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CERAMICS

INTERNATIONAL
Available online at www.sciencedirect.com
Ceramics International 40 (2014) 1598115984
Structural disorder-dependent upconversion in Er
3
/Yb
3
-doped
calcium titanate
Ariadne C. Eduardo
a
, Alberthmeiry T. de Figueiredo
a,n
, Maximo Siu Li
b
, Elson Longo
c
a
Department of Chemistry UFG campus Catalo, 75.704-020, Catalo, Brazil
b
Institute of Physics, 13.566590, USP-SO CARLOS, So Carlos, Brazil
c
INCTMN, Institute of Chemistry, UNESP, 14.801970, Araraquara, Brazil
Received 26 June 2014; received in revised form 22 July 2014; accepted 24 July 2014
Available online 7 August 2014
Abstract
In this work, we evaluated the photoluminescence of distinct Er/Yb-doped CaTiO
3
powders prepared by the polymeric precursor method, i.e.,
the crystalline form (structurally ordered) and another form (structurally disordered) before structural order was reached. Upconversion
luminescence and photoluminescence are correlated to structural orderdisorder. The CT:Er,Yb material presents broad-band emission under UV
irradiation and green upconversion luminescence under IR irradiation.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Titanate; Upconversion; Orderdisorder effect; Photoluminescence
1. Introduction
Rare-earth (RE) doped materials are widely used in optical
devices such as sensors, ampliers, waveguides, solid-state
lighting and lasers, as well as in biological applications [15].
They are characterized mainly due to their partially lled 4f
shells, which results various unique optical features.
The host materials play an important role in photolumines-
cence (PL) emission. Alkaline earth metal titanate is a good
luminescent matrix due to its excellent chemical stability and
the appropriate band gap, which makes it one of the most
interesting luminescent material. In addition, rare earth ion-
doped calcium titanate (CaTiO
3
) phosphors have been studied
extensively due to their well-known chemical stability. In
recent years, CaTiO
3
:Pr
3
has attracted much attention
because high red-light emission appears only starting from
the
1
D
2
(Pr
3
) level in this material [610].
Several such materials show high-frequency upconversion
luminescence on excitation with comparatively lower
frequency excitation due to excited state absorption through
metastable states. Upconversion is an anti-Stokes emission
process that converts long-wavelength pump sources into
short-wavelength emission. Usually only two-photon upcon-
version processes are observed, and the mechanism of these
two-photon transitions has been extensively analyzed in Er/
Yb-codoped materials [1116]. Yang et al. [13] studied the
reduction of upconversion emission in CaTiO
3
:Yb,Er, while
Deren et al. [17] showed upconversion emission in CaTiO
3
:
Er
3
nanocrystals.
The literature describes a series of structurally disordered
perovskites synthesized by a soft chemical process called the
polymeric precursor method, which shows intense PL at room
temperature. To observe such PL emissions, certain localized
states must be present in the forbidden band gap. Localized
states can exist in materials if the structure contains a certain
number of oxygen vacancies, impurities, and/or tilts, i.e.,
structural disorder. Such structural disorder is important for
the formation of electron-hole pairs and for their nal
recombination [1824].
The objective of this work was to synthesize Er and Yb-
doped CaTiO
3
powders by the polymeric precursor method.
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http://dx.doi.org/10.1016/j.ceramint.2014.07.127
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
n
Corresponding author.
E-mail address: alberth@ufg.br (A.T. de Figueiredo).
The structure and optical properties were evaluated by X-ray
diffraction (XRD), and photoluminescence analysis. The
material showed upconversion emission.
2. Experimental details
The Ca
0.98
Er
0.01
Yb
0.01
TiO
3
-doped (CT:Er,Yb) powders stu-
died in the present work were synthesized following a soft
chemical method, the so-called Polymeric Precursor Method.
The details of the processing have already been published
elsewhere [23]. Precalcined CT:Er,Yb powder was further
heat-treated at 450, 500, 550, and 600 1C for 2 h. Powders
were structurally characterized by X-ray diffraction (XRD) (Cu
K

