Universidade de São Paulo

Biblioteca Digital da Produção Intelectual - BDPI

Departamento de Física e Ciências Materiais - IFSC/FCM Artigos e Materiais de Revistas Científicas - IFSC/FCM

2014-12

Structural disorder-dependent upconversion in

Er3+/Yb3+ - doped calcium titanate

Ceramics International, Amsterdam : Elsevier, v. 40, n. 10, part A, p. 15981-15984, Dec. 2014
http://www.producao.usp.br/handle/BDPI/50357

Downloaded from: Biblioteca Digital da Produção Intelectual - BDPI, Universidade de São Paulo
 Available online at www.sciencedirect.com

CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 15981–15984
www.elsevier.com/locate/ceramint

Structural disorder-dependent upconversion in Er3 þ /Yb3 þ -doped

calcium titanate
Ariadne C. Eduardoa, Alberthmeiry T. de Figueiredoa,n, Maximo Siu Lib, Elson Longoc
a
Department of Chemistry – UFG campus Catalão, 75.704-020, Catalão, Brazil
b
Institute of Physics, 13.566–590, USP-SÃO CARLOS, São Carlos, Brazil
c
INCTMN, Institute of Chemistry, UNESP, 14.801–970, 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 CaTiO3 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 order–disorder. 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; Order–disorder effect; Photoluminescence

1. Introduction frequency excitation due to excited state absorption through

Rare-earth (RE) doped materials are widely used in optical
devices such as sensors, amplifiers, waveguides, solid-state
lighting and lasers, as well as in biological applications [1–5].
They are characterized mainly due to their partially filled 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 (CaTiO3) phosphors have been studied
extensively due to their well-known chemical stability. In
recent years, CaTiO3:Pr3 þ has attracted much attention
because high red-light emission appears only starting from
the 1D2 (Pr3 þ ) level in this material [6–10].
Several such materials show high-frequency upconversion
luminescence on excitation with comparatively lower
n
Corresponding author.
E-mail address: alberth@ufg.br (A.T. de Figueiredo).
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 [11–16]. Yang et al. [13] studied the
reduction of upconversion emission in CaTiO3:Yb,Er, while
Deren et al. [17] showed upconversion emission in CaTiO3:
Er3 þ 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 final
recombination [18–24].
The objective of this work was to synthesize Er and Yb-
doped CaTiO3 powders by the polymeric precursor method.

