Dynamics of the Yb3+ to Er3+ energy transfer in LiNbO3

The energy transfer dynamics between Yb³⁺ and Er³⁺ ions in lithium niobate is investigated after ytterbium-pulsed excitation at 920 nm. The sensitisation of the LiNbO₃:Er³⁺ system with Yb³⁺ ions does not modify the lifetime of the ⁴I_13/2 erbium level (1.5-μm emission), whereas it induces a marked, concentration-dependent change in the lifetime of the ²F_5/2 (Yb³⁺) and ⁴S_3/2 (Er³⁺) multiplets (1060-nm and 550-nm emissions, respectively). The results are analysed by using the rate-equation formalism and cross-relaxation model for the energy transfer. Received: 15 October 1998 / Revised version: 24 November 1998 / Published online: 24 February 1999     

Spectroscopic characterisation of LaGaO3:Er3+ crystals

LaGaO₃ crystals doped with Er³⁺ ions were grown by the Czochralski method and their optical properties were examined. The Er³⁺ energy levels have been determined from the low-temperature absorption and emission spectra. The results of Judd–Ofelt analysis are presented and compared with experimental data. The emission cross sections are determined for the ⁴ I _13/2→⁴ I _15/2 (1.55 μm) and ⁴ I _11/2→⁴ I _13/2 (2.85 μm) transitions of erbium. Received: 6 December 1999 / Revised version: 10 February 2000 / Published online: 27 April 2000     

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     

Enhancement of upconversion intensity in Er3+ doped tellurite glass in presence of Yb3+

TeO₂–PbO glasses doped/codoped with Er³⁺/Er³⁺-Yb³⁺ ions have been fabricated by melting and quenching method. Efficient frequency upconversion emissions spanning from blue to red regions corresponding to the ²H_11/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions, respectively, upon excitation with 976 nm diode laser radiation have been observed. The variations observed in the intensity of whole upconversion emission spectra due to the presence of the Yb³⁺ ions are reported and discussed in detail.     

Luminescence of transparent glass ceramics containing Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> zirconate-titanate nanocrystals

Luminescence regularities have been studied in new erbium/ytterbium materials based on glasses and glass ceramics of a magnesium-aluminosilicate system containing nanoscale erbium/ytterbium zirconate titanate crystals with the pyrochlore structure. Lifetimes of Yb³⁺ and Er³⁺ ions in the ² F_5/2 state and in the ⁴I_11/2 and ⁴I_13/2 states, respectively, and the efficiency of Yb³⁺ → Er³⁺ energy transfer have been evaluated. The identified spectral-luminescent characteristics of the studied glasses and glass ceramics co-doped with erbium and ytterbium ions show that these materials are promising media for producing laser generation in the spectral range around 1.5 μm.     

Raman study on vapor-phase equilibrated Er:LiNbO3 and Er:Ti:LiNbO3 crystals

Raman spectra of Er:LiNbO₃ crystal and Ti-diffusedEr:LiNbO₃ strip waveguide, in which the Li/Nb ratio was altered using a vapor-phase equilibration (VPE) technique, were measured at room temperature in the wave-number range 50–3500 cm^-1. Both 488 and 514.5 nm radiations were used to excite Raman scattering, A₁(TO) and E(TO) modes were recorded at backward scattering geometry. The results indicated that the lattice vibrational spectra of the as-grown Er:LiNbO₃ are almost the same as those of pure LiNbO₃ except for the little shift of the peak position and the change of relative intensity of some peaks. In comparison with the spectra of as-grown Er:LiNbO₃ crystal the vapor-phase equilibrated Er:LiNbO₃ and Er:Ti:LiNbO₃ crystals in the lattice vibrational region exhibit the following features: firstly, Raman peaks become narrow, indicating that the VPE process has brought Er:LiNbO₃ and Er:Ti:LiNbO₃ crystals closer to a stoichiometric composition; secondly, relative intensity of some peaks varies with the VPE time; and finally, slight blue shifting in peak position was observed. Some of these features were correlated with the NbO₆ octahedra and with the site distribution of the doped Er ions. In addition, green fluorescence peaks and/or bands associated with the electron transitions ² H _11/2?⁴ I _15/2 and ⁴ S _3/2?⁴ I _15/2 of the doped Er³⁺ were also observed. For 488 nm excitation they appear in the wavenumber range of 1200–3000 cm^-1 and are well separated from lattice vibrational region; for 514.5 nm excitation, however, these fluorescence peaks shift towards the low wavenumber region and overlap partially with the lattice vibrational spectra. Received: 24 May 2000 / Accepted: 29 May 2000 / Published online: 13 September 2000     

