ISSN 1063-7745, Crystallography Reports, 2007, Vol. 52, No. 6, pp. 1088–1093. © Pleiades Publishing, Inc., 2007.
Original Russian Text © S.F. Burachas, A.A. Vasil’ev, M.S. Ippolitov, V.I. Man’ko, Yu.A. Savel’ev, G. Tamulaitis, 2007, published in Kristallografiya, 2007, Vol. 52, No. 6,
pp. 1124–1130.
1088
INTRODUCTION
Currently, high optical transparency and radiation
hardness of oxide crystals are important for their prac-
tical application. The nature of absorption centers in the
transparency region of oxide crystals and changes in the
color of crystals subjected to irradiation or annealing
have not been properly studied. Deviation from stoichi-
ometry in oxygen [1] is considered to be a characteristic
defect of complex oxides. An oxygen deficit is inherent
in oxides of heavy metals with a variable valence [2].
Analysis of the data in the literature on the specific fea-
tures of the production of a number of crystals (PbWO
4
,
LiNbO
3
, SrTiO
3
, and YAlO
3
) showed that deviation
from stoichiometry is a typical cause of the formation
of defects in these crystals.
In lead tungstate (PbWO
4
) crystals, tungsten ions
can have a variable valence, from 4 to 6. It is possible
that, owing to the deviation from stoichiometry during
crystal growth, inclusions of tungsten oxide are formed
in the melt and then are incorporated into the regular
lattice [3–8]. In [9–12], it was suggested that the main
cause of the deviation from stoichiometry in lithium
niobate (LiNbO
3
) crystals is the oxygen deficit in nio-
bium oxide (Nb
2
O
5 – x
) used for preparation of the start-
ing melt. In [13–15], it was believed that, along with the
deviation from stoichiometry in oxygen in strontium
titanate (SrTiO
3
), some part of regular Ti
4+
ions pass to
the Ti
3+
state upon reductive annealing and form a char-
acteristic “blue spot” defect. In [16], it was suggested
that crystals of yttrium aluminate YAlO
3
:Cr subjected
to reductive annealing contain aluminum in different
valence states: Al
2
O
3
, AlO, and Al
2
O. The presence
of such complexes in YAlO
3
was confirmed in [17].
In this study, by the example of PbWO
4
, LiNbO
3
,
SrTiO
3
, and YAlO
3
crystals, we consider the causes of
defect formation in oxide crystals with an oxygen defi-
cit.
INVESTIGATION OF THE TRANSPARENCY
OF PbWO
4
AND LiNbO
3
CRYSTALS
We studied the effect of irradiation and annealing on
the optical characteristics of PbWO
4
and LiNbO
3
crys-
tals. Two elements 22 × 22 × 180 mm
3
in size and cut
from PbWO
4
crystals grown from a charge and doped
with gadolinium (80 ppm) were analyzed. The crystals
were colorless before irradiation. After irradiation
(with a total irradiation dose up to 1 × 10
13
neutrons/cm
2
for 15 h), as well as after reductive annealing at a tem-
perature of 850°C for 20 h in the atmosphere with an
oxygen content of 0.001%, the crystals acquired a vio-
let tint. Comparison of the transmittance distribution
along the length of the elements (before and after
annealing for the first element and before and after irra-
diation for the second element (Figs. 1, 2)) shows that
the absorption spectra recorded after irradiation and
reductive annealing are almost identical. This fact indi-
cates the same origin of the crystal coloring under these
external actions. However, the color of the annealed
crystals differs from the color of the irradiated ones.
Influence of Cluster Defects of Variable Composition
on the Optical and Radiative Characteristics of Oxide Crystals
S. F. Burachas
a
, A. A. Vasil’ev
a
, M. S. Ippolitov
a
, V. I. Man’ko
a
,
Yu. A. Savel’ev
b
, and G. Tamulaitis
c
a
Russian Research Centre Kurchatov Institute, pl. Akademika Kurchatova 1, Moscow, 123182 Russia
e-mail: sburachas@inbox.ru
b
North Crystals Company, Apatity, Murmansk oblast, Russia
c
Vilnius University, Vilnius, Lithuania
Received October 30, 2006
Abstract—It is shown that oxide crystals contain cluster defects of variable composition, which cause absorp-
tion of light in the transparency region of crystals. The model based on the presence of cluster defects in oxide
crystals explains well the experimental data on the thermal and radiative coloring of these crystals. It is noted
that cluster defects accumulate oxygen in oxide crystals. These defects are responsible also for the photochro-
mic effect in them. Application of the noted model made it possible to fabricate lead tungstate scintillators at
North Crystals Company for the ALICE project (CERN) with almost 100% reproducibility of their operating
characteristics.
PACS numbers: 61.72.-y
DOI: 10.1134/S1063774507060259
PHYSICAL PROPERTIES
OF CRYSTALS