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Transparent Oxyfluoride Glass Ceramics

Article in Journal of Fluorine Chemistry January 2015
DOI: 10.1016/j.jfluchem.2015.01.009
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Journal of Fluorine Chemistry 172 (2015) 2250
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry

journal homepage: www.elsevier.com/locate/fluor
Review, Review Article
Transparent oxyuoride glass ceramics

P.P. Fedorov a,*, A.A. Luginina a,b, A.I. Popov c
a
General Physics Institute RAS, 38 Vavilov Street, Moscow 119991, Russia

All-Russian Institute of Scientic and Technical Information (VINITI), 20 Usievich Street, Moscow 125190, Russia
c
Cardinal Intellectual Property, Aston, PA 19014, USA
b
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 9 December 2014
Received in revised form 13 January 2015
Accepted 22 January 2015
Available online 31 January 2015
The present review article covers the history, featured properties and modern state of inorganic, physical
and materials chemistry of transparent oxyuoride glass ceramics. The subjects discussed include the
preparation methods for these materials (e.g., synthesis from starting glass and/or amorphous matrices,
devitrication, etc.), comparative description of their spectral and luminescent properties, formation of
rare earth-containing nanouoride phases in oxide glass matrices by oriented attachment mechanism,
distribution of dopants in oxyuoride glass ceramics as well as the practical application of the latter
materials.
2015 Elsevier B.V. All rights reserved.
Keywords:
Inorganic oxyuorides
Glass ceramics
Nanoparticles
Nanouorides
Nanocomposites
Oriented attachment
Contents
1.
2.
3.
4.
5.
6.
7.
8.
9.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
General history of glass ceramics. . . . . . . . . . . . . . . . . . . .
1.1.
History of oxyuoride glass ceramics . . . . . . . . . . . . . . . .
1.2.
Features of oxyuoride glass ceramics . . . . . . . . . . . . . . .
1.3.
Representation of oxyuoride glass ceramics in scientic
1.4.
Types of glass ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Crystallization and devitrication (devitriheation) of glasses . . .
Fundamentals of glass crystallization [8] . . . . . . . . . . . . .
3.1.
Micro-liquation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Preparation of transparent glass ceramics . . . . . . . . . . . . . . . . . .
Properties of glass ceramics and methods of their studying . . . .
Oriented attachment of nanoparticles . . . . . . . . . . . . . . . . . . . . .
Phase and chemical composition of the nanocrystals . . . . . . . . .
Spectral and luminescent properties of glass ceramics . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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22
22
23
23
24
24
29
29
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31
33
40
41
44
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46
46
1. Introduction
1.1. General history of glass ceramics
* Corresponding author. Tel.: +7 4995038292; fax: +7 4991357744.
E-mail addresses: ppfedorov@yandex.ru, ppf@lst.gpi.ru (P.P. Fedorov).
http://dx.doi.org/10.1016/j.juchem.2015.01.009
0022-1139/ 2015 Elsevier B.V. All rights reserved.
Natural and man-made glass ceramic materials, i.e., materials