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.
15982 A.C. Eduardo et al. / Ceramics International 40 (2014) 15981–15984
The structure and optical properties were evaluated by X-ray
diffraction (XRD), and photoluminescence analysis. The
material showed upconversion emission.
2. Experimental details
The Ca0.98Er0.01Yb0.01TiO3-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
Kα radiation) in the mode of θ-2θ scan (θ 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 CaTiO3, ICDD card
no. 42–423 (Pbnm). Also, a literature survey revealed that the
peak position is not affected significantly when CaTiO3 is
doped with a low concentration [8,25,26]. Therefore, no
significant change was detected in the position of the peaks
at the concentration used here. Samples heat-treated at 450 and
Fig. 1. XRD diffractograms for CT:Er,Yb annealed at 450, 500, 550, and
600 1C.
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 order–disorder 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 order–disorder
[22–24,27]. 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 order–disorder 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 Er3 þ and Yb3 þ 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 electron–phonon interaction to be evaluated.
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) 15981–15984
Fig. 3. Normalized PL spectra for CT:Er,Yb annealed at 450, 500, 550, and
600 1C. All samples excited at 350.7 nm.
Fig. 4. Upconversion emission spectra for CT:Er,Yb annealed at 450, 500,
550, and 600 1C with excitation wavelength at 972 mm.
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
electron–phonon 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 efficient energy transfer of Er3 þ and Yb3 þ ions.
Hence, structural disorder does not favor the transfer process.
The upconversion process was found to be so efficient that
green emission was easily visible to the naked eye. The sample
showed typical Er3 þ emission bands, i.e., green light emission
15983
bands centered at 530 and 553 nm, corresponding, respec-
tively, to 2H11/2 and 4S3/2 transitions to the 4I15/2 ground state.
The red light emission bands centered at 650 nm correspond to
the 4F9/2 transition to the 4I15/2 ground state, while the near-
infrared light bands from 780 to 850 nm correspond to the 4I9/2
transition to the 4I15/2 ground state [12,14,28].
These transitions were enabled by the efficient energy
transfer process of Er3 þ and Yb3 þ ions. The mechanisms of
energy transfer in co-doped Er3 þ /Yb3 þ 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 Ca0.98Er0.01Yb0.01TiO3 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 intraconfigurational 4f-4f electronic transitions
were also observed in lanthanide-doped samples on UV
excitation in fully ordered Ca0.98Er0.01Yb0.01TiO3 crystal”
Acknowledgments
The authors thank the Brazilian research financing institu-
tions FAPEG, CAPES and CNPq for their funding of this
work. This work was supported by INCTMN.
References
[1] G. Nemova, R. Kashyap, Laser cooling with rare-earth-doped direct
band-gap semiconductors, J. Opt. Soc. Amer. B: Opt. Phys 30 (2013)
1141–1147.
[2] A. Jha, B. Richards, G. Jose, T. Teddy-Fernandez, P. Joshi, X. Jiang,
J. Lousteau, Rare-earth ion doped TeO2 and GeO2 glasses as laser
materials, Prog. Mater. Sci. 57 (2012) 1426–1491.
[3] G.A. Kumar, M. Pokhrel, D.K. Sardar, Intense visible and near infrared
upconversion in M2O2S: Er (M¼ Y, Gd, La) phosphor under 1550 nm
excitation, Mater. Lett. 68 (2012) 395–398.
[4] C. Bouzigues, T. Gacoin, A. Alexandrou, Biological Applications of
Rare-Earth Based Nanoparticles, Acs Nano 5 (2011) 8488–8505.
[5] F. Zhang, R.C. Haushalter, R.W. Haushalter, Y.F. Shi, Y.C. Zhang, K.
L. Ding, D.Y. Zhao, G.D. Stucky, Rare-Earth Upconverting Nanobar-
codes for Multiplexed Biological Detection, Small 7 (2011) 1972–1976.
[6] A.V. Shlyakhtina, D.A. Belov, S.Y. Steafanovich, E.A. Nesterova, O.
K. Karyagina, L.G. Shcherbakova, Optimization of synthesis conditions
for rare-earth titanate based oxygen ion conductors, Solid State Ionics 230
(2013) 52–58.
[7] Y. Inaguma, T. Tsuchiya, Y. Mori, Y. Imade, N. Sato, T. Katsumata,
D. Mori, Temperature dependence of luminescence properties of
praseodymium-doped perovskite CaTiO3:Pr3þ , Thermochim. Acta 532
(2012) 168–171.
[8] H.K. Yang, J.W. Chung, B.K. Moon, B.C. Choi, J.H. Jeong, J.S. Bae, K.
H. Kim, Significant reduction of upconversion emission in CaTiO3: Yb,
