ISSN 1087-6596, Glass Physics and Chemistry, 2013, Vol. 39, No. 2, pp. 174–181. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © V.A. Aseev, P.A. Burdaev, E.V. Kolobkova, N.V. Nikonorov, 2013, published in Fizika i Khimiya Stekla.
174
INTRODUCTION
The creation of the technology of preparation of
oxyfluoride glass ceramics was started in the 1970s. An
attempt to synthesize oxyfluoride glasses containing
Ln
2
O
3
(Ln = Y, La, Gd, Lu, Yb), PbF
2
, and M
n
O
m
(M= B, P, Te, Si, Ge) activated by Er
2
O
3
or Tm
2
O
3
was undertaken in [1]. As a result, opaque glass
ceramic materials containing microcrystals with a
radius of the order of 10 μm having a luminescence
efficiency several times higher than that of LaF
3
: Yb :
Er reference luminophores. Later, in 1993, the first
work on the synthesis of transparent glass ceramics
containing a cubic fluoride phase activated by erbium
and ytterbium ions was published [2]. Materials com-
bining all advantages of aluminosilicate glass matrix
with optical characteristics of low phonon fluoride
crystals were prepared for the first time.
Recently, fluorine-containing transparent glass-
crystalline materials activated by REI included in flu-
orite like nanocrystalline phases have attracted atten-
tion due to a certain set of valuable spectroscopic
properties. It is obvious that the optimal materials to
create active laser media, luminescent convectors, and
luminophores are those which are distinguished by the
low frequency phonon spectrum and low content of
OH groups because this makes it possible to reduce the
losses of excitation through the multiphonon quench-
ing process. It was believed for a long time that only
fluorine-containing materials (oxygen-free fluoride
glasses and crystals) are optimal for solution of the
mentioned problem. However, recently, the synthesis
of glass-crystalline materials, namely oxyfluoride sili-
cate glasses, became a priority direction [3–11]. Such
composite materials combine optical parameters of
low phonon fluoride crystals with high mechanical,
thermal, and chemical characteristics of silicate
glasses. It was found that the formation of fluoride
nanocrystals activated by REI in the process of heat
treatment of an initial glass was possible for some oxy-
fluoride glass-like materials. Therefore, the materials
obtained combine all the best properties of fluoride
nanocrystals influencing optical and spectral-lumi-
nescent properties of REI, as well as simplicity of
preparation and excellent performance characteristics
of oxide glasses (chemical stability, mechanical and
thermal strength, optical quality). It is known that
minimization of losses due to light absorption and
scattering is a critical question when developing opti-
cally transparent glass ceramics, including that
applied in optical waveguides. The Rayleigh scattering
occurring on microinhomogeneities that are close in
terms of size to wavelength of the radiation is a limiting
factor when using such materials and imposes strict
restrictions on the sizes of the separated crystalline
phase. According to the concepts of the Rayleigh the-
ory, the crystals dispersed in glass should have a radius
of no more than 15 nm for the visible region of the
spectrum. The difference in values of the refractive
index between crystalline phase and an amorphous
matrix should not exceed 0.1. These restrictions were
subsequently somewhat alleviated. The possibility of
preparation of a transparent glass ceramics with
nanocrystals having sizes of up to 30 nm and with dif-
ference in the refractive indices of no more than 0.3
was demonstrated on the basis of the model [3].
Fluorophosphate Nanostructured Glass Ceramics
Activated by Erbium Ions
V. A. Aseev
a
, P. A. Burdaev
b
, E. V. Kolobkova
a
, and N. V. Nikonorov
a
a
St. Petersburg State University of Information Technologies, Mechanics, and Optics,
Kronverkskii pr. 49, St. Petersburg, 197101 Russia
e-mail: kolobok106@rambler.ru
b
St. Petersburg State Technological Institute (Technological University), Moskovskii pr. 26, St. Petersburg, 190013 Russia
Received November 18, 2011
Abstract—Possibility of preparation of transparent nanostructured glass crystalline materials based on fluo-
rophosphate glasses with high fluoride content is demonstrated. The influence of concentration of rare earth
ions (REI) on the crystallization process is studied. We determined the conditions of heat treatment to form
nanocrystals containing REI whose growth is evidenced by the results of X-ray phase analysis changes in the
absorption and luminescence spectra and in the lifetime of the excited level of trivalent erbium.
Keywords: nanocrystals, glasses, rare earth ions-activators
DOI: 10.1134/S108765961302003X