Low-temperature time-resolved VUV luminescence spectroscopy of SrF<Subscript>2</Subscript>: Er<Superscript>3+</Superscript> crystals

Time-resolved excitation and emission spectra of SrF₂: Er³⁺ upon selective excitation with synchrotron radiation in the VUV and ultrasoft x-ray ranges at T = 8 K were studied. The VUV luminescence of SrF₂: Er³⁺ derives from high-energy interconfiguration 4f¹⁰5d-4f¹¹ transitions in the Er³⁺ ion. The VUV emission spectrum revealed, in addition to the 164.5-nm band (millisecond-range kinetics), a band at 146.4 nm (with a decay time of less than 600 ps). The formation of excitation spectra for the f-f and f-d transitions in the Er³⁺ ion is discussed.     

Time-Resolved Vacuum Ultraviolet Spectroscopy of Er<Superscript>3+</Superscript> Ions in the SrF<Subscript>2</Subscript> Crystal

The photoluminescence and photoexcitation spectra as well as the luminescence decay kinetics of Er³⁺ ions in the visible ultraviolet and vacuum ultraviolet (VUV) regions have been studied by the method of low-temperature, time-resolved VUV-spectroscopy on excitation by synchrotron radiation. In the VUV spectral region of the luminescence of SrF₂:1% Er³⁺, the 146.5-nm band with a time of decay of less than 0.6 nsec was revealed together with the well-known emission band at 164.3 nm (decay constant in the microsecond range). Its possible nature is discussed. The specific features of the formation of photoexcitation spectra of the f-f and f-d transitions in the Er³⁺ ion are considered. Competition between the processes of excitation of f-f and d-f luminescence has been revealed. It manifests itself in the inverse relationship of their photoexcitation spectra in a range of energies of incident photons that are close to the position of the 4fⁿ⁻¹5d configuration levels. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 519–523, July–August, 2005.     

Luminescence spectroscopy of Er-doped and Er, Yb-codoped LaPO4 single crystals

LaPO₄ single crystals lightly doped with Er³⁺, and codoped with Er³⁺ and Yb³⁺ have been grown by spontaneous nucleation in a lead phosphate flux. Absorption and luminescence spectra have been measured in the visible and near-IR regions and the excited state dynamics has been studied upon pulsed laser excitation. The obtained results have allowed the evaluation of the effective emission cross-sections around 1.5 μm, that have been found to be similar to important oxide laser crystals doped with Er³⁺. Efficient visible upconversion has been observed upon excitation at 980 nm in the codoped crystals. This behaviour is attributed to Yb³⁺-Er³⁺ energy transfer processes.     

Facile synthesis of well-dispersed SrF2:Yb/Er upconversion nanocrystals in oleate complex systems

Well oil-dispersible SrF₂:Yb³⁺/Er³⁺ upconversion (UC) nanocrystals (NCs) were easily synthesized in the water-ethanol-oleic acid-sodium oleate complex systems. The as-prepared NCs all show size-uniformity, and their sizes, morphologies can be controlled by varying the solvent and reaction time, and rectangular SrF₂:Yb³⁺/Er³⁺ nanosheets with the sizes of 5-25 nm can be obtained. The possible mechanism on the nucleation and growth of nanocrystals occurred at the oleic acid/sodium oleate interface was also discussed. The size and morphology dependent UC luminescence behaviors have been observed in SrF₂:Yb³⁺/Er³⁺ NCs, and their UC luminescence transitions were proposed. The as-prepared UC nanocrystals are expected to fulfill the demand for biological applications.     

Structure and Metastability of MF<Subscript>2</Subscript> (M = Ca,Sr, Ba) Fine Powders Mechanochemically Doped with Er<Superscript>3+</Superscript> Ions

In the paper thermal treatment investigations of the MF₂ (M = Ca, Sr, Ba) fine powders mechanochemically doped with Er³⁺ ions using electron paramagnetic resonance and X-ray diffraction are presented. It is shown that the prepared samples are found in the nonequilibrium metastable state characterized by the high concentration of the cationic vacancies and prevalence of the cubic symmetry-doped Er³⁺ ion centers. Vacancies formed when the deformation exceeds the elastic limit serve both as the means for a nonlocal charge compensation and a route for mechanically activated diffusion. Annealing brings the powders to the ground state with the most of the vacancies healed and the trigonal symmetry of the impurity Er³⁺ centers in SrF₂ and BaF₂ due to the local compensation by the interstitial fluorine ion.     

