15/05/12 - Oral Communications Afternoon (16h00 - 17h45) 1

Oral Communications Afternoon

(16h00 - 17h45)
PREPARATION AND OPTICAL CHA-
RACTERIZATION OF MATERIALS
[15/05/12 - 16h00 - Room 1]
Crystal growth: from bulk to microcrystals.,
S. L. Baldochi, J. R. Moraes, G. H. G. Naka-
mura, F. R. Silva, L. R. L. Soares, Instituto de
Pesquisas Energeticas e Nucleares - IPEN - CNEN/SP
Crystal growth is an amazing activity. It is one -
eld usually not directly classied as physics in view of
chemistry and materials engineering approaches, howe-
ver, for a deep understanding of crystal growth, requi-
red to achieve the fabrication of useful crystalline ma-
terials, basic principles of physics are needed. Ther-
modynamics is essential to understand a phase dia-
gram denoting equilibrium states plotted as functions
of temperature and concentration, fundamental para-
meters on crystal growth. The heat and mass trans-
port phenomena also play a signicant role in crystal
growth theory and in the control of defects in crys-
tals hosts. The knowledge about the arrangement of
atoms in solids (crystallography) and the inuence of
the crystals geometry is also relevant. The crystal-
lographic direction may be a main parameter on the
defects propagation or growth rate during the fabrica-
tion of a single crystal. In view of multi-phenomena
and multi-scale interactions present in crystal growth
process, advances in this eld have been driven by a
combination of experimental eort (motivated from new
devices and applications), characterization process and
development of theoretical models. The present work
aims to discuss the motivation for, some important early
results, and some current works of our laboratory on
bulk and micro crystal growth. We review the crystal
growth technologies employed (Czochraslki, Zone mel-
ting and micro pulling down) and describe progress of
our group in the last years in optimizing crystal growth
of uorides (BiY F
4
, LiY F
4
, BaY
2
F
8
) and tungsta-
tes (NaLa(WO
4
)
2
, LiLa(WO
4
)
2
) materials aiming the
development of optical applications (mainly laser hosts
and scintillators). The requirements with respect to
size and quality of crystals for dierent applications and
with respect to complexity of crystal growth problems
are discussed based on thermal, optical and structural
characterizations of the obtained samples.
[15/05/12 - 16h30 - Room 1]
Optical and magnetic properties of the single
crystal system Cs
2
NaAlF
6
with Cr
3+
as substitu-
tional impurity, Sandra da Silva Pedro, Mario
Souza Reis, UFF - RJ - Brazil, Sandra da Silva
Pedro, Lilian Pantoja Sosman, UERJ - RJ - Bra-
zil, Heloisa Nunes Bordallo, University of Cope-
nhagen - Copenhagen - Denmark, European Spallation
Source - Lund - Sweden, Ricardo Borges Barthem,
UFRJ - RJ - Brazil, Fabiano Yokaichiya, LNLS -
SP - Brazil Insulating materials doped with transi-
tion metals have been studied in the last years with a
great interest by its optical properties and technological
applications as, for example, tunable solid state lasers,
optical sensors, communications, electronics devices. In
these compounds, the electronic transitions inside the
incomplete shell leads to a broad absorption and emis-
sion bands, with high quantum yield, depending on the
dynamics of the crystalline environment to which the
impurity ion is inserted. The aim of this work is to pre-
sent photoluminescence and excitation spectra at room
and low temperatures and some preliminary magnetic
measurements of the system Cs
2
NaAlF
6
with several
concentrations of Cr
3+
ion as substitutional impurity.