radiation) in the mode of -2 scan ( is the diffraction


angle), recorded on a Shimadzu XRD 6100 diffractometer. The
PL measurements were collected with a Thermal Jarrel-Ash
Monospec 27 monochromator and a Ge photodetector linked
with a data acquisition system composed of a SR-530 lock-in
controlled by microcomputer. The 350.7 nm exciting wave-
length of a krypton ion laser (Coherent Innova) was used with
the output of the laser kept at 200 mW. The 972 nm exciting
wavelength of a laser diode with the output of the laser kept at
500 mW was used to upconversion measurements. All mea-
surements were taken at room temperature.
3. Results and discussion
X-ray diffraction patterns of CT:Er,Yb powder heat-treated
at 450, 500, 550 and 600 1C were recorded (Fig. 1). The XRD
patterns of the CT:Er,Yb indicated that these crystal structures
are isostructural to that of orthorhombic CaTiO
3
, ICDD card
no. 42423 (Pbnm). Also, a literature survey revealed that the
peak position is not affected signicantly when CaTiO
3
is
doped with a low concentration [8,25,26]. Therefore, no
signicant change was detected in the position of the peaks
at the concentration used here. Samples heat-treated at 450 and
500 1C did not display diffractions peaks, which was attributed
to the fact that they were structurally disordered. On the other
hand, samples heat-treated at 550 and 600 1C presented
diffractions peaks and showed structural order.
Fig. 2 shows PL spectra of the CT:Er,Yb samples obtained at
350.7 nm with the excitation wavelength of a krypton ion laser.
When the annealing temperature was increased, the PL intensity
changed. The CT:Er,Yb sample annealed at 500 1C yields most
intense PL emission. This behavior was attributed to the
structural orderdisorder present in environmental samples.
The samples, which were prepared by the polymeric precursor
method, initially showed high structural disorder. Several
reports in the literature describe the favorable conditions for
PL emission in materials possessing a degree of orderdisorder
[2224,27]. The system cannot be fully disordered owing to a
minimal order in its structure, i.e., the system has an order
disorder rate that favors the phenomenon of PL.
Thus, the sample heat-treated at 500 1C presented more
intense PL than the sample heat-treated at 450 1C. These
samples showed high structural disorder, but the sample heat-
treated at 500 1C showed a degree of orderdisorder that
favored the PL phenomenon. On the order hand, the samples
heat-treated at 550 and 600 1C presented high structural order,
as indicated by the diffraction peaks in their XRD patterns, as
well as low PL.
The samples heat-treated at 550 and 600 1C also showed
peaks corresponding to f-f transitions. In the absorption
process of the CT:Er,Yb powder annealed at 450 and
500 1C, both the CT lattice and the rare earth ions absorbed
light, and the intensity of PL emission of the lattice was higher
than that of the characteristic Er
3
and Yb
3
emission peak.
The intensity of PL emission of the CT matrix decreased in the
material heat-treated at 550 and 600 1C, and erbium emission
was observed.
The difference between the excitation energy and the
maximum emission, which is called the Stokes shift, allows
the strength of the electronphonon interaction to be evaluated.
Fig. 1. XRD diffractograms for CT:Er,Yb annealed at 450, 500, 550, and
600 1C.
Fig. 2. PL spectra for CT:Er,Yb annealed at 450, 500, 550, and 600 1C. All
samples excited at 350.7 nm.
A.C. Eduardo et al. / Ceramics International 40 (2014) 1598115984 15982
PL spectra recorded at the 350.7 nm wavelength excitation
were normalized to evaluate the Stokes shift (Fig. 3).
The increase from the lowest maximum energy emission of
from CT:Er,Yb heat-treated at 450 1C to the sample heat-
treated at 600 1C was consistent with the dependence of the
electronphonon interaction at the temperature of thermal
treatment, and was associated with a nonuniform energy
transition.
Under NIR excitation at 972 nm, CT:Er,Yb heat-treated at
600 1C showed intense upconversion emission (Fig. 4), while
samples heat-treated at lower temperatures showed no upcon-
version emission. Full structural order in a sample is necessary
for the efcient energy transfer of Er
3
and Yb
3
ions.
Hence, structural disorder does not favor the transfer process.
The upconversion process was found to be so efcient that
green emission was easily visible to the naked eye. The sample
showed typical Er
3
emission bands, i.e., green light emission
bands centered at 530 and 553 nm, corresponding, respec-
tively, to
2
H
11/2
and
4
S
3/2
transitions to the
4
I
15/2
ground state.
The red light emission bands centered at 650 nm correspond to
the
4
F
9/2
transition to the
4
I
15/2
ground state, while the near-
infrared light bands from 780 to 850 nm correspond to the
4
I
9/2
transition to the
4
I
15/2
ground state [12,14,28].
These transitions were enabled by the efcient energy
transfer process of Er
3
and Yb
3
ions. The mechanisms of
energy transfer in co-doped Er
3
/Yb
3
materials have been
well reported previously [11,12,14,15]. Based on the energy
matching conditions and the quadratic dependence on excita-
tion power, the possible upconversion mechanisms were
achieved.
4. Conclusions
In summary, orthorhombic Ca
0.98
Er
0.01
Yb
0.01
TiO
3
powders
were synthesized via a soft chemical method. Synthesized
powders exhibits broad emission band pertaining to structu-
rally disordered titanates, on 350.7 nm laser excitation. More-
over, bright intracongurational 4f-4f electronic transitions
were also observed in lanthanide-doped samples on UV
excitation in fully ordered Ca
0.98
Er
0.01
Yb
0.01
TiO
3
crystal
Acknowledgments
The authors thank the Brazilian research nancing institu-
tions FAPEG, CAPES and CNPq for their funding of this
work. This work was supported by INCTMN.
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