11 MARCH 2002

980 nm excited upconversion in an Er-doped ZnO– TeO2 glass
Fiorenzo Vetrone, John-Christopher Boyer, and John A. Capobiancoa)
Department of Chemistry and Biochemistry, Concordia University, 1455 de Maisonneuve Boulevard West, Montreal, Canada, H3G-1M8

Adolfo Speghini and Marco Bettinelli
` Dipartimento Scientifico e Tecnologico, Universita di Verona, Ca’ Vignal, Strada Le Grazie 15, 1-37 134 Verona, Italy

Received 20 September 2001; accepted for publication 4 January 2002 In this letter, we investigate the upconversion properties of 19ZnO– 80TeO2 – 1Er2 O3 glass after excitation into the 4 I 11/2 level using 980 nm radiation. At an excitation power density of 880 W/cm2, green emission ( 2 H 11/2 , 4 S 3/2)→ 4 I 15/2 dominates the upconversion spectrum with an efficiency of 0.16%. Temporal studies reveal that the 4 I 11/2 level is the intermediate state by which the two-step upconversion process occurs. Excited-state absorption and phonon-assisted energy transfer are discussed as possible mechanisms for the upconversion. © 2002 American Institute of Physics. DOI: 10.1063/1.1458073

Vitreous hosts doped with rare-earth ions yield inhomogeneously broadened emission profiles since no positional order exists over a macroscopic distance. This arises because the dopant ion sits in a variety of environments and, hence, experiences different crystal fields.1 As a result of the absence of any long-range order, rare-earth-doped glasses are attractive since the possibility of building tunable solid-state upconversion lasers becomes possible. Numerous studies have been carried out on the upconversion process of disordered matrices doped with the 4 f 11 lanthanide ion Er3 . The erbium ion is an excellent candidate for upconversion since it provides intermediate levels ( 4 I 11/2 and 4 I 13/2 with long lifetimes, which are easily accessible with near-infrared NIR radiation. Several processes, which can lead to emission at wavelengths shorter than the excitation wavelength, have been observed. In general, the most efficient are energy-transfer upconversion ETU and excited-state absorption ESA processes in the case of the Er3 ion. The ZnO– TeO2 host is a suitable glass for an all-solidstate upconversion laser, as it is composed of relatively heavy atoms. As a result, it provides a low multiphonon loss compared to other oxide glasses.2 The nonradiative decay of the excited electronic states of rare-earth ions in solids is dominated by the highest-energy phonons.3 If these vibrations are characterized by frequencies that are too high, they can prove deleterious to the upconversion process as the ion relaxes via the emission of phonons rather than photons. Therefore, the multiphonon relaxation rates are critical in determining the upconversion efficiency. Consequently, the search for laser materials has led to the development of glass hosts with low-phonon energies. Fluoride glass is one such host with a cutoff phonon energy of approximately 500 cm 1. Although fluoride-based glasses have lower phonon energies, it has been suggested that tellurite glasses may be somewhat better hosts because of their high-thermal stability and resistance against devitrification combined with a higha

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refractive index, which is beneficial for radiative transitions in rare-earth ions.4 Er3 upconversion in ZnO– TeO2 glasses excited with 800 nm radiation has been previously investigated.5 However, upconversion of Er3 in a zinc tellurite glass after excitation with 980 nm is important, as this is a convenient wavelength due to the availability of high-power diodes and is technologically important as it is often utilized in telecommunications.6 In this letter, we investigate the upconversion properties as well as propose a mechanism for this multiphoton process. Zinc tellurite glasses of molar composition 19ZnO– 80TeO2 – 1Er2 O3 were prepared by melting 10 g batches composed of analytical grade TeO2 , ZnO, and Er2 O3 in an alumina crucible for 40 min at 750 °C, followed by quenching in air on a stainless-steel plate. Samples were annealed for 17 h at 250 °C, and subsequently cut and carefully polished for the optical measurements. Upconversion luminescence spectra were measured by exciting at 980 nm using a Spectra-Physics model 3900 titanium–sapphire laser pumped by the 514 nm line of a coherent Sabre Innova Ar laser. The visible emissions were then collected and dispersed using a Jarrel-Ash 1 m Czerny Turner double monochromator. The signals were monitored with a thermoelectrically cooled Hamamatsu R43-02 photomultiplier tube. The photomultiplier signals were processed by a preamplifier model SR440 Stanford Research Systems SRS . A SRS gated photon counter model SR400 data acquisition system was used as an interface between the computer and the spectroscopic hardware. The signal was recorded under computer control using the Stanford SR465 software data acquisition/analyzer system. The laser beam was modulated using a SRS SR540 optical chopper. The temporal dependence was recorded using a digital oscilloscope Tektronix TDS-520A and the beam was modulated at 40 Hz. In a previous paper,7 Bettinelli et al. have reported and discussed the absorption and NIR emission spectra of the ZnO– TeO2 – Er2 O3 glass under investigation and have also