The optical spectra were analyzed from Tanabe-Sugano
theory. The luminescence spectra at 300 K show a
broad band whose intensity depends on the impurity
concentration. The band was attributed to the spin-
allowed transition
4
T
2
(
4
F)
4
A
2
(
4
F) of Cr
3+
ions
in octahedral sites. At 5 K the spectra show a very
rich structure, with a zero-phonon line, attributed to
the
2
E(
2
G)
4
A
2
(
4
F) spin-forbidden electronic tran-
sition with vibrational modes associated to the octahe-
dral Cr
3+
ion. The spectra also show that the Cr
3+
ion
occupies two non-equivalent sites. In the obtained ex-
citation spectra for samples doped with 0.1% and 1.0%
of Cr
3+
were observed the spin-allowed electronic tran-
sitions
4
A
2
(
4
F)
4
T
1
(
4
F),
4
A
2
(
4
F)
4
T
2
(
4
F) and
4
A
2
(
4
F)
2
E(
2
G). With Tanabe-Sugano energy ma-
trices for the d
3
conguration, the values of the crystal
eld parameter Dq, the Racah parameters B and C
were calculated and the position of the energy transiti-
ons
4
A
2
(
4
F)
4
T
1
(
4
P) and
4
A
2
(
4
F)
2
T
1
(
2
G) were
estimated. Heat capacity measurements were realized
with magnetic elds of 0 T, 5 T and 10 T between 2
and 50 K at the 1.0% and 30.0% samples. The change
in specic heat measurements was observed at tempe-
ratures below 10 K. This behavior was attributed to the
Schottky eect caused by the splitting of the crystal -
eld of the dopant ion energy levels. Preliminary analysis
indicates the presence of additional magnetic eects at
low temperatures with change of magnetic eld.
Acknowledgments: FAPERJ and CAPES for nancial
support, and Prof. Dr. Fernando Iikawa (IFGW-
UNICAMP) by collaboration in the optical measure-
ments.
[15/05/12 - 16h45 - Room 1]
Luminescence mechanisms of the phosphor
CdSiO
3
produced via sol-gel route,
Carolina Melo de Abreu, Z elia Soares Ma-
cedo, UFS - SE - Brasil Cadmium silicate CdSiO
3
is a long lasting phosphorescent material of high
technological interest. This material has potential
applications in areas such as emergency lights, opto-
electronic devices and coating of ceramic tiles for
use in radiodiagnostic rooms. It presents intrinsic
luminescence with long lasting emission, with light
persistence of about 3 h. Traditionally, this phosphor
is prepared by a solid state reaction. In this work,
CdSiO
3
was produced via a modied sol-gel route.
The phosphorescent properties were determined for the
material in pure state, doped with Mn
2+
and Gd
3+
,
and also co-doped with (Mn
2+
, Gd
3+
). The starting
materials used to produce the gel were cadmium oxide
(CdO) and tetraethylorthosilicate (TEOS). During
the synthesis, several parameters such as stability
conditions, time and temperature of the calcinations
2 Oral Communications Afternoon (16h00 - 17h45) - 15/05/12
were tested to produce single crystalline phase CdSiO
3
.
The single crystalline phase CdSiO
3
was obtained after
calcination at 1000
o
C for 3 h. The optical properties
of the synthesized powders were studied via optical
absorption (OA), photoluminescence (PL), lifetime
measurements and radioluminescence (RL). The opti-
cal absorption measurements suggest the presence of
the band gap of CdSiO
3
at 5,6 eV (221 nm). These
measurements also presents an absorption band at 4,7
eV (263 nm) possibly related to the absorption of self-
trapped excitons. The PL and RL emission spectra of
the pure, doped and co-doped samples presented broad
emission bands near 408 nm, 480 nm and 590 nm with
dierent relative intensities. Lifetime measurements
presented three decay processes. Combining AO results
with PL and RL spectra, three possible luminescent
channels were identied: (i) direct recombination of
electrons from the conduction band with holes from
the valence band (
em
= 408 nm); (ii) recombination
of excitons (
em
= 480 nm); (iii) emission from color
centers possibly related to impurities, intrinsic defects
and dopants present at low concentration (
em
=
590 nm). The luminescence intensities and lifetimes
increase signicantly with the presence of dopant. This
work enabled the development of phosphors CdSiO
3
with violet (CdSiO
3
undoped), blue (CdSiO
3
:Gd
3+
)
and orange (CdSiO
3
:Mn
2+
; CdSiO
3
:Mn
2+
, Gd
3+
)
emission.