containing one or more crystalline phases evenly distributed
P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250
within the glass phase, have been known for ages. People used hard
and brittle obsidian (volcanic glass with imbedded tiny crystals)
for their tools as early as the Stone Age. The rst glass articles
prepared in Ancient Egypt, Syria and Mesopotamia in the middle of
the 3rd millennium BC were not entirely made of glass: they
contained admixtures of crystallized materials. However, for ages,
people considered glasses with detectable (visible) amounts of
crystalline phases as substandard and not suitable for their
designated use. This approach to the glass material quality did not
interfere with the parallel development and further application of
such glass ceramics as enamel, glaze, majolica and smalt for
decorative purposes (dishware, mosaic, etc.), where material
inhomogeneities were viewed as advantages not drawbacks. The
situation changed in the 1950s with an unexpected discovery
made by American chemist Stanley Donald Stookey, who studied
photosensitive glasses at Corning Glass Works in Corning, New
York since the 1940s [13]. Overheating of one of his glass samples
led to the formation of non-transparent material with superior
mechanical qualities. Stookey found that if the photosensitive glass
is heated higher than the normal temperature for the thermal
treatment of photosensitive glass, this glass would not melt.
Instead, it loses transparency and forms polycrystalline ceramics
with unusually high mechanical strength.
This accidental nding opened the way for the abundant use of
a whole class of materials labeled as glass ceramics (sometimes
these materials were also named as semiglasses and/or vitroceramics). Stookeys observation led to the conclusion that
heterogeneous glass ceramics are not inferior in comparison with
homogeneous glasses. In fact, glass ceramics may have much
better (i.e., more suitable) properties and, thus, much broader
application, different from the use of similar entirely glassy
materials [4]. However, in order to achieve such properties, the
preparation of glass ceramics has to be carried out under quite
specic controlled conditions, so the synthesized material would
have desired properties.
Stookeys discovery was kept hidden for some time due to the
specic areas of applications for his new material (e.g., making the
nosecones for missiles, etc.). Later, Stookey received several
patents protecting his discoveries and Corning Glass Works
announced his ndings on May 23, 1957 naming the new material
as Pyroceram [5]. This research achievement did not go unnoticed,
and other researchers began similar studies: for example, in
1958 the Soviet chemist I. I. Kitaigorodskii prepared glass ceramics
that he called Sitall (the rst letter was taken from steklo, a Russian
name for glass, and the rest of this name came from kristall, a
Russian name for crystal) [6].
Transparent glass ceramics may be viewed as composite
materials that combine the advantages of all their components,
glasses and crystals. Glass ceramics contain crystalline objects of
different sizes inside their bodies. If these micro-crystals are less
than the wavelength of visible light, then these materials are called
as transparent glass ceramics [7]. We will use the latter term in this
paper for the sake of convenience.
Since the 1980s, scientists have focused their attention on the
synthesis and the properties of these transparent glass ceramics
with 1030 nm crystallites, for these inclusions cause minimal
light scattering [8].
Incorporation of semiconducting, ferroelectrical and non-linear
optical phases in glass matrices can produce very promising
materials for modern industry [712]. This is especially important
for transparent glass ceramics with photonics applications,
because of the feasibility of its industrial scale production. Such
materials, activated by rare earth elements, play a crucial role in
optical ampliers, up-conversion bers, solid-state lasers, medical
sensors, optical electronic chips, luminescence labels, 3D displays,
etc. [1315].
23
1.2. History of oxyuoride glass ceramics

Stookey prepared uoride glass ceramics [16], but they were
not doped [17,18] and were never designated for use as optical
materials (e.g., as luminescent materials, etc.).
In 1993, Wang and Ohwaki [19] rst reported the synthesis of
doped transparent oxyuoride glass ceramics which contained
crystalline PbxCd1xF2 cubic uoride phase activated by erbium
and ytterbium ions and distributed in the oxide glass matrix. This
novel material, named as oxyuoride glass ceramics, combined
advantages of aluminosilicate matrices with optical features of
low-phonon uoride crystals, thus opening a different venue in the
area of potential luminescence and laser materials [2024].
It is worth noting that transparent glass ceramics, in addition to
possessing various novel features, have advantages of glasses and
single crystals and lack drawbacks which are typical these
materials. Similar to glasses, glass ceramics can be easily treated
and used to manufacture bers; they have a large capacity to
accommodate activating dopants, are isotropic and have evenly
distributed activators within their bodies. Similar to single crystals,
glass ceramics contain rare earth dopants within strictly ordered
ligand surroundings. As a result, their luminescence lines have
higher intensities and lower half-widths compared to similar
dopants in glasses, i.e., their spectral and luminescence properties
are similar to those of single crystals. The relatively small size of
the crystalline particles imbedded in the glass matrices may
signicantly affect the phonon spectra of the former component;
and changes in phonon spectra affect the luminescent properties of
the whole composite material, including lifetimes of the excited
states, making them different from the same properties of the
entirely crystalline specimens.
1.3. Features of oxyuoride glass ceramics
Oxyuoride glass ceramics are unique materials, and before we
proceed further in our description of their features and advantages,
we would like to highlight their relations with other types of
inorganic substances.
Oxyuoride glass ceramics differ from the other inorganic
oxyuorides (crystals, glasses, etc.) not only by their inhomogeneity they contain glass and at least one crystalline phase but also
by their additional unusual and very specic feature: crystals
imbedded in the glass matrix are mainly uoride crystals, whereas
the glass matrix itself has a predominantly oxide nature.
Originally, it was thought that such a feature would provide
oxyuoride ceramics with a very important advantage over entire
class of uoride glass ceramics and/or uoride glasses, especially
when considering that because oxyuoride glass ceramics contain
rare earth element dopants primarily allocated in the crystalline
phases, the spectroscopic properties of such oxyuoride glass
ceramics are similar to the properties of uoride single crystals.
Fluoride nanocrystals, contained in oxyuoride glass ceramics, are
characterized by a narrow phonon spectrum, high luminescence
quantum yield, and a long lifetime for the metastable state.
However, the reality appeared to be more complex [25,26] (please
see Section 7).
The second advantage of oxyuoride glass ceramics over other
doped uoride optical materials (including crystals, glasses and
uoride glass ceramics) stems from the ability of the former class
of materials to stabilize metastable crystalline uoride phases that
cannot be otherwise prepared and/or preserved at room temperature. This could happen because of the following two reasons. First,
the formation of nanoparticles is a highly non-equilibrium process,
and the sequence of crystallizing phases occurs in accordance with
Ostwalds step rule. Moreover, oxide matrices (both glass-like and
crystalline) as well as oxygen impurities are known for their
24
unusual and unexpected effects of stabilizing otherwise unstable