Er inverse opals, Solid State Sci. 13 (2011) 1420–1423.
[9] H. Takashima, K. Ueda, M. Itoh, Red photoluminescence in
praseodymium-doped titanate perovskite films epitaxially grown by
pulsed laser deposition, Appl. Phys. Lett. 89 (2006) 261915.
15984 A.C. Eduardo et al. / Ceramics International 40 (2014) 15981–15984
[10] L.A. Dunyushkina, E.A. Mashkina, I.Y. Nechaev, A.A. Babkina, N.
O. Esina, D.V. Zhuravlev, A.K. Demin, Electrophysical properties of
titanates of alkaline-earth metals, Ionics 8 (2002) 293–299.
[11] Y. Onodera, T. Nunokawa, O. Odawara, H. Wada, Upconversion
properties of Y2O3:Er,Yb nanoparticles prepared by laser ablation in
water, J. Lumin. 137 (2013) 220–224.
[12] X.H. Pan, J.D. Yu, Y. Liu, S. Yoda, M.H. Zhang, F. Ai, F. Jin, H.M. Yu,
W.Q. Jin, Infrared to visible upconversion luminescence in Er3þ /Yb3þ
doped titanate glass prepared by containerless processing, J. Lumin. 132
(2012) 1025–1029.
[13] Z.W. Yang, K. Zhu, Z.G. Song, D.C. Zhou, Z.Y. Yin, L. Yan, J.B. Qiu,
Significant reduction of upconversion emission in CaTiO3: Yb, Er
inverse opals, Thin Solid Films 519 (2011) 5696–5699.
[14] X. Pan, J. Yu, Y. Liu, S. Yoda, H. Yu, M. Zhang, F. Ai, f. Jin, W. Jin,
Thermal, mechanical, and upconversion properties of Er(3þ )/Yb(3þ )
co-doped titanate glass prepared by levitation method, J. Alloys Comp.
509 (2011) 7504–7507.
[15] J. Zhou, W. Zhang, T. Huang, L. Wang, J. Li, W. Liu, B. Jiang, Y. Pan,
J. Guo, Optical properties of Er,Yb co-doped YAG transparent ceramics,
Ceram. Int. 37 (2011) 513–519.
[16] H. Guo, N. Dong, M. Yin, W.P. Zhang, L.R. Lou, S.D. Xia, Green and
red upconversion luminescence in Er3þ-doped and Er3þ/Yb3þ -
codoped SrTiO3 ultrafine powders, J. Alloys Comp 415 (2006) 280–283.
[17] P.J. Deren, R. Mahiou, R. Pazik, K. Lemanski, W. Strek, P. Boutinaud,
Upconversion emission in CaTiO3: Er3þ nanocrystals, J. Lumin. 128
(2008) 797–799.
[18] K.P. Beh, F.K. Yam, L.L. Low, Z. Hassan, One-step growth of curled
GaN nanowires using chemical vapor deposition method, Vacuum 95
(2013) 6–11.
[19] Z.Q. Liu, G.Q. Liu, Y.H. Chen, K. Huang, Y. Hu, X.N. Zhang, Z.J. Cai,
X.S. Liu, G.L. Fu, Modification of spontaneous emission from fluorescent
spheres by partially disordered photonic crystals, Mater. Lett. 101 (2013)
44–46.
[20] L.L. Zhu, X. Li, Q. Zhang, X. Ma, M.H. Li, H.C. Zhang, Z. Luo,
H. Agren, Y.L. Zhao, Unimolecular Photoconversion of Multicolor
Luminescence on Hierarchical Self-Assemblies, J. Amer. Chem. Soc.
135 (2013) 5175–5182.
[21] Y.I. Mazur, V.G. Dorogan, M. Benamara, M.E. Ware, M. Schmidbauer,
G.G. Tarasov, S.R. Johnson, X. Lu, S.Q. Yu, T. Tiedje, G.J. Salamo,
Effects of spatial confinement and layer disorder in photoluminescence of
GaAs1-xBix/GaAs heterostructures, J. Phys. D: Appl. Phys 46 (2013)
065306.
[22] R.F. Goncalves, J.T.O. Figueiredo, A.T. de Figueiredo, M.S. Li,
E. Longo, M.J. Godinho, Photoluminescence of core-shell nanoparticles
made from yttrium stabilized zirconia powder grain coated with alumina,
Crystengcomm 15 (2013) 3292–3295.
[23] A.T. de Figueiredo, V.M. Longo, R.O. da Silva, V.R. Mastelaro,
A. Mesquita, R.W.A. Franco, J.A. Varela, E. Longo, Structural XANES
characterization of Ca0.99Sm0.01TiO3 perovskite and correlation with
photoluminescence emission, Chem. Phys. Lett. 544 (2012) 43–48.
[24] V.M. Longo, L.S. Cavalcante, M.G.S. Costa, M.L. Moreira, A.T. de
Figueiredo, J. Andres, J.A. Varela, E. Longo, First principles calculations
on the origin of violet-blue and green light photoluminescence emission
in SrZrO3 and SrTiO3 perovskites, Theor. Chem. Acc. 124 (2009)
385–394.
[25] N. Suriyamurthy, B.S. Panigrahi, Investigations on luminescence of rare
earths doped CaTiO(3):Pr(3 þ ) phosphor, J. Rare Earths 28 (2010)
488–492.
[26] S.Y. Yin, D.H. Chen, W.J. Tang, Y.H. Peng, Synthesis of CaTiO3: Pr
persistent phosphors by a modified solid-state reaction, Mater. Sci. Eng.
B 136 (2007) 193–196.
[27] L.H. Oliveira, A.P. de Moura, T.M. Mazzo, M.A. Ramirez, L.
S. Cavalcante, S.G. Antonio, W. Avansi, V.R. Mastelaro, E. Longo, J.
A. Varela, Structural refinement and photoluminescence properties of
irregular cube-like (Ca-1_Cu-x(x))TiO3 microcrystals synthesized by the
microwave-hydrothermal method, Mater. Chem. Phys. 136 (2012)
130–139.
[28] I.K. Battisha, Y. Badr, N.M. Shash, M.G. El-Shaarawy, A.G.A. Darwish,
Detection of up-conversion in nano-structure BaTiO3 co-doped with
Er3 þ and Yb3þ ions, J. Sol-Gel Sci. Technol. 53 (2010) 543–550.