Oxyfluoride lead borate glasses singly doped with Nd3+ and Er3+ ions have been studied before and after thermal treatment. The orthorhombic PbF2 crystallites are formed during thermal treatment, which was evidenced by X-ray diffraction analysis. Near-infrared luminescence spectra at 1.06 μm and 1.53 μm have been registered for samples before and after annealing, which correspond to the main 4F3/2–4I11/2 and 4I13/2–4I15/2 laser transitions of Nd3+ and Er3+ ions, respectively. Luminescence decays from 4F3/2 state of Nd3+ and 4I13/2 state of Er3+ have been analyzed in detail. Contrary to Nd-doped samples, the luminescence lines obtained for Er-doped transparent oxyfluoride glass-ceramics are more intense and narrowed, whereas the luminescence decays from 4I13/2 state of Er3+ are slightly longer in comparison to precursor glasses

Dominiak-Dzik, G.

Goryczka, Tomasz

Pisarska, Joanna

Pisarski, Wojciech A.

Ryba-Romanowski, W.

Optica Applicata

English

Repozytorium Uniwersytetu Śląskiego RE-BUŚ

             Title: Near-infrared luminescence of rare earth ions in oxyfluoride lead borate glasses and transparent glass-ceramic materials  Author: Joanna Pisarska, W. Ryba-Romanowski, G. Dominiak-Dzik, Tomasz Goryczka, Wojciech A. Pisarski  Citation style: Pisarska Joanna, Ryba-Romanowski W., Dominiak-Dzik G., Goryczka Tomasz, Pisarski Wojciech A. (2008). Near-infrared luminescence of rare earth ions in oxyfluoride lead borate glasses and transparent glass-ceramic materials. "Optica Applicata" (2008, iss. 1, s. 211-216).  Optica Applicata, Vol. XXXVIII, No. 1, 2008Near-infrared luminescence of rare earth ions in oxyfluoride lead borate glasses and transparent glass-ceramic materialsJOANNA PISARSKA1, WITOLD RYBA-ROMANOWSKI2, GRAŻYNA DOMINIAK-DZIK2, TOMASZ GORYCZKA3, WOJCIECH A. PISARSKI3*1Silesian University of Technology, Department of Materials Science, Krasińskiego 8, 40-019 Katowice, Poland2Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-422 Wrocław, Poland3University of Silesia, Institute of Materials Science, Bankowa 12, 40-007 Katowice, Poland*Corresponding author: wpisarsk@us.edu.plOxyfluoride lead borate glasses singly doped with Nd3+ and Er3+ ions have been studied beforeand after thermal treatment. The orthorhombic PbF2 crystallites are formed during thermaltreatment, which was evidenced by X-ray diffraction analysis. Near-infrared luminescence spectraat 1.06 μm and 1.53 μm have been registered for samples before and after annealing, whichcorrespond to the main 4F3/2–4I11/2 and 4I13/2–4I15/2 laser transitions of Nd3+ and Er3+ ions,respectively. Luminescence decays from 4F3/2 state of Nd3+ and 4I13/2 state of Er3+ have beenanalyzed in detail. Contrary to Nd-doped samples, the luminescence lines obtained for Er-dopedtransparent oxyfluoride glass-ceramics are more intense and narrowed, whereas the luminescencedecays from 4I13/2 state of Er3+ are slightly longer in comparison to precursor glasses.Keywords: oxyfluoride glasses, transparent glass-ceramics, rare earth ions, luminescence.1. IntroductionThermal treatment causes a transformation from glassy material to the glass-ceramicone. There is a convenient way of obtaining several transparent systems containingcrystalline domains with nano- or micrometric size [1]. The narrowing of spectral linesand elongation in lifetimes of luminescent states of rare earths are the spectroscopicconsequences of this transformation. This is due to structural changes in theenvironment surrounding rare earth ions. Controlled crystallization (devitrification)and the luminescence properties of Nd3+ [2–6] and Er3+ [7–11], due to the main212 J. PISARSKA et al.4F3/2–4I11/2 and 4I13/2–4I11/2 laser transitions, have been extensively studied fortransparent oxyfluoride glass-ceramics.The present work is concerned with the luminescence properties of rare earth ionsin oxyfluoride lead borate glasses and transparent glass-ceramics. The rare earthswere limited to Nd3+ and Er3+ ions. They are the most widely studied luminescentions emitting near-infrared light especially for laser devices using 4F3/2–4I11/2 and4I13/2–4I15/2 transitions at 1.06 μm and 1.55 μm, respectively.2. Experimental techniquesThe characteristic temperatures were determined by a Perkin Elmer differentialscanning calorimeter (DSC). The DSC curves were acquired with the heating rate of10 deg/min. The XRD patterns were obtained using