uoride compounds and structures.
The third advantage of oxyuoride glass ceramics is that in this
material (as a particular case of more general class of glass
ceramics) the glass phase simply prevents nanoparticle agglomeration.
The fourth advantage of glass ceramics (including oxyuoride
caramics) is that it contains crystalline nanoparticles imbedded in
the glass matrix, and the latter circumstance naturally solves one
of very important problems of modern nanotechnologyinactivation of the highly developed and active surface of the nanoparticles. This is especially important in the case of uoride
nanoparticles, as their luminescence can easily be quenched by
the adsorption of water on their surfaces.
The glass component of oxyuoride glass ceramics is quite
chemically inert, and this results in the lowered toxicity of glass
ceramics in comparison to that of crystalline uorides.
Glass ceramics are relatively inexpensive. They have better
mechanical and thermal properties than glasses. They can be easily
obtained by the thermal treatment of starting glass under the
specic heating conditions. Glass ceramics also maintain the
advantages of glass as a functional material; for example, they
allow the manufacturing of optical bers [22,28].
1.4. Representation of oxyuoride glass ceramics in scientic
literature
The number of publications about transparent glass ceramics,
including oxyuoride glass ceramics and certain trademarked
materials, has steadily grown over last couple of decades,
especially, after 2000 (Fig. 1). This includes papers dedicated to
pyroceram, vitroceram, sitall (astrositall) and others (Fig. 1) and
indicates a sustained interest of modern researchers in oxyuoride
glass ceramics: there were about 5 publications in this area in
19931998, 10 papers in 19992000, 80+ articles in 20012005
and 200+ publications in 20062010.
There have been several review articles pertinent to the topic of
oxyuoride glass ceramics, among which, we would like to note
the following.
The rst paper is a 1999 Beall and Pinckney [10] analysis of
information about nanophase glass ceramics. The authors [10]
described transparent oxyuoride glass ceramics as a new class of
materials that combines all the best properties of uoride
Fig. 1. Annual numbers of publications on oxyuoride* + transparent +

glass* + ceramic* as per Web of ScienceAll Databases deduplicated records
(2014 data are incomplete and they are presented as of January 1, 2015).
nanocrystals responsible for control of the spectral properties of