Site-selective spectroscopy of Er3+:Ti:LiNbO3 waveguides

Starting from previous investigations in LiNbO₃ bulk crystals, we studied the optical properties of Er³⁺ ions in Ti:LiNbO₃ channel waveguides and investigated the waveguide-specific lattice environment of the Er³⁺ ions (“sites”) caused by the doping method used and the presence of a large number of Ti⁴⁺ ions. For that purpose the method of combined excitation–emission spectroscopy was applied for the first time to waveguides at low temperatures. Comparing the spectroscopic results obtained for the green, red, and near-IR luminescence (λ≈550, ≈650 and ≈980 nm) under direct (450 nm), 2-step (980 nm), and 3-step (1.5 μm) laser excitation, we found several distinguishable Er³⁺ sites which in terms of energy levels and relative numbers are similar to those in bulk material, but exhibit significantly different up-conversion efficiencies and strongly inhomogeneously broadened transitions. Moreover, we were able to distinguish isolated and cluster Er³⁺ sites by their characteristic excitation and emission transition energies and studied the respective excitation/relaxation channels. The cluster sites are most efficient in the up-conversion process, especially under 3-step excitation. Using accepted microscopic models for Er³⁺ and Ti⁴⁺ incorporation into the LiNbO₃ crystal lattice, the site distribution and up-conversion mechanisms are elucidated and their consequences for laser applications in different spectral regions are discussed. Received: 16 November 2000 / Published online: 21 March 2001     

Er3+离子掺杂钡镓锗玻璃上转换发光机理研究

研究了Er³⁺离子掺杂钡镓锗玻璃的吸收光谱、拉曼光谱和上转换光谱.分析了Er³⁺离子在钡镓锗玻璃中的上转换发光机理.结果表明：玻璃的最大声子能量为828cm^-1，紫外截止波长为275nm.采用800nm和980nmLD激发玻璃样品，在室温下观察到强烈的上转换绿光和红光发射.随着Er³⁺离子浓度的增加，绿光发光强度先增加后减小，而红光发光强度呈单调递增趋势.能量分析表明：800nmLD激发产生的绿光主要源于Er³⁺离子4I_13/2能级的激发态吸收过程；红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程.980nmLD激发产生的绿光主要源于Er³⁺离子4I_11/2能级之间的能量转移过程；而红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程和4I_13/2能级的激发态吸收过程.通过量子效率分析，发现采用800nmLD激发Er³⁺离子掺杂浓度为1mol% 的样品时，上转换绿光发光效率最高. 关键词： 上转换发光机理 3+离子掺杂')" href="#">Er³⁺离子掺杂 钡镓锗玻璃     

The fluorescence properties of Yb3+ and Er3+ Co-doped YAl3(BO3)4 powders prepared by sol-gel method

Yb³⁺ and Er³⁺ co-doped YAB powders were prepared by sol-gel method. The structure and fluorescence properties were investigated. XRD pattern indicated that the single phase was obtained at 1150°C and the structure belonged to rhombohedral. Under 379 nm excitation, two emissions around 983 nm and 1531 nm were observed and the effect of Yb³⁺ ion concentration on the emission intensity was discussed. The energy transfer was observed under 930 nm excitation and the energy transfer efficiencies for all samples were calculated. The lifetimes of ² F _5/2 level of Yb³⁺ ion and ⁴ I _13/2 level of Er³⁺ ion were measured and the effect of Yb³⁺ ion concentration on the lifetime was also discussed. The results indicated that there was an additional mechanism for the decay of ⁴ I _13/2 level in powder samples. The Yb³⁺ and Er³⁺ co-doped YAB powders should be a potential candidate for ceramic laser materials.     

Thermal and optical properties of Er-doped oxyfluorotellurite glasses

Er³⁺-doped oxyfluorotellurite glasses with four different concentrations of Er³⁺ ions have been prepared and investigated their thermal, optical absorption, excitation and luminescence properties. From the DSC spectra, glass transition and onset of crystallization temperatures have been found. Judd-Ofelt intensity parameters have been derived from the absorption spectrum and are in turn used to calculate radiative properties for the important luminescent levels of Er³⁺ ions. The calculated radiative properties are comparable to experimental values. The glasses show intense green and weak red emission under normal excitation with 451 nm. The decrease in emission intensities and lifetimes of the ⁴S_3/2 level with concentration of Er³⁺ ions has been explained as due to energy transfer processes between Er³⁺ ions. The stimulated emission cross-sections and quantum efficiencies of the green and infrared emissions have been determined. The results indicate that the glasses may be suitable for use as a laser medium in making solid-state green laser by normal pumping route and as laser medium and optical amplifier in the 1.5 μm region.     