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centered at 535 and 550 nm.. This two-step upconversion can occur by only two distinct processes capable of populating the green emitting ( 4 S 3/2) level. at 300 K. 978. Phys.166. FIG. two weak bands were detected at 455 and 490 nm. respectively. Green emission is observed and is attributed to the transitions from the thermalized 2 H 11/2 and 4 S 3/2 states to the 4 I 15/2 ground state. respectively. we postulate that the upconversion occurs via an ESA process Fig. Energy-level diagram of Er3 ions in 19ZnO– 80TeO2 – 1Er2 O3 showing the two-photon ESA and PET upconversion processes responsible for populating the 4 F 7/2 and 4 F 5/2 levels. FIG. and v 4 S 3/2→ 4 I 13/2 . we extend the study by investigating the upconversion emission properties after excitation with NIR radiation 980 nm . No inflection was observed in the power study. 2. following 980 nm excitation. Temporal behavior of the 19ZnO– 80TeO2 – 1Er2 O3 upconverted emission following 980 nm excitation. 80. So. Following 980 nm excitation. thereby eliminating photon avalanche PA as a possible mechanism. thereby indicating a two-photon process. In this letter. 2. 4 S 3/2)→ 4 I 15/2 emission is shown in Fig. iii 4 F 9/2→ 4 I 15/2 .Appl. calculated the corresponding Judd–Ofelt parameters. No. The upconverted green luminescence is very bright and can be observed by the naked eye after pumping with as low as 20 mW. They are assigned to the 4 F 5/2 → 4 I 15/2 and 4 F 7/2→ 4 I 15/2 transitions. An exhaustive site-selective upconversion study will elucidate this point. The dependence of the upconverted luminescence on pump power is quadratic. which is in good agreement with the lifetime of the 4 I 11/2 level 400 s measured by Sidebottom et al. Red and NIR emission was observed from the 4 F 9/2 670 nm . energy transfer ET and excited-state absorption. 4 S 3/2)→ 4 I 15/2 and 4 F 9/2→ 4 I 15/2 transitions in the upconversion spectrum differs from those in the direct emission spectrum. 1753 FIG. and 986 nm and have observed that the above-mentioned transitions have slightly different peak shapes in each upconversion spectrum depending on the excitation wavelength. 1. The Er3 ion is excited to the 4 I 11/2 level. Figure 1 presents the emission spectra of the ZnO– TeO2 – Er2 O3 glass upon direct excitation with 488 nm and after exciting into the 4 I 11/2 ( exc 980 nm) excited state of the erbium ion. Lett. 4 I 9/2 800 nm excited states to the ground state and for the 4 S 3/2→ 4 I 13/2 transition at 850 nm. 3 . We hypothesize that each exciting wavelength tunes into a specific ESA process specific to only a subset of Er3 sites in the glass matrix. respectively ( exc 980 nm). In . The rise time. see http://apl.205. after which a second photon from the pump beam brings the ion to the 4 F 7/2 level. is 440 s.8 The temporal behavior of the green upconverted ( 2 H 11/2 .aip. Examination of the energy-level diagram for Er3 shows that there is an energy level lying at twice the excitation energy of 980 nm. the longlifetime state ( 4 I 11/2) contributes as an intermediate state in the upconversion process.9 Clearly. ii 4 S 3/2 → 4 I 15/2 . 11 March 2002 Vetrone et al. Nonradiative relaxation in turn populates the 4 S 3/2 level. 3. We have also performed the upconversion at 971. Room-temperature luminescence of 19ZnO– 80TeO2 – 1Er2 O3 upon excitation with a 488 nm and b 980 nm. Redistribution subject to AIP license or copyright. It should be noted that the peak shape of the ( 2 H 11/2 . iv 4 I 9/2→ 4 I 15/2 .213. 10. i 2 H 11/2→ 4 I 15/2 . Downloaded 07 Sep 2010 to 193.