rare earth dopants and excellent macroscopic features of oxide
glasses (such as chemical stability, mechanical tenacity and optical
quality).
Mortier and Dantelle [30] briey described synthetic protocols
for the preparation of transparent oxyuoride glass ceramics
containing PbF2, CdF2, CaF2 and LaF3 crystals. They also discussed
the thermal and optical properties of these materials and
compared spectral luminescence characteristics of transparent
oxyuoride glass ceramics with the similar features of starting
glass precursors.
Fedorov et al. [29] emphasized that transparent oxyuoride
ceramics attract researchers attention because they have uoride
nanocrystals as their crystalline component with a narrow phonon
spectrum, high quantum yield luminescence and long life-times
for metastable states. Fedorov et al. [29] specically mentioned
the nanocomposite nature of transparent oxyuoride ceramics and
stated that its glass matrix naturally prevented agglomeration of
imbedded nanoparticles (the latter is the key problem for modern
nanotechnology).
Finally, Pablos-Martin, Duran, and Pascual suggested a mechanism for crystallization and photonic properties of nanocrystallization in oxyuoride systems [31].
The present review describes various transparent oxyuoride
glass ceramics doped by rare earth elements and their properties,
analyzes different methods of their preparation, discusses spectral
luminescence properties of these materials and compares them
with the optical characteristics of glasses and single crystals.
2. Types of glass ceramics
In addition to the aforementioned classication of glass
ceramics into 2 types according to their transparency (transparent
and non-transparent glass ceramics), they also can be classied on
the basis of their glass composition type, of the crystalline phase
type(s) and dopant type(s).
Depending on their chemical composition, oxyuoride glass
ceramics can be of oxide (silicate, quartz, germinate, phosphate,
borate), chalcogenide, halogenide or mixed nature. These materials
have different refraction coefcients: n = 1.46 for quartz glasses,
n = 1.401.55 for silicate glasses, n = 1.61.7 for germanate glasses
and n = 1.76 for borate glasses [3234]. Glass phase composition
determines the initial conditions of starting glass precursor
preparation: the glass melting temperature can vary from ca.
1700 8C for quartz glasses to ca. 14001600 8C for silicate glasses
and to ca. 1200 8C for germinate or borate glasses. Preparation of
glass ceramics from of aluminosilicate [3540], silicate [41],
silicoborate [4244], lead-silicate [4547], quartz [4853], leadgermanate [5456], tellurate-germanate [57], zinc-tellurate [58],
lithium-borate, potassium-borate, barium-borate [59,60], tungsten-lead-phosphate [61] and others glasses with high metal
uoride content is thoroughly described in the literature (see
Table 1).
Despite the seeming diversity of the data in Table 1, their
analyses demonstrate that the majority of the used glass matrices
are aluminosilicate glasses modied by different supplements,
such as various uorides and oxides of alkali and/or alkali earth
metals, zinc, and even anhydrides of boric and phosphoric acids.
Additions of the latter simplify glass formation. Fig. 2 shows a
composition tree for alumosilicate glasses used to synthesize
oxyuoride glass ceramics. Similar classication has been done for
uoroindate and uoroaluminate glasses earlier [233,234]. It is
worth noting that usually the glass compositions are quite
complex. Fedorov [231,232] indicate that this specic number of
57 components corresponds to the highest possible stability of
the glasses formed in multicomponent systems.
25
Method
Table 1
Oxyuoride nano-glassceramics.
Nanoparticles**
50SiO220Al2O330CaF2
49SiO230Al2O320CaF21SmF3
49SiO230Al2O320CaF21EuF3
42SiO2-23Al2O332CaF23ErF3
42SiO223Al2O333CaF22YbF3
45SiO215Al2O335CaF24Yb2O31Er2O3
SiO2Al2O3CaF2LaF3
60SiO220Al2O320CaF21TmF3xYbF3 (x 8)
50SiO220Al2O320CaF2(10 x)CeF3xDyF3,
CaF2 (2027 nm)

CaF2:Sm3+(15150 nm)
CaF2:Eu2+(65 nm)
CaF2:Er3+, 9122 nm
CaF2:Yb3+
CaF2:Yb3+/Er3+
Ca1xLaxF2+x
CaF2: Yb 3+/Tm3+ 7.4 nm
CeOF:Dy3+ 6 nm
[62]
[37,63]
[64]
[65]
[66]
[67]
[68]
[69]
[70]
45SiO220Al2O310CaO25CaF21.5Tb2O30.75Gd2O3
45SiO220Al2O310CaO25CaF20.1Eu2O3
45SiO220Al2O310CaO25CaF21Tb2O3
45SiO220Al2O315CaO20CaF20.125Tb4O70.7Sm2O3
45SiO220Al2O310CaO22CaF22YbF31ErF3
50SiO220AlF35CaO25CaF2
45SiO220Al2O310CaO24.9CaF20.1DyF3
45SiO220Al2O310CaO(25x)CaF2xRF3
SiO2Al2O3CaOCaF2YbF3RF3 (R = Er, Tm)
CaF2:R3+ (R = Tb/Gd) 24 nm