INEL diffractometer with Cu Kαradiation. The diffractometer is equipped with curved position sensitive detectorCPS 120 which allows data to be collected in 2θ  range from 0° to 120°. Luminescencewas recorded with a Continuum Model Surelite I OPO pumped by a third harmonicof a Nd:YAG laser. Luminescence was dispersed by a 1-meter double gratingmonochromator and detected with a photomultiplier with S-20 spectral response.The luminescence spectra were recorded using a Stanford SRS 250 boxcar integratorcontrolled by a computer. The luminescence decay curves were recorded and storedby a Tektronix TDS 3052 oscilloscope. All measurements were carried out at roomtemperature.3. PreparationGlasses in 18B2O3–9PbF2–63PbO–6Al2O3–3WO3–1LnF3 (in wt%) systems (whereLn = Nd or Er) were prepared. Anhydrous oxides and lead fluoride (99.99% purity,Aldrich) were used as starting materials. A homogeneous mixture was heated inthe protective atmosphere of dried argon. Glasses were melted at 850 °C in Ptcrucibles, then poured into preheated copper moulds and annealed below the glasstransition temperature. After this procedure, the samples were slowly cooled tothe room temperature.Transparent glass-ceramics (TGC) were successfully obtained by thermaltreatment of the precursor oxyfluoride glasses [12]. The glass transition temperatureTg equal to 350 °C for the oxyfluoride Ln-doped samples was determined fromDSC measurements. The samples were thermally treated above Tg, at 400 °C, for 1, 5,10 and 15 h, respectively. The X-ray diffraction was used to verify the devitrificationof the glasses. Figure 1 presents X-ray diffraction patterns of glass and glass-ceramicobtained after thermal treatment at 400 °C for 15 h. The experimental data arecompared to those obtained for the heat-treated sample (72% PbF2, 400 °C/5 h), wherePbO was totally substituted by PbF2 in chemical composition. Independently ofthe kind of rare earths (Nd or Er) and lead fluoride content (9 or 72%) in glasscomposition, several narrowed and relatively intense diffraction peaks were obtainedNear-infrared luminescence of rare earth ions in oxyfluoride lead borate glasses ... 213after thermal treatment, which corresponded to orthorhombic PbF2 phase (PDF-2card no.: P411086) with the following lattice parameters: a0 = 6.44 Å, b0 = 3.90 Å,c0 = 7.65 Å. The orthorhombic PbF2 phase was identified contrary to other lead-basedTGC systems containing cubic β-PbF2 phase such as PbF2–PbO–SiO2 [13] orPbF2–PbO–GeO2 [14], which are well known from the literature data.4. Results and discussionThe near-infrared luminescence properties of rare earth ions in oxyfluoride lead borateglasses have been analyzed before and after thermal treatment. Selected Nd-dopedglass samples were thermally treated for different times at 400 °C. Figure 2 presentsthe luminescence spectra recorded for Nd3+ ions in oxyfluoride lead borate glassesbefore and after (400 °C/15 h) thermal treatment. Luminescence bands at 1.06 μmcorrespond to the main 4F3/2–4I11/2 laser transition of Nd3+ ions. In all the cases,the luminescence intensities and linewidths as well as the values of 4F3/2 fluorescentlifetime for Nd3+ ions in glass-ceramics (τ ~ 86 μs) were nearly the same in comparisonto precursor glass. This suggests that transparent oxyfluoride glass-ceramics weresuccessfully prepared but the Nd3+ ions are rather not incorporated into crystallinephase. They are situated in the oxide glassy matrix. This phenomenon is probablyconnected with chemical and structural nature of the host matrices investigated. It canbe that borate units bond Nd3+ ions and block their movement to the crystalline phase.Additionally, the phonon energy of the host due to stretching vibrations of BO3 units(hν = 1300 cm–1) is relatively higher. It was evidently found that Nd3+ ions arepreferentially incorporated into crystalline phases with small phonon energies. Forthat reason, fluoride nanocrystals including Nd3+ ions are difficult to generate intransparent oxyfluoride glass-ceramics based on B2O3–PbF2. On the other hand, someresults obtained for oxyfluoride glass-ceramics indicate that Nd3+ ions are moreFig. 