Infrared, visible and upconversion emission of CaAl12O19 powders doped with Er3+, Yb3+ and Mg2+ ions

CaAl₁₂O₁₉ powders doped with Er³⁺, Yb³⁺, and Mg²⁺ ions have been prepared by a low-temperature combustion synthesis technique. Formation and chemical compositions were analysed by powder X-ray diffraction and energy-dispersive spectroscopy. The visible luminescence spectra of the doped phosphor upon excitation with ∼378 nm radiation from a Xenon lamp have been studied. A broad band emission in the range of 1400–1700 nm with a peak around 1.5 μm and FWHM of about ∼80 nm responsible for the eye-safe telecommunication window has been observed upon direct excitation with a NIR laser into the ⁴I_11/2 level of Er³⁺. The effect of co-doping with Yb³⁺ and Mg²⁺ ions in the CaAl₁₂O₁₉:Er³⁺ matrix on the photoluminescence intensity corresponding to the ²H_11/2,⁴S_3/2→⁴I_15/2, ⁴F_9/2→⁴I_15/2 and ⁴I_13/2→⁴I_15/2 transitions of Er³⁺ is elaborated and discussed in detail.     

Optical properties of Eu3+ and Ho3+ in fluoride glasses

Conclusions Emission and excitation spectra as well as the lifetime and the Judd-Ofelt parameters were determined for the different sites occupied by Eu³⁺ ions in a fluorzirconate glass. As has been observed in borate glasses, the Ω₄ parameter increases with the excitation energy of the⁷F₀→⁵D₀ transition, while Ω₄ is nearly constant [5, 6]. These parameters are lower than in borate glasses by a factor of close to 3. The optical properties of the Eu³⁺ ions in the studied glass appear to be dominated by only one class of sites; however, the presence of a second class of sites is possible. Efficient energy transfer from Eu³⁺ to Ho³⁺ is observed, but the energy transfer parameter does not depend appreciably on the excitation wavelength. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 4, pp. 185–190, July–August, 1995.     

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     

Confocal micro-luminescence of Zn-diffused LiNbO3:Tm channel waveguides

Zinc-diffused channel waveguides fabricated in thulium-doped LiNbO₃ have been analyzed by means of confocal micro-luminescence techniques. Modifications induced by Zn²⁺ ions in the doped-crystal substrate are characterized following the evolution of the ³H₄→³H₆ luminescence of thulium ions at 795 nm, showing the existence of two different regions in the waveguide. Several Raman modes of LiNbO₃ have been used as well to study the differences between the waveguide and the bulk material.     

Infrared energy transfer in Tm3+:LiNbO3

The infrared optical properties of LiNbO₃ crystals doped with variable thulium concentrations have been studied. In particular, the infrared emissions that appear after direct pumping to the ³H₄ multiplet (795 nm) have been analyzed. The emission spectra, as well as the lifetimes, show that an efficient energy transfer between ³F₄ and ³H₄ levels takes place. The concentration dependence of the lifetimes has been studied and the transfer probability has been characterized.     

Observation of fine structure in the photoluminescence spectrum of an Er3+ ion in an amorphous silicon matrix

A multicomponent Stark structure corresponding to a 4I _13/2→4I _15/2 transition in the 4f ¹¹ shell of Er³⁺ ions is observed in hydrogenated amorphous silicon (a-Si:H) subjected to low-temperature (150 °C) anneal. The observation of narrow, strong components indicates that the erbium ions form a highly ordered local surrounding (Er-O-Si nanoclusters) in the labile, disordered structural network of a-Si:H. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 12, 780–783 (25 December 1999) Deceased.     

