APPLIED PHYSICS LETTERS

VOLUME 80, NUMBER 10

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
cm1. 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

Electronic mail: capo@vax2.concordia.ca

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
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 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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1752
2002 American Institute of Physics
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Appl. Phys. Lett., Vol. 80, No. 10, 11 March 2002

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 .

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 ( exc980 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 specific ESA process
specific 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 inflection 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

Vetrone et al.

1753

FIG. 2. Temporal behavior of the 19ZnO 80TeO2 1Er2 O3 upconverted

emission following 980 nm excitation.

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

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 ( exc980 nm).
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1754

Vetrone et al.

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

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 (310 200 cm1 ). 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:
4 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 cm1 must be satisfied. The highest phonon energy in
the zinc tellurite host11 is 773 cm1, therefore, two or three
phonons would fill 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 efficiency for this transition was, therefore,
calculated. Upconversion efficiency is given by4

emited green light power

P emitted

.
P absorbed
absorbed IR light power

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 first determine luminescence quantum yield q for 488 nm excitation:12

emitted light power

exp
,

absorbed radiation power 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

( 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 q absorbed radiation density.

Also, the absorbed light intensity, P abs , can be calculated

from the absorption coefficient, 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

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 efficiency was measured using a pump power of 350
mW 880 W/cm2. We obtained an upconversion efficiency
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 efficiency 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 financial support.
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