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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 Scientico 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 efciency 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 proles 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 elds.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 efcient 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 efciency. 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 uoride-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 devitrication combined with a higha

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refractive index, which is benecial 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 titaniumsapphire 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 preamplier 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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Appl. Phys. Lett., Vol. 80, No. 10, 11 March 2002

Vetrone et al.


FIG. 1. Room-temperature luminescence of 19ZnO 80TeO2 1Er2 O3 upon excitation with a 488 nm and b 980 nm. i 2 H 11/2 4 I 15/2 , ii 4 S 3/2 4 I 15/2 , iii 4 F 9/2 4 I 15/2 , iv 4 I 9/2 4 I 15/2 , and v 4 S 3/2 4 I 13/2 .

FIG. 2. Temporal behavior of the 19ZnO 80TeO2 1Er2 O3 upconverted emission following 980 nm excitation.

FIG. 3. 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, respectively ( exc 980 nm). Downloaded 07 Sep 2010 to Redistribution subject to AIP license or copyright; see

calculated the corresponding JuddOfelt parameters. In this letter, we extend the study by investigating the upconversion emission properties after excitation with NIR radiation 980 nm . 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. 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, centered at 535 and 550 nm, respectively. Red and NIR emission was observed from the 4 F 9/2 670 nm , 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. Following 980 nm excitation, two weak bands were detected at 455 and 490 nm. They are assigned to the 4 F 5/2 4 I 15/2 and 4 F 7/2 4 I 15/2 transitions, respectively. It should be noted that the peak shape of the ( 2 H 11/2 , 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. We have also performed the upconversion at 971, 978, 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. We hypothesize that each exciting wavelength tunes into a specic ESA process specic to only a subset of Er3 sites in the glass matrix. An exhaustive site-selective upconversion study will elucidate this point. The upconverted green luminescence is very bright and can be observed by the naked eye after pumping with as low as 20 mW. The dependence of the upconverted luminescence on pump power is quadratic, thereby indicating a two-photon process. This two-step upconversion can occur by only two distinct processes capable of populating the green emitting ( 4 S 3/2) level; energy transfer ET and excited-state absorption. No inection was observed in the power study, thereby eliminating photon avalanche PA as a possible mechanism.8 The temporal behavior of the green upconverted ( 2 H 11/2 , 4 S 3/2) 4 I 15/2 emission is shown in Fig. 2. The rise

time, following 980 nm excitation, is 440 s, which is in good agreement with the lifetime of the 4 I 11/2 level 400 s measured by Sidebottom et al. at 300 K.9 Clearly, the longlifetime state ( 4 I 11/2) contributes as an intermediate state in the upconversion process. Examination of the energy-level diagram for Er3 shows that there is an energy level lying at twice the excitation energy of 980 nm. So, we postulate that the upconversion occurs via an ESA process Fig. 3 . The Er3 ion is excited to the 4 I 11/2 level, after which a second photon from the pump beam brings the ion to the 4 F 7/2 level. Nonradiative relaxation in turn populates the 4 S 3/2 level. In


Appl. Phys. Lett., Vol. 80, No. 10, 11 March 2002

Vetrone et al.

general, it has been shown that energy transfer between dopant ions can be neglected in samples with a concentration of 0.5 mol % or lower.10 The sample used in this study is doped with 1 mol % Er3 and as a result, ET should be taken into account in the upconversion process. Inspection of the blue region of the upconversion spectrum gives further proof of this. We observe emission from the 4 F 5/2 level, however, two photons of 980 nm do not have the necessary energy to populate this level. A nonradiative decay to this level from a three-photon ESA process is ruled out. The energy-level diagram reveals that there is no energy level resonant at three times the excitation wavelength (3 10 200 cm 1 ). Similarly, if the ion nonradiatively decays to the 4 I 13/2 , an exciting photon has no resonant energy level for which to populate. Therefore, an energy transfer upconversion mechanism must be operative. 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. The lifetime of the ( 2 H 11/2 , 4 S 3/2) states at 488 nm is 22 s, while upon excitation at 980 nm the lifetime of the same states is 40 s. The ET upconversion Fig. 3 occurs by the following mechanism:

( 2 H 11/2 , 4 S 3/2) states was obtained from the JuddOfelt analysis and was determined to be 186 s for the ZnOTeO2 glass. The experimental lifetime at room temperature, following 488 nm excitation, was found to be 22 s. The luminescence quantum yield was calculated to be 12%. The emission light intensity can be determined as follows: P emitted

absorbed radiation density.