Ultraviolet excitation of rare-earth-doped YSZ crystals

Abstract

The optical properties of nominally pure and Er³⁺- or Pr³⁺ -doped yttria-stabilized zirconia single crystals were investigated under UV light excitation. In the excitation spectra of both types of doped crystals, a broad UV band is observed. Under excitation with light of different wavelengths inside this band, the luminescence features of the doped crystals are different. YSZ: Pr³⁺ samples exhibit the characteristic 4f → 4f emission of the Pr³⁺ ions. In YSZ: Er³⁺ crystals, both the Er³⁺ ion and the intrinsic luminescence are observed. Host to Er³⁺ ion radiative energy-transfer is also demonstrated. No dependence of the transfer process with the excitation wavelength was found. These results suggest that the UV band in Er³⁺ -doped crystals is associated with the lattice-dopant ion interaction rather than with the 4f5d interconfigurational band of the Er^3? ions.     

Site selective spectroscopy of rare earth doped ThO2

The individual sites present in ThO₂ doped with Eu³⁺ and Er³⁺ have been studied by site selective spectroscopy. A cubic site corresponding to a rare earth charge compensated distantly and two sites having local charge compensation have been identified. One of the locally compensated sites is present only at moderate temperature while the other is formed at higher temperatures and is stable to high temperatures. The measurements are related to catalytically excited fluorescence of ThO₂, previous luminescence measurements, and magnetic resonance experiments that observe the presence of local F^_ charge compensation of rare earth dopants.     

Infrared-to-visible frequency upconversion in SrAl2O4 powders containing Er3+ and Yb3+

The phenomenon of frequency upconversion (UC) is observed in Er³⁺:Yb³⁺:SrAl₂O₄ powders prepared by combustion synthesis. Strong UC emission at the green (bands peaked at 521, 538, 547, and 562 nm) and weak UC emission at the red (bands peaked at 659 and 682 nm) corresponding to 4f–4f transitions of Er³⁺ were observed when the samples were irradiated with near-infrared laser excitation at ～980 nm. Saturation of UC emission is observed for concentrations of 1.5 wt.% of Er³⁺ and 1.5 wt.% of Yb³⁺. The green-to-red intensity ratio, on the other hand, increases linearly with Er³⁺ concentration (Er³⁺ concentration varying from 0.5 to 1.5 wt.%) while keeping Yb³⁺ concentration fixed (at 1.5 wt.%). The green UC decay time was measured and Er³⁺–Er³⁺ interaction was suggested as a possible mechanism to explain the luminescence quenching effect observed.     

Influence of MgO codoping on the optical properties of Er3+-doped near-stoichiometric LiNbO3

Four near-stoichiometric lithium niobate (NSLN) crystals codoped with Er³⁺ (1 mol%) and MgO (0, 0.5, 1.0, and 2.0 mol%) were grown from K₂O-based flux in air using top seeded solution growth technique. The [Li]/[Nb] ratio, estimated from the blueshift of ultraviolet absorption edge, is 97.2% in NSLN:Er. MgO; codoping can increase the segregation coefficient of Er³⁺ in NSLN:Er:MgO crystal. The photorefractive damage threshold is enhanced by three orders of magnitude for NSLN:Er codoped with 1 mol% MgO, it coincides with the peak shift of OH⁻ absorption spectrum from 3481 to 3535 cm⁻¹. Judd–Ofelt theory based on absorption spectra is used to analyze the influence of MgO concentration on the Judd–Ofelt intensity parameter, transition strength, fluorescence branching ratio, and stimulated emission cross section. From the time-resolved emission spectra and the comparison among emission spectra, two Er³⁺ crystal-field sites are ascertained in NSLN:Er codoped with 2 mol% MgO, this coincides with the bimodal structure in X-ray photoelectron spectrometry spectra. The upconversion processes under pulse excitation is proposed based on the pump energy dependence and decay kinetics. The distribution of Er³⁺-clustered sites in NSLN:Er:MgO series is discussed based on the nonexponential decay curves monitored at 550 nm under two-photon excitation.     