CaF2:Eu2+(1118 nm), 35 nm
CaF2: Tb 3+ (15-27 nm)
CaF2:Sm3+/Tb3+
CaF2:Yb3+/Er3+ (2040 nm)
CaF2 (1070 nm)
CaF2:Dy3+ (1018 nm)
CaF2: Sm 3+/Dy3+/Tm3+ 30 nm
CaF2:Yb3+/Er3+/Tm3+
[38]
[36,71]
[72]
[73]
[74]
[75]
[76]
[77]
[81]
55SiO220Al2O35Na2O20CaF20.5PrF3yYbF3 (y = 016)
45SiO225Al2O310Na2O20CaF2xErF3 (x = 15)
45SiO225Al2O310Na2O20CaF20.1PrF3yYbF3(y = 0.1, 0.3, 0.5, 1.0, 1.5)
45SiO225Al2O310Na2O20CaF2RF3 (R = Tm, Ho)
CaF2:
CaF2:
CaF2:
CaF2:
45SiO225Al2O35CaO10NaF15CaF2xErF3 (x = 0.12)
45SiO225Al2O35CaO10NaF15CaF2xNdF3 (x = 0.12)
45SiO225Al2O35CaCO310NaF15CaF20.5ErF3xYbF3 (x = 0; 0.5)
45SiO225Al2O35CaCO310NaF15CaF2R F3
44.5SiO224.8Al2O39.9NaF5.0CaO14.8CaF2x ErF3
40.4SiO220.6Al2O34.7CaO12.2NaF
16.0CaF22.8NiO0.5ErF32.8YbF3
43SiO222Al2O35CaO13NaF17CaF23NiO0.5ErF3
41.5SiO221.3Al2O34.8CaO12.6NaF16.4CaF22.9NiO0.5ErF3
1
1
1
1
CaF2:Er3+, 1020 nm
CaF2:Nd3+
CaF2:Er3+/Yb3+(1525 nm)
CaF2: Yb 3+/Eu3+ (912 nm)
CaF2:Er3+(1218 nm)
[39,83]
[84]
[85,86]
[87]
[88]
3
3
3
CaF2:Er3+/Yb3+ (1719 nm)

CaF2:Er3+
CaF2:Er3+
[89]
[90]
[91,92]
55.4SiO25.9Al2O310.9CaO0.9ZnO10CaF28.9Na2O7.9 K2O0.04Ag2O
0.03CeO2
(63.45 x)SiO25.77Al2O310.58CaO12.5CaF27.69 K2OxNa2O
45SiO225Al2O310Na2CO318CaF22Ca CO30.5TmF3xYbF3 (x = 0;1)
45SiO215Al2O310Na2CO34Ca CO318NaF8LuF30.5YbF30.1TbF3
CaF2:Ce3+, Ag
[93]
CaF2 950 nm
CaF2: Tm 3+/Yb3+
NaLuF4: Tb 3+/Yb3+
[94]
[95]
[96]
50SiO220Al2O320SrF2(10 x)NaFxEuF3 (x = 05)

42SiO223Al2O332SrF2(2.9 x)GdF3xYbF30.1PrF3 (x = 0,1)
55SiO210Al2O315Na2O10ZnO10SrF2
60.3SiO23.7Al2O312.3SrO8.3Na2O5.3 K2O10.4SrF2
SrF2:Eu2+ (2037 nm)

SrF2: Pr 3+/Yb3+ (1314 nm)
SrF2: Tm 3+
SrF29 nm
[97]
[98]
[99]
[100]
45SiO215Al2O310Na2O24BaF26Y2O3
BaYF5:Ce3+
BaYF5:Pr3+
Ba1xRxF2+x:Eu3+
Ba2LaF7:Eu2+/Tb 3+/Sm3+
BaF2: Pr3+, 8 nm
BaF2: Tb3+/Yb3+:Ag
BaF2 1319 nm
BaF2: Yb 3+/Tm3+/Ho3+ 23 nm
BaF2 (520 8Ccubic,1030 nm;
> 550E mix. with orthorhomb.)
BaYF5:Er3+ 25 nm
[101]
[102]
[103]
[104]
[41]
[105]
[106]
[107]
[108]
[109]
[110]
BaYF5:Yb3+/Ho3+ (1525 nm)