Also, the absorbed light intensity, P abs , can be calculated from the absorption coefcient, the incident light power, and the sample length. It should be noted that using this method requires calibration of the detecting equipment. In order to avoid the calibration step, we incorporate the ratio of the upconversion luminescence and direct excitation luminescence intensities4 obtained under identical collecting conditions:

P abs visible P abs IR

I emitted upconversion , I emitted direct

I 11/2 , 4 I 11/2 4 F 5/2 , 4 I 15/2 .

Energy transfer upconversion involves another Er3 ion in close proximity. After the ion is excited to the 4 I 11/2 level by the laser beam, a neighboring Er3 ion also in the 4 I 11/2 state transfers its energy to the initial ion, thereby exciting it to the 4 F 5/2 level. We point out that there is not perfect resonance between the 4 I 11/2 and 4 F 5/2 states. In order for the 4 F 5/2 state to be populated after 980 nm excitation, an energy gap of 1750 cm 1 must be satised. The highest phonon energy in the zinc tellurite host11 is 773 cm 1, therefore, two or three phonons would ll the necessary gap. The 19ZnO80TeO2 1Er2 O3 glass yields a predominantly green emission ( 2 H 11/2 , 4 S 3/2) 4 I 15/2)] in the upconversion spectrum excited by 980 nm radiation. The upconversion efciency for this transition was, therefore, calculated. Upconversion efciency is given by4 P emitted P absorbed emited green light power . 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. The upconversion efciency was measured using a pump power of 350 mW 880 W/cm2 . We obtained an upconversion efciency of 0.16% In this letter, we have reported and discussed the visible upconversion emission of a 19ZnO80TeO2 1Er2 O3 glass following excitation into the 4 I 11/2 level, which yields a visually dominant green emission, as well as having evaluated the upconversion efciency 0.16% for the emission from the thermalized ( 2 H 11/2 , 4 S 3/2) states. We have shown that the upconversion occurs via a two-photon ESA and PET process, and the temporal studies revealed that 4 I 11/2 is the intermediate level from which the upconversion occurs. ` The authors gratefully thank Erica Viviani Universita di Verona, Italy for expert technical assistance. The authors acknowledge the Natural Science and Engineering Research Council of Canada and MURST of Italy, for nancial support.
W. M. Yen, in Optical Spectroscopy of Glasses, edited by I. Zschokke Reidel, Dordrecht, 1986 , pp. 23 64. 2 W. Ryba-Romanowski, S. Golab, and G. Dominiak-Dzik, J. Phys. Chem. Solids 54, 153 1993 . 3 C. B. Layne, W. H. Lowdermilk, and M. J. Weber, Phys. Rev. B 16, 10 1977 . 4 Z. Pan, S. H. Morgan, K. Dyer, A. Ueda, and H. Liu, J. Appl. Phys. 79, 8906 1996 . 5 N. Jaba, A. Kanoun, H. Mejri, A. Selmi, S. Alaya, and H. Maaref, J. Phys.: Condens. Matter 12, 4523 2000 . 6 A. Yariv, Optical Electronics in Modern Communications, 5th ed. Oxford University Press, Oxford, U.K., 1997 . 7 ` R. Rolli, K. Gatterer, M. Wachtler, M. Bettinelli, A. Speghini, and D. Ajo, Spectrochim. Acta, Part A 57, 2009 2001 . 8 M. F. Joubert, Opt. Mater. 11, 181 1999 . 9 D. L. Sidebottom, M. A. Hruschka, B. G. Potter, and R. K. Brow, J. Non-Cryst. Solids 222, 282 1997 . 10 J. P. van der Ziel, F. W. Ostermayer, and L. G. Van Uitert, Phys. Rev. B 2, 4432 1970 . 11 T. Sekiya, N. Mochida, and A. Ohtsuka, J. Non-Cryst. Solids 168, 106 1994 . 12 D. C. Yeh, W. A. Sibley, M. Suscavage, and M. G. Drexhage, J. Appl. Phys. 62, 266 1987 . 13 M. J. Weber, Phys. Rev. 157, 262 1967 .

The emitted green light power after NIR excitation can be estimated by comparing it with that obtained after direct 488 nm excitation. It is necessary that we rst determine luminescence quantum yield q for 488 nm excitation:12

emitted light power absorbed radiation power

exp R

where exp is the lifetime of the level determined experimentally after excitation at 488 nm while R is the radiative lifetime. The radiative lifetime of the upper level i is calculated by13

1 , jAi j

where j is the summation to all the lower levels. The total spontaneous emission probabilities, A i j , were calculated in a previous paper.7 The radiative lifetime of the thermalized

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