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11 MARCH 2002
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
0003-6951/2002/80(10)/1752/3/$19.00
1752
2002 American Institute of Physics
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Vetrone et al.
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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 (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 .
.
P absorbed
absorbed IR light power
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
P abs visible
P abs IR
I emitted upconversion
,
I emitted direct
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