[15/05/12 - 17h00 - Room 1]
Correlation between molecular dynamics and
packing and optical properties on phenylene-
vinylene/aliphatic multiblock copolymers,
O.D. Bernardinelli, Instituto de Fsica de Sao Car-
los - Universidade de Sao Paulo, S.M. Cassemiro,
Paulo Scarpa Polymer Laboratory - Federal University
of Parana, L.A.O. Nunes, Instituto de Fsica de Sao
Carlos - Universidade de Sao Paulo, T.D.Z. Atvars,
Chemistry Institute - State University of Campinas,
L. Akcelrud, Paulo Scarpa Polymer Laboratory
- Federal University of Parana, E.R. deAzevedo,
Instituto de Fsica de Sao Carlos - Universidade de Sao
Paulo Optoelectronic devices with polymer lms as
active layers have become an important topic in science
and technology of todays electronic engineering.
Chemical modications to conne the degree of the
polymer conjugation to well dened values opens the
possibility of engineering materials with tunable gaps
to control the color of the devices emission. One way of
achieving that is preparing multiblock conjugated/non-
conjugated copolymers where the non-conjugated units
are aliphatic spacers. This work reports a detailed
spectroscopy study of a series of multi block conjugated
non conjugated copolymers built by p-phenylene type
units (PV) and an octamethylene spacers, namely,
poly(1,8-octanedioxy-2,6-dimethoxy-1,4-phenylene-1,2-
ethenylene) (LaPPS18). The relative proportions of
the PV and aliphatic segments were estimated based
on Solid-state nuclear magnetic resonance spectroscopy
NMR and Raman spectroscopy. The morphology was
characterized by Wide Angle X-ray Diraction;
1
H Wi-
deline Dipolar Chemical Shift Correlation (DIPSHIFT)
and Centerband-Only Detection of EXchange (CO-
DEX) NMR data, that together with glass transition
temperatures allowed us to identify the groups involved
in the molecular dynamics. These dierent structural
properties were used to explain the photoluminescence
properties in terms of peak position and spectral
prole. Putting all data together, we concluded that
the higher amount of nano-scale crystalline phase is
responsible for both the well resolved vibronic structure
of the photoluminescence band and for the higher T
g
value of the copolymer with greater relative content of
PV units.
[15/05/12 - 17h15 - Room 1]
Inuence of co-dopant in the Eu reduction in
the SrAl
2
O
4
host, P. J. R Montes, , Instituto
Federal de Sergipe, Felipe M. S. Soares, Claudi-
ane dos Santos, M. V. dos S. Rezende, M. E. G.
Valerio, Universidade Federal de Sergipe Rare-
earth-doped aluminates serve as an important class of
phosphor for commercial applications, especially in the
areas of safety improvement and energy saving. Stron-
tium aluminates (SrAl
2
O
4
:Eu
2+
, Dy
3+
) and barium
aluminates (BaAl
2
O
4
:Eu
2+
, Dy
3+
) represent a class of
materials that may exhibit long lasting phosphorescence
and luminescence when doped with trivalent and diva-
lent rare-earth ions. Most aluminates are activated by
Eu
2+
ions, and to obtain the rare earth with this va-
lence the trivalent rare earth oxide is usually used as
the starting material. To reduce the rare earth from
Eu
3+
- Eu
2+
it is necessary to use particular schemes
in the production of the rare earth containing sample.