BaGdF5:Tb3+, 1827 nm CeF3:Dy3+ 18 nm
[111]
[112]
[113]
Glass composition
Lit.
43SiO215Al2O310Na2CO34CaO18BaF210LuF3
45SiO215Al2O37La2O312Na2O15BaF20.3EuF22.7TbF33SmF3
68SiO215BaF213 K2CO33La2O31Sb2O3
45SiO220BaF220Na2CO315 x yLa2O3xTb4O7yYbO3
69.6SiO27.52Al2O315.04 K2O1.88Na2O6BaF2
40SiO225Al2O315Na2O5BaCO315BaF2xYbF3yTmF3zHoF3
70.41SiO27.52Al2O314.29 K2O1.79Na2O6BaF2
40SiO225Al2O315BaCO310YF310BaF2xErF3 (x = 0.5, 1.0, 2.0 and 3.0)
40SiO225Al2O315BaCO310YF310BaF20.5HoF3xYbF3 (x = 0.5, 1.0, 2.0 and
3.0)
45SiO215Al2O310Na2O24BaF24GdF32Tb2O3
50SiO220Al2O320BaF2(10 x)CeF3xDyF3(x = 010)
Pr 3+/Yb3+ 815 nm
Er 3+
Pr 3+/Yb3+ 815 nm
Tm3+/Ho3+
[78]
[79]
[80]
[82]
50SiO217Al2O323MgF210NaF0.25EuF3xMnF2 (x = 0.5, 1, 3, 6, 9)
MgF2:Eu2+/Mn2+
30SiO215 Al2O329CdF21.5YF32.5HoF3
CdF2: Ho
40SiO220Al2O340PbF22.5Yb2O31Er2O3
55SiO210Al2O335PbF20.5ErF3
28SiO222Al2O340.9PbF210PbO(4.8 x)GdF30.1NdF3xYbF30.1TmF3
40SiO210AlO1.540PbF25AlF3
PbF2:Yb 3+/Er3+
PbF2:Er3+
PbF2:Tm 3+/Yb 3+ 17.2 nm
PbF2: Yb 3+/Er 3+/Tm 3+
[115]
[116]
[117]
[118]
48SiO211Al2O37Na2CO310CaO10PbO11PbF23ErF3
Pb5Al3F19:Er; Er3Si3O10F; Er4Si3O11F2
[119]
[28]
30SiO215AlO1.524PbF220CdF210YbF31ErF3
PbxCd1xF2:Yb 3+/Er3+ 20 nm
PbF2:Y3+/Yb3+/Er3+/Tm3+25 nm
(R10Pb25F65, R = rare earth)
MF2: Tm3+/Tb 3+/Eu3+
PbF2:Yb 3+/Er3+
PbF2
PbF2:Er3+ 12 nm
PbxCd1xF2:Yb 3+/Er3+ 20 nm
PbF2:Yb 3+/Er3+ (460500 8C)
PbRF5 (520560 8C)
[19]
30SiO215Al2O329CdF222PbF21.5YF31.5YbF30.5ErF30.5TmF3
33SiO29.5AlO1.520.5PbF233.5CdF23.5RF3
30SiO2(16 x)Al2O340PbF210CdF24Yb2O3xEr2O3 (x = 0.54)
44SiO25Al2O340PbF210CdF21NdF3
32SiO29Al2O331.5CdF218.5PbF25.5ZnF23.5ErF3
30SiO215Al2O328PbF222CdF24Er2O31Yb2O3
30SiO215.5Al2O340PbF210CdF20.5Er2O34Yb2O3
3+
[114]
[120]
[121]
[122]
[26]
[123]
[124]
[125]
26
Glass composition
Method
Table 1 (Continued )
Nanoparticles**
Lit.
PbF2: Yb 3+/Ho
PbF2: Nd 3+
PbF2: R3+
30.9SiO215.5Al2O330.9PbF222.7CdF23YbF30.5HoF3
(49 x)SiO2x Al2O310CdF240PbF21NdF3 (x= 015)
40SiO210Al(OH)F330PbF217.6CdF21.7YbF30.7TbF3
3+
[126]
[127]
[128]
50SiO215AlF310BaF215PbF2(9.3 x)GdF30.5YbF30.2TmF3xHoF3
(x = 0.020.5)
PbF2: R3+
[129]
32SiO29AlO1.531.5CdF218.5PbF25.5ZnF23.5RF3
[130132]
30SiO215Al2O317PbF229CdF25ZnF24YF3
30SiO215AlO1.518PbF229CdF25ZnF23RF3
32SiO29AlO1.531.5CdF218.5PbF25.5ZnF23.5HoF3
30SiO29AlO1.529CdF217PbF25ZnF24ErF3
30SiO215AlO1.529CdF218PbF25ZnF23ErF3
30SiO215AlO1.529CdF218PbF25ZnF23EuF3
30SiO215Al2O318PbF229CdF25ZnF23YF3
Pb1xRxF2+x, (x 0.29)
R = Er,Yb,Eu,Dy,Ho,Tm
PbxCd1xF2 1918 nm
PbROF3 (R =CeLu)
PbF2: Ho 3+ 6 nm
PbF2: Er 3+
Pb2yCdyErxF2+x (1625 nm)
PbF2:Eu3+ (2530%) 100 nm
PbYOF3: Er3+
[20]
[133]
[134]
[135]
[136]
[137]
[47]
55SiO26Al2O320ZnF220SrF24YbF30.05TmF3
(60 x)SiO220ZnF219.6BaF20.4HoF3xYbF3
59SiO220ZnF220BaF21TmF3xHoF3
SrF2: Yb3+/Tm3+, 13 nm
BaF2 (1020 nm)
BaF2: Ho 3+/Tm3+
[138]
[139]
[140]
40SiO210Al2O320ZnF230MF2 (M = Ca,Sr,Ba)
50SiO210Al2O320ZnF220SrF2
50SiO210Al2O320ZnF216SrF22YbF3
50SiO210Al2O320ZnF216SrF24CaF2
50SiO210Al2O320ZnF216SrF24CaF22YbF3
50SiO210Al2O320ZnF220SrF2RF3
CaF2, SrF2, BaF2; ZnF2