Mesoporous silica-coated NaYF4:Yb3+, Er3+ particles for drug release

NaYF₄:Yb³⁺, Er³⁺ nanoparticles were successfully prepared by a polyol process using diethyleneglycol (DEG) as solvent. These NaYF₄:Yb³⁺, Er³⁺ nanoparticles can be coated with mesoporous silica using nonionic triblock copolymer EO₂₀PO₇₀EO₂₀ (P 123) as structure-directing agent and other materials. The composites can load ibuprofen and release the drug in the phosphate buffer solution (PBS). The composites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen absorption/desorption isotherms, fluorescence spectra, and UV/Vis absorption spectra, respectively. The composites have the mesoporous structure. In addition, the composites emit red fluorescence (from Er³⁺) under 980 nm near infrared laser excitation, which can be used as fluorescent probes in the drug-delivery system.     

Influence of Yb doping concentration on upconversion luminescence of Er in Lu2O3 phosphor

Cubic phase Lu₂O₃:Er³⁺/Yb³⁺ nanocrystal phosphors were prepared by sol–gel method. Fourier transform infrared (FT-IR) spectra were measured to evaluate the vibrational feature of the samples. Green and red radiations were observed upon 980 nm diode laser excitation. Laser power and Er³⁺ or Yb³⁺ doping concentration dependence of upconversion luminescence were studied to understand upconversion mechanisms. Excited state absorption, cross relaxation and energy transfer processes are the possible mechanisms for the visible emissions.     

Mutual quenching of Er photoluminescence under two laser excitation in GaN:Er

Erbium photoluminescence in GaN:Er was studied with above-band-gap excitation, provided by a He–Cd laser and below-band-gap excitation by a tunable Ti–Sa laser. The spectra obtained with these two lasers exhibit different spectral shapes. When both lasers are used at the same time, we observe that the Er³⁺ photoluminescence induced by each of the lasers is partly quenched by the illumination of the other laser. In this experiment, one of the lasers is modulated and a lock-in amplifier is used to filter the corresponding photoluminescence signal. The spectra recorded this way are found to be linear combinations of spectra obtained with each of the lasers used separately. This effect is explained by the presence of defects mediating the excitation towards the Er³⁺ ions. These defects act as electron traps, which can be populated by one specific laser excitation and are photo-ionized by the other laser leading to a large quenching of Er³⁺ emission.     

Erbium ion luminescence of silicon nanocrystal layers in a silicon dioxide matrix measured under strong optical excitation

The photoluminescence (PL) spectra and kinetics of erbium-doped layers of silicon nanocrystals dispersed in a silicon dioxide matrix (nc-Si/SiO₂) are studied. It was found that optical excitation of nc-Si can be transferred with a high efficiency to Er³⁺ ions present in the surrounding oxide. The efficiency of energy transfer increases with increasing pumping photon energy and intensity. The process of Er³⁺ excitation is shown to compete successfully with nonradiative recombination in the nc-Si/SiO₂ structures. The Er³⁺ PL lifetime was found to decrease under intense optical pumping, which implies the establishment of inverse population in the Er³⁺ system. The results obtained demonstrate the very high potential of erbium-doped nc-Si/SiO₂ structures when used as active media for optical amplifiers and light-emitting devices operating at a wavelength of 1.5 μm.     

Dependence of the Er<Subscript>2</Subscript>O<Subscript>3</Subscript> selective emission on the intensity of laser thermal excitation

The dependence of the selective emission (SE) spectra of erbium oxide (Er₂O₃) in the visible and near-IR spectral ranges on the laser excitation intensity at a wavelength of 10.6 μ m is experimentally studied. The intensity ratio for the Er³⁺ electronic and vibronic transitions in the SE spectra is varied with an increase in the laser intensity to 10 kW/cm². The mechanism for the multiphonon fluctuation excitation of electronic states and a possibility for the SE application in the observation of the thermo-photo-laser effect are discussed.     

氟化物、氟磷酸盐和磷酸盐玻璃中Er3+离子的发光研究

测定了氟化物、氟磷酸盐和磷酸盐玻璃中Er³⁺离子的吸收、荧光和激发光谱,解释了基质玻璃对Er³⁺离子发光的影响。进一步研究了在这三种基质玻璃中Er³⁺离子发光的浓度效应和温度效应,讨论了Er³⁺离子内和离子间的能量转移过程。 关键词：