Many such schemes have been used and developed. The
most common scheme is to use N
2
-H
2
or H
2
, or CO
2
or CO as reducing agents when the rare earth contai-
ning sample is calcined. In this work, the DXAS te-
chnique (Dispersive X-ray Absorption Spectroscopy) is
used to follow the XANES spectrum of the Eu ions du-
ring the calcinations program in H
2
atmospheres in the
SrAl
2
O
4
:Eu
2+
, RE
3+
(RE= Ce
3+
, Gd
3+
, Dy
3+
, Er
3+
,
Y
3+
) samples. Analysis of the reduction dynamics can
give information of the synthesis process and DXAS
technique can be used to follow it. The pre-calcined
samples of SrAl
2
O
4
:Eu
2+
, RE
3+
(RE= Ce
3+
, Gd
3+
,
Dy
3+
, Er
3+
, Y
3+
) samples were prepared at 600
o
C via
a sol-gel proteic route. DXAS spectra were obtained
as a function of temperature excited at the LIII edge
of Eu ions during the synthesis. DXAS spectra exhi-
bit changes of absorption edge position associated to
the LIII edge of the Eu ions during heating and coo-
ling of samples. The ratio of absorption edge Eu
3+
/
Eu
2+
was investigated to verify the eciency of reduc-
tion agents in the stability of Eu
2+
ion in the matrix.
Eu
2
O
3
was used as reference sample. The results show
that the reduction of Eu occur at the calcinations tem-
perature (1100
o
C), but the process is reversible upon
cooling down to room temperature. The results also
shows that the ratio of absorption edge Eu
3+
/ Eu
2+
chance with dierent co-dopant.(This work was parti-
ally supproted by CAPES, CNPq, FINEP and LNLS.
MVSR acknowledge the PhD grant from CNPq).
[15/05/12 - 17h30 - Room 1]
Radioluminescence mechanism of Pr-doped
BaY2F8, Adriano Borges Andrade, Ana Ca-
rolina Santana de Mello, Marcos Vinicius dos
15/05/12 - Oral Communications Afternoon (16h00 - 17h45) 3
Santos Rezende, M ario Ernesto Giroldo Va-
lerio, Universidade Federal de Sergipe - UFS, Sonia
Licia Baldochi, Instituto de Pesquisas Energeticas e
Nucleares - Centro de Laser e Aplicac oes CLA-IPEN
In this work were used the techniques XAFS (X-
Ray Absorption Fine struture) and XEOL (X-Ray Ex-
cited Optical Luminescence), held in Brazilian Synch-
rotron Light laboratory in Campinas-SP, for the study
of processes that cause the luminescence of the scin-
tillator BaY
2
F
8
:2%Pr
3+
. Important new properties on
the mechanism of the luminescent material were ob-
served. The spectrum XEOL the of BaY
2
F
8
:2%Pr
3+
showed the typical emissions ion Pr
3+
, with emissions
at 482, 525, 555, 607, 642 and 722 nm corresponding
to transitions
3
P
2
-
3
H
5
,
3
P
1
+
1
I
6
-
3
H
5
,
3
P
2
-
3
F
4
,
1
D
2
-
3
H
5
,
3
P
2
-
3
F
4
and
1
D
2
-
3
H
5
, respectively. The
XEOL emission intensity measured as function of pho-
ton energy X-ray at the absorption edges L
I
, L
II
and
L
III
to Ba
2+
, and was less intense in edge L
III
of Pr
3+
because it is a dopant. The XEOL is however very dif-
ferent from a characteristic absorption curve measured
in the X-ray transmission mode after edges absorption
intensity XEOL (already normalized by the intensity of
X-ray beam incident) increases monotonically with the
excitation energy, revealing that the eciency scintilla-
tion is greater the greater the energy of photons. These
results suggest a model for the mechanism of scintilla-
tion BaY
2
F
8
:2%Pr
3+
when excited by X-ray, due to the
charge generating process based on absorption of X-ray
photons on the trac of carriers between the bands of
conduction/valence and traps and in the process of radi-
ative recombination of carriers that transfer light energy
for the Pr
3+
. (Work supported by Capes/Fapitec and
CNPq)