band edge and the Neel temperature of antiferromagnets has been revealed. Properties of the doubly forbidden d-d transitions in the studied crystals and in other antiferromagnets are explained within the framework of the model of the exchange-vibronic pair absorption, which is theoretically analyzed in detail. The model permitted us to determine the connection between parameters of d-d absorption bands (intensity, width and their temperature dependences), on the one hand, and the exchange, spin-orbit and electron-lattice interactions, on the other hand.     

The Yb to Er energy transfer in YAl3(BO3)4 crystal

The Yb³⁺ to Er³⁺ energy transfer in yttrium aluminum borate (YAB) crystal is investigated with the rate equation without considering the back energy transfer. The energy transfer coefficients (W₂₅) in the crystals with different Yb³⁺ concentrations are determined and compared with those in other crystals. The transfer efficiencies and the micro-parameters of energy transfer and migration are also determined. The results show that the energy transfer from Yb³⁺ to Er³⁺ in YAB crystal is very efficient and the Yb³⁺–Er³⁺ co-doped YAB crystal may be a good candidate for the 1.55 μm laser media.     

Luminescence optimization of Eu-doped LnAl3(BO3)4 (Ln=Y, Gd) red phosphor using spray pyrolysis

LnAl₃(BO₃)₄:Eu³⁺ (Ln=Y, Gd) red phosphor particles were prepared by spray pyrolysis and the luminescent intensity under vacuum ultraviolet (VUV) excitation was investigated by changing Eu³⁺ content, Y/Gd molar ratio, and boron content. The concentration quenching for Eu³⁺ activator was observed at 5 at%. The highest luminescent intensity at 615 nm due to the ⁵D₀→⁷F₂ transitions of Eu³⁺ was achieved when the ratio of Gd to Y was 0.55. The R/O ratio (obtained by dividing the red emission intensity at 615 nm with the orange one at 592 nm), however, was not influenced by the G/Y ratio. Using excess boron, up to 135% of the stoichiometric quantity, improved the emission intensity of LnAl₃(BO₃)₄:Eu³⁺ red phosphor. According to XRD analysis, the sample prepared using boron of a stoichiometric quantity had YBO₃ phase as a minor phase. Such YBO₃ phase progressively disappeared with an increase in the excess quantity of boron, which was responsible for the enhancement of emission intensity. In addition, the R/O ratio became larger and larger by increasing the excess content of boron due to a reduction in the symmetry of Y site. Consequently, both the emission intensity and the color coordinate of LnAl₃(BO₃)₄:Eu³⁺ red phosphors were successfully optimized in terms of the Y/Gd ratio and the excess quantity of boron in spray pyrolysis.     

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.