SrF2 (1420 nm)
Sr1xYbxF2+x
CaxSr1xF2
CaxSr1xRyF2+y
Sr1xRxF2+x R = Yb/Er, x0.28,
R = Yb/Er/Tb, (620 nm)
R = Yb/Tb, (1028 nm)
R = Yb, x = 0.510, 30 nm
[141]
[62]
[62]
[62]
[62]
[142]
[143]
[144]
[145]
50SiO215Al2O3(35 x)LaF3xCeF3 (x = 017.5): Sb2O3
LaF3: Ce
44SiO228Al2O317NaF11RF3
TbF3:Yb3+, 22 nm
LaF3:Eu3+
b-YF3:Nd3+/Yb3+
b-YF3:Tm3+ bYF3:Tm3+,Er3+,Yb3+
bYF3:Tm3+,Yb3+
bYF3:Pr3+,Yb3+, b-YF3:Tm3+,Yb3+,Nd3+
b-YF3:Ho3+, Yb3+, Ce3+
b-YF3:Ho3+, Tm3+, Yb3+
b-YF3:Tm3+,Yb3+,Gd,2028 nm
1
1
1
1
SiO2Al2O3NaFRF3 (R = LaLu, Y)
34SiO222Al2O327NaF(17 x)YF3xTbF3yYbF3
40SiO228Al2O317NaF15CeF3
3+
RF3 2030 nm
NaYF4:Tb3+/Yb3+ 10 nm(cubic)
CeF3
[146]
[147]
[148]
[149]
[150]
[151]
[40]
[152]
[153]
[154]
[155]
[156]
[157]
[22]
[158]
40SiO230Al2O318Na2O12LaF3
41.2SiO229.4Al2O317.6Na2CO311.8LaF3xNdF3
45SiO225Al2O315Na2O15LaF33RF3
55SiO221.3Al2O314.5Na2O9.2AlF37.5La2O3
55SiO219.3Al2O316.5BaO9.2AlF37.5La2O3
64.9SiO216.5Al2O34.3Na2CO31.6AlF312.7LaF30.006RF3 (R = Er, Tm, Pr)
1
1
1
1
1
1
40SiO225Al2O319Na2CO312LaF31TbF33YbF3
55SiO220Al2O315Na2O10ErF3
50SiO227Al2O310Na2O13LaF3RF3 (R = Ho, Tm)
51.7SiO227.6Al2O313.2Na2O0.5AlF3(710.7)RF3
1
1
1
1
1
1
70SiO27Al2O38Na2O8K2O7LaF3
70SiO27Al2O38Na2O8 K2O7LaF3
40SiO225Al2O320Na2O15LaF33NiO
1
1
3
LaF3 20 nm
LaF3:Nd3+ 1015 nm
LaF3:R3+
LaF3 15 nm
LaF3:R3+ (R= Pr,Er)
LaF3:Pr3+ (71/29% cryst./glass)
LaF3:Er3+ (2/98% cryst./glass)
LaF3:Tb3+/Yb3+, 15 nm
ErF3
LaF3
LaF3, LaF3:Tm3+
LaF3: Tm3+/Ho3+
RF3 (R = Y, La,Tb, Gd)
LaF3:Eu3+ 1020 nm
NaLaF4 20 nm
NaLaF4:Tm3+, 30 nm hexagonal
LaF3
[159]
[160]
[161]
[162]
55SiO26Al2O323Li2O(16 x)LaF3xYbF31TbF3
[170]
40SiO225Al2O318Na2CO37NaF10RF3 (R = Y,Ho,Yb)
40SiO225Al2O315Na2CO310NaF10RF3 (R = Y,Nd,Yb,Dy)
40SiO225Al2O318Na2CO310YF37NaF
NaYF4: Ho 3+/Yb3+
Cubic NaYF4: Nd 3+/Yb3+;
Yb 3+/Dy3+;Nd 3+/Dy3+ NaYF4:Er3+ 22 nm
[171]
[172]
[173,174]
42SiO226Al2O321LiF11YbF3
47SiO228Al2O312YF313LiF
43SiO223Al2O317YF327LiF
40SiO220Al2O320LiF20GdF3
41SiO210Al2O324LiF23SrF22ErO3
LiYbF4::Eu3+/Tb3+ 2030 nm
LiYF4: Tm3+/Yb3+/Er3+ 10 nm
LiYF4: Er3+/8 nm
LiGdF4:R3+ (R = Eu, Tb, Tm) 2050 nm
SrF2:Er3+
[175]
[176]
[177]
[178]
[179]
29.4SiO218.0Al2O312.0P2O520CaCO318.0CaF20.3La2O30.5Li2CO3
0.3B2O30.5ZrO21.0Nd2O3
30SiO220Al2O312P2O520CaO18.0CaF2xEr2O3 (x = 0.21.0)
Ca5(PO4)3F:Nd3+
[180]
29.4SiO218.0Al2O312.0P2O520CaCO318.0SrF20.3La2O30.5Li2CO3
0.3B2O30.5ZrO21Eu2O3
Ca5(PO4)3F:Eu3+
[163]
[164]
[165]
[166]
[166,167]
[82]
[21]
[166,168]
[169]
[90]
[181]
[182]
27
Method
Table 1 (Continued )
Nanoparticles**
29.4SiO218.0Al2O312.0P2O520SrCO318.0SrF20.3La2O30.5Li2CO30.3B2O3
0.5ZrO20.3Nd2O3
Sr5(PO4)3F:Nd3+ 40 nm
[183]
Xerogels (95SiO25CaF2):1Er3+
Xerogels (95SiO25CaF2):1Eu3+
89 SiO25CaF25YbF31ErF3
2
2
2
CaF2:Er3+ 1020 nm
CaF2:Eu3+ 16 nm
CaF2:Yb3+/Er3+
[184]
[50,185]
[186]
97.5(90SiO210SrF2) 2.5Al2O30.5ErF3
SrF2: Er3+ 20 nm
[187]
(SiO2BaF2):R3+ (R = Eu, Sm, Dy, Ho, Pr)