Local crystallization in an oxyfluoride glass doped with Er3+ ions using a continuous argon laser

Local crystalline formation in erbium doped oxyfluoride glass has been obtained under a cw Argon laser irradiation up to 1.8 W pumping power. By exciting at 514 nm, the emission from 800 nm and 850 nm corresponding to the ⁴S_3/2(²H_11/2)→⁴I_13/2 electronic transitions have been analyzed both inside and outside the irradiated area. The changes in the emission spectra indicate that the high power Ar laser irradiation has resulted in a localized desvitrification process. The temperature dependence of the fluorescence intensity ratio of the 800 nm and 850 nm emission bands has been used to determine the temperature of the irradiated zone. Moreover, the average lifetime of the ⁴S_3/2(²H_11/2) thermalized levels have been measured as a function of the excitation spot position. An important decrease is observed at the irradiated area. These results confirm that a localized cristalline phase has been created by the laser action.     

The kinetic limitation of anti-stokes luminescence of Er3+ and Yb3+ doped infrared upconversion materials

Infrared-to-visible wave-length conversion in the Yb³⁺−Er³⁺ doped phosphors system has been described by a simple three level model based on two ions mechanism. The excitation in the range of 900–1000 nm of an IR-photon is first absorbed by Yb³⁺ ion as a sensitizer attributed to the resonant energy transition in Er³⁺ ion from ⁴ I _3/2 → ⁴ S _15/2 and ¹ F _9/2 → ⁴ I _15/2, respectively for green and red emission. The essential energy transfer processes in this system i.e. upconversion from ⁴ I _11/2 and ¹ I _13/2, cross-relaxation from ⁴ S _3/2 and ¹ F _9/2 are taken into account. The limitations of the rate-equation approach are examined with a focus on the underlying dynamics of this rare-earth system.     

IR luminescence of thulium-activated crystals of double sodium yttrium fluoride Na0.4Y0.6F2.2:Tm3+: Self-quenching of luminescence from the 3H4 level

Na_0.4Y_0.6F_2.2:Tm³⁺ crystals with thulium contents of 0.5–20% have been grown by the Stockbarger-Bridgman method. The concentration dependences of the steady-state spectra and luminescence kinetics from the ³ H ₄ and ³ F ₄ thulium levels upon selective laser excitation of a series of Na_0.4Y_0.6F_2.2:Tm³⁺ crystals (0.5–20% Tm) are investigated. It is shown that the luminescence from the ³ H ₄ level becomes significantly quenched with an increase in the concentration due to the nonradiative energy transfer. No concentration quenching of luminescence from the ³ F ₄ level is observed. Possible schemes of self-quenching are considered for the ³ H ₄ thulium level, the self-quenching microparameters and macrorates are estimated using model quantum-mechanical calculation, and the most likely self-quenching mechanisms and schemes are found from comparison of the calculated and experimental self-quenching rates. Good agreement is obtained between the experimental and calculated kinetic curves. It is shown that, under pumping near ∼0.8 μm, self-quenching of the ³ H ₄ thulium level leads to effective occupation of the ³ F ₄ level and increases the luminescence intensity in the range of 1.7–1.9 μm. It is concluded that Na_0.4Y_0.6F_2.2:Tm³⁺ crystals are promising active media for tunable lasers in the range of 1.7–1.9 μm, with small thermal loss under laser-diode pumping near 0.8 μm. Original Russian Text ? S.é. Ivanova, A.M. Tkachuk, A.A. Mirzaeva, F. Pellé, 2009, published in Optika i Spektroskopiya, 2009, Vol. 106, No. 6, pp. 922–930.     

Photoluminescence of erbium ions in titanium oxide xerogel in porous anodic alumina matrices

It is shown that the structures of erbium-doped titanium oxide xerogel/porous anodic alumina manifest strong photoluminescence at 1.53 µm due to the ⁴I_13/2–⁴I_15/2 transition of Er³⁺ ions in the xerogel. In the titanium oxide xerogel, two phases — anatase and rutile — have been detected by the x-ray analysis method. The luminescence excitation spectrum of erbium at 1.53 µm consists of a set of lines that correspond to the intracenter transitions of Er³⁺ ions with a maximum band at 524 nm caused by the ⁴I_15/2–²H_11/2 transition. The lifetime of erbium in such structures is 1.8 msec.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 94–98, January–February, 2005.     

