CHEMIJA. 2009. Vol. 20. No. 3. P. 169–174
© Lietuvos mokslų akademija, 2009
© Lietuvos mokslų akademijos leidykla, 2009
Sol–gel synthesis of RE
3+
-activated CaWO
4
phosphores
Artūras Žalga
1
*,
Rokas Sažinas
1
,
Edita Garškaitė
1
,
Aivaras Kareiva
1
,
Tomas Bareika
2
,
Gintautas Tamulaitis
2
,
Remigijus Juškėnas
3
,
Rimantas Ramanauskas
3
1
Faculty of Chemistry, Vilnius University,
Naugarduko 24, LT-03225 Vilnius, Lithuania
2
Institute of Materials Science and
Applied Research, Vilnius University,
Saulėtekio 9, LT-10222 Vilnius, Lithuania
3
Institute of Chemistry, A. Goštauto 9,
LT-01108 Vilnius, Lithuania
A series of red-emitting phosphores containing CaWO
4
: RE (RE = Tb
3+
, Eu
3+
, Sm
3+
) was
prepared by an aqueous sol–gel method using tungsten (VI) oxide, WO
3
, calcium nitrate
tetrahidrate, Ca(NO
3
)
2
· 4H
2
O, terbium oxide, Tb
4
O
7
, europium oxide, Eu
2
O
3
, and samar-
ium oxide, Sm
2
O
3
as starting materials. Synthesized ceramics were characterized using in-
frared spectroscopy (IR), X-ray difraction (XRD), scanning electron microscopy (SEM),
and photoluminescence (PL) measurements. Te obtained results clearly show that only
CaWO
4
: Eu phosphor can be efectively excited under photoexcitation at 280, 360 and
460 nm and exhibits red emission in the vicinity of 620 nm.
Key words: CaWO
4
phosphores, sol–gel synthesis, lanthanide doping, photolumines-
cence
* Corresponding author. E-mail: arturas.zalga@chf.vu.lt
INTRODUCTION
Photoluminescence study of diferent crystalline multinary
metal oxide ceramics, either pure or doped, mainly with rare
earth ions such as Eu
3+
, Er
3+
, Nd
3+
etc., revealed a considerable
potential of these materials in optoelectronic applications [1,
2]. Tese compounds could be widely used as phosphores in
cathode-ray tubes, feld emission, vacuum fuorescent and
electroluminescent displays as well as scintillators in X-ray
and positron emission tomographs [1–5]. Te specifc lumi-
nescence behaviour of crystalline ceramics is highly sensitive
to the initial composition of the host material, dopant or sub-
stitutant concentration and processing conditions. Te opti-
cal properties of trivalent rare-earth ions (RE
3+
) in tungstate
materials with scheelite (CaWO
4
) structure have been widely
investigated [6–9], especially due to their attractive third-
order nonlinear dielectric susceptibilities [10, 12]. It is well
known that rare-earth elements can form a series of isomor-
phous tungstates with the general formula RE
x
(WO
4
)
3
[13].
Because of their attractive luminescence and structural prop-
erties, tungstates have been intensively studied and found ap-
plications in many felds such as lasers, fuorescent lamps,
and scintilators during the last few decades. Tungstates can
be divided into two groups with a diferent crystal structure:
scheelites (CaWO
4
, BaWO
4
, SrWO
4
, RE
2
(WO
4
)
3
and PbWO
4
)
and wolframites (MgWO
4
, CdWO
4
, ZnWO
4
and others) [13,
14]. Calcium tungstate CaWO
4
is a representative example of
tungstates with the scheelite structure containing Ca
2+
ions
and WO
4
2–
groups with the coordination number of eight for
Ca
2+
and four for W
6+
, and is considered to be a highly func-
tional material due to its prominent luminescence properties.
When excited by short-wavelength ultraviolet radiation, X-
rays or cathode rays, CaWO
4
shows an efcient blue emission.
Moreover, many researchers focused their attention on euro-
pium (III) and samarium (III) ions as luminescence centres
in red light phosphores with excellent emission properties.
Tus, CaWO
4
, whether doped or substituted by rare-earth el-
ements, is an important optical material which has already