181 1999 . The luminescence quantum yield was calculated to be 12%. Selmi. Phys. Joubert. P. 4 Also. Rolli. Ueda. Gatterer. The lifetime of the ( 2 H 11/2 . Solids 222. Similarly. W. The highest phonon energy in the zinc tellurite host11 is 773 cm 1. can be calculated from the absorption coefficient. M. see http://apl. Dyer. Sekiya. Sidebottom. pp. while upon excitation at 980 nm the lifetime of the same states is 40 s. we incorporate the ratio of the upconversion luminescence and direct excitation luminescence intensities4 obtained under identical collecting conditions: q P abs visible P abs IR I emitted upconversion . Bettinelli. Oxford University Press. L. Drexhage. were calculated in a previous paper. It should be noted that using this method requires calibration of the detecting equipment. Acta. The authors acknowledge the Natural Science and Engineering Research Council of Canada and MURST of Italy. This is evident as the decay time of the green ( 4 S 3/2→ 4 I 15/2) upconverted emission is longer than exciting directly in the emitting level. Speghini. which yields a visually dominant green emission. B. W. Rev. Spectrochim. 4 Z. No. ET should be taken into account in the upconversion process. an energy gap of 1750 cm 1 must be satisfied. Energy transfer upconversion involves another Er3 ion in close proximity. Solids 54. Italy for expert technical assistance. S. 8906 1996 . 4 S 3/2) states. Matter 12. The upconversion efficiency for this transition was. 11 T.K. Golab. Zschokke Reidel.. J. Redistribution subject to AIP license or copyright. Sibley. Ostermayer. 1997 . Potter. 4432 1970 . . 11 March 2002 Vetrone et al. 4 I 15/2 . S. jAi j 3 where j is the summation to all the lower levels. H. Hruschka. Ohtsuka. Rev. Vol. it has been shown that energy transfer between dopant ions can be neglected in samples with a concentration of 0. 157. Brow. The energy-level diagram reveals that there is no energy level resonant at three times the excitation wavelength (3 10 200 cm 1 ). A. 2009 2001 . A. edited by I. ` The authors gratefully thank Erica Viviani Universita di Verona. general. 7 ` R. 153 1993 . 10. Rev. Ajo. a neighboring Er3 ion also in the 4 I 11/2 state transfers its energy to the initial ion. The upconversion efficiency was measured using a pump power of 350 mW 880 W/cm2 . Layne. 282 1997 . 4 S 3/2)→ 4 I 15/2)] in the upconversion spectrum excited by 980 nm radiation. J. Phys. and the temporal studies revealed that 4 I 11/2 is the intermediate level from which the upconversion occurs. 9 D. and L.166. Weber. J. It is necessary that we first determine luminescence quantum yield q for 488 nm excitation:12 q emitted light power absorbed radiation power exp R . B 16. 79. J. In order to avoid the calibration step. H. C. Solids 168. 4523 2000 . Oxford. Non-Cryst. as well as having evaluated the upconversion efficiency 0. if the ion nonradiatively decays to the 4 I 13/2 . 11. Chem. Inspection of the blue region of the upconversion spectrum gives further proof of this. F.aip. S. The ET upconversion Fig. Therefore. G.10 The sample used in this study is doped with 1 mol % Er3 and as a result. Morgan. the incident light power. Optical Electronics in Modern Communications. B. A. Part A 57. and M. 4 S 3/2) states at 488 nm is 22 s. for financial support. Phys. 13 M. 10 1977 . The experimental lifetime at room temperature. Appl. two or three phonons would fill the necessary gap. 2 where exp is the lifetime of the level determined experimentally after excitation at 488 nm while R is the radiative lifetime. 80. calculated. Lowdermilk. Non-Cryst. The total spontaneous emission probabilities.5 mol % or lower. however. Phys. an energy transfer upconversion mechanism must be operative. A nonradiative decay to this level from a three-photon ESA process is ruled out. Wachtler. 4 S 3/2) states was obtained from the Judd–Ofelt analysis and was determined to be 186 s for the ZnO–TeO2 glass. Alaya. 262 1967 . and R. K. Phys. N. absorbed IR light power 1 where P abs visible is the absorbed light power for direct excitation with 488 nm and P abs IR is the absorbed light power for upconversion with 980 nm excitation. Yeh. therefore. following 488 nm excitation. 12 D. A..16% In this letter. 1986 . J. Kanoun. therefore. Yen. Mochida. The emission light intensity can be determined as follows: P emitted q absorbed radiation density. The 19ZnO–80TeO2 – 1Er2 O3 glass yields a predominantly green emission ( 2 H 11/2 . W.16% for the emission from the thermalized ( 2 H 11/2 . Mejri. K. J. In order for the 4 F 5/2 state to be populated after 980 nm excitation. Phys. Pan. 3 occurs by the following mechanism: 4 ( 2 H 11/2 . and A.213. and M. F. I emitted direct 5 I 11/2 . in Optical Spectroscopy of Glasses. Appl. U. Suscavage. and D. M. and the sample length. B 2. we have reported and discussed the visible upconversion emission of a 19ZnO–80TeO2 – 1Er2 O3 glass following excitation into the 4 I 11/2 level. H. M. Lett.1754 Appl. 6 A. Van Uitert. A i j . 1 The emitted green light power after NIR excitation can be estimated by comparing it with that obtained after direct 488 nm excitation. M. Phys. 23– 64. 2 W. was found to be 22 s.: Condens. 62. Opt. A. Dominiak-Dzik. Jaba.7 The radiative lifetime of the thermalized Downloaded 07 Sep 2010 to 193. W. A. Weber.205. Liu. and H. After the ion is excited to the 4 I 11/2 level by the laser beam. We have shown that the upconversion occurs via a two-photon ESA and PET process. Yariv. Mater. P abs . thereby exciting it to the 4 F 5/2 level. 106 1994 . two photons of 980 nm do not have the necessary energy to populate this level. Phys. G. van der Ziel. We observe emission from the 4 F 5/2 level. J. 5th ed. K. 10 J. an exciting photon has no resonant energy level for which to populate. Upconversion efficiency is given by4 P emitted P absorbed emited green light power . 5 N. G. the absorbed light intensity. Ryba-Romanowski. We obtained an upconversion efficiency of 0. We point out that there is not perfect resonance between the 4 I 11/2 and 4 F 5/2 states. Dordrecht. and G. 8 M. J. 3 C. and H. 266 1987 . The radiative lifetime of the upper level i is calculated by13 R 1 . M. 4 I 11/2 → 4 F 5/2 .