Erbium incorporation in LiNbO3 by diffusion-doping

 The erbium incorporation into LiNbO₃ by diffusion doping is investigated in detail by means of Secondary Ion Mass Spectrometry, Secondary Neutral Mass Spectrometry, Rutherford Backscattering, Atomic Force Microscopy, X-ray Standing Wave technique and optical site-selective spectroscopy. The diffusion of erbium in LiNbO₃ can be described by Fick’s laws of diffusion with a concentration-independent diffusion coefficient. The diffusion constants and activation energies for Z-cut (X-cut) LiNbO₃ are 4.8×10^-5 cm²/s (12.0×10^-5 cm²/s) and 2.28 eV (2.44 eV), respectively. A limited solubility of erbium in LiNbO₃ has to be taken into account increasing exponentially with rising temperature. During the first step of diffusion an Er _x Nb _y -oxide layer is formed at the surface of the sample acting as diffusion reservoir. Erbium is incorporated into LiNbO₃ on vacant Li-sites slightly shifted from the original Li-position along the (-c)-direction. Site-selective spectroscopy found four distinguishable energetically different erbium centres at this lattice site resulting from locally different symmetries of the crystal field. Received: 21 March 1996 / Accepted: 12 August 1996     

Comparison of selected optical properties of oxyfluoride glass fibers doped with Er3+ and co-doped with Er3+ Yb3+

The method of manufacturing and spectroscopic evaluation of the Er³⁺ ions doped and Er³⁺–Yb³⁺co-doped SiO₂–Al₂O₃–Na₂CO₃–CaO–PbO–PbF₂ oxyfluoride glass fibers is presented in the paper. Both optically active elements erbium and ytterbium were introduced into the batch in the form of fluorides. The X-ray diffraction (XRD) technique was applied at each stage of fibers manufacturing in order to control an amorphous structure of the preforms and fibers. Optical studies of glass preforms and fibers (reflection/transmission, absorption, emission, and excited state absorption (ESA)) were directed to examine their suitability as fiber amplifiers at 1.55 μm band.     

Laser spectroscopy of optical centers in borosilicophosphate glass, coactivated by erbium and ytterbium ions

Based on analysis of the laser emission spectra of borosilicophosphate glass, coactivated by Er³⁺ and Yb³⁺ ions, we have determined the structure of the Stark splitting of the luminescence band for the erbium ion in the 1.5 μm region (the transition ⁴I_13/2 → ⁴I_15/2). In the wavelength interval 1532–1547 nm, we identified 12 sets of lines belonging to different types of optical centers of predominantly cubic symmetry. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 483–487, July–August, 2006.     

Crystalline structure and optical spectroscopy of Er3+-doped KGd(WO4)2 single crystals

4 )₂ single crystals doped with Er³⁺ have been grown by the flux top-seeded-solution growth method. The crystallographic structure of the lattice has been refined, being the lattice constants a=10.652(4), b=10.374(6), c=7.582(2) Å, β=130.80(2)°. The refractive index dispersion of the host has been measured in the 350–1500 nm range. The optical absorption and photoluminescence properties of Er³⁺ have been characterised in the 5–300 K temperature range. At 5 K, the absorption and emission bands show the (2J+1)/2 multiplet splittings expected for the C₂ symmetry site of Er in the Gd site. The energy positions and halfwidths of the 72 sublevels observed have been tabulated as well as the cross sections of the different multiplets. Six emission band sets have been observed under excitation of the ⁴F_7/2 multiplet. The Judd–Ofelt (JO) parameters of Er³⁺ in KGW have been calculated: Ω₂=8.90×10^-20 cm², Ω₄=0.96×10^-20 cm², Ω₆=0.82×10^-20 cm². Lifetimes of the ⁴S_3/2, ⁴F_9/2, and ⁴I_11/2 multiplets have been measured in the 5–300 K range of temperature and compared with those calculated from the JO theory. A reduction of the ⁴S_3/2 and ⁴I_11/2 measured lifetimes with increasing erbium concentration has been observed, moreover the presence of multiphonon non-radiative processes is inferred from the temperature dependence of the lifetimes. Received: 15 December 1997/Revised version: 10 July 1998