1. X-ray diffraction patterns for oxyfluoride lead borate glasses before and after thermal treatment.214 J. PISARSKA et al.difficult to be incorporated into crystalline phase than other rare earth ions like Er3+.Selected Er-doped glass samples were thermally treated under the same conditions(temperature and time) as the ones for Nd-doped systems. Figure 3 presentsluminescence spectra recorded for Er3+ ions in oxyfluoride lead borate glasses beforeand after (400 °C/15 h) thermal treatment. NIR luminescence bands at 1.53 μmcorrespond to the main 4I13/2–4I15/2 laser transition of Er3+ ions. The 4I13/2 luminescencelifetime of Er3+ ions increases from 600 μs to 660 μs for samples before and afterheat treatment, respectively. Moreover, the luminescence intensity increases, whereaslinewidth for the main 4I13/2–4I15/2 laser transition of Er3+ ions in oxyfluoride leadFig. 2. Luminescence spectra at 1.06 μm recorded for Nd3+ ions in glass samples before and after thermaltreatment. NIR luminescence bands correspond to the main 4F3/2–4I11/2 laser transition of Nd3+ ions.Fig. 3. Luminescence spectra at 1.53 μm recorded for Er3+ ions in glass samples before and after thermaltreatment. NIR luminescence bands correspond to the main 4I13/2–4I15/2 laser transition of Er3+ ions.Near-infrared luminescence of rare earth ions in oxyfluoride lead borate glasses ... 215borate glass-ceramics slightly decreases in comparison to the precursor glass. Thissuggests that Er3+ ions exist in small amounts in crystalline phase. The same situationhas been observed for up-conversion luminescence registered for Er3+ ions inoxyfluoride lead borate glasses and transparent glass-ceramic materials [15].5. ConclusionsSelected rare earth doped oxyfluoride lead borate glasses have been investigatedbefore and after thermal treatment for near-infrared luminescence. The results obtainedfor Nd3+ and Er3+ ions in multicomponent oxyfluoride glasses and transparentglass-ceramic materials lead to the following conclusions:1. Transparent glass-ceramic materials were successfully prepared. Severalnarrowed and relatively intense diffraction lines have been formed after heat treatment.Phase identification reveals that crystalline peaks can be related to the orthorhombicPbF2 phase.2. Near-infrared luminescence spectra at 1.06 μm and 1.53 μm were registered forrare earths in oxyfluoride lead borate glasses before and after thermal treatment.Luminescence bands correspond to the main 4F3/2–4I11/2 and 4I13/2–4I15/2 lasertransitions of Nd3+ and Er3+ ions, respectively.3. The results obtained for oxyfluoride glass-ceramic materials indicate that Nd3+ions are more difficult to be incorporated into crystalline phase than other rare earthions like Er3+. Neodymium ions do not rather exist in crystalline phase, becausethe 4F3/2 fluorescence lifetime is not changed in comparison to precursor glass. Quitea different situation is observed for Er-doped TGC systems, which are characterizedby relatively more intense and narrowed luminescence lines in contrast to the samplesbefore annealing. Moreover, the elongation in lifetimes of the luminescent states ofEr3+ ions was also achieved.Acknowledgement – The Ministry of Science and Higher Education supported this work under researchproject N N507 3617 33.References[1] STOCH L., Nanocrystalline glass-ceramics formation, Optica Applicata 33(1), 2003, pp. 115–23.[2] CHEN D., WANG Y., YU Y., HU Z., Crystallization and fluorescence properties of Nd3+-dopedtransparent oxyfluoride glass ceramics, Materials Science and Engineering B 123(1), 2005, pp. 1–6.[3] YU Y., CHEN D., CHENG Y., WANG Y., HU Z., BAO F., Investigation on crystallization and influenceof Nd3+ doping of transparent oxyfluoride glass-ceramics, Journal of the European CeramicSociety 26(13), 2006, pp. 2761–7.[4] YU Y., CHEN D., MA E., WANG Y., HU Z., Spectroscopic properties of Nd3+ doped transparentoxyfluoride glass ceramics, Spectrochimica Acta Part A: Molecular and BiomolecularSpectroscopy 67(3–4), 2007, pp. 709–13.[5] LIU F., WANG Y., CHEN D., YU Y., Investigation on crystallization kinetics and microstructure ofnovel transparent glass ceramics containing Nd:NaYF4 nano-crystals, Materials Science andEngineering B 136(2–3), 2007, pp. 106–10.216 J. 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Near-infrared luminescence of rare earth ions in oxyfluoride lead borate glasses and transparent glass-ceramic materials

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Near-infrared luminescence of rare earth ions in oxyfluoride lead borate glasses and transparent glass-ceramic materials

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