90SiO210(Ba0.97Eu0.03)MgF4
2
2
BaF2:R3+
BaMgF4:Eu2+
[188]
[189]
90SiO2(10 x)LaF3xEuF3 and SiO2LaOF

(90SiO210YF3): 0.1Eu3+/0.1Sm3+
2
2
LaF3:Eu3+
YF3:Eu3+/Sm3+ 11 nm
[51]
[190]
(90SiO210YF3): xYb3+/0.1Tm3+ (x = 0.5; 1; 1.5)

95SiO25NaYF4:0.1Eu3+
SiO2
SiO2
2
2
2
2
YF3:Yb3+/Tm3+
NaYF4: Eu3+. cubic
LiYF4:Nd3+ and YF3:Nd3+
LiYF4:Nd3+
[52]
[191]
[192]
60SiO220ZnO20BaF2
BaF2: Tm3+/Ho3+
[82]
90SiO210PbF2:RF3 (R = 0.3Yb and 0.1Er)

75SiO225PbF2:RF3
R = Eu3+,Sm3+, Tb3+; Eu3+/Tb3+; Sm3+/Tb3+
89.5SiO210PbF20.5RF3
PbF2:Er3+/Yb3+, 1020 nm
PbF2:Er3+/Yb3+, 25 nm
PbF2:R3+
PbF2:Yb3+/Er3+/Tm3+
PbF2:Yb3+/Ho3+/Tm3+
Orthorhombic PbF2
PbF2:Er3+
[53]
[193]
[194]
[49]
55 SiO2(3020)PbO(515)PbF210Na2O
50SiO245PbF25PbO1ErF3
2
2
2
2
2
2
1
68 SiO213 K2O(69)BaF2(911)YF31Sb2O3
68 SiO213 K2CO315BaF22.75La2O31Sb2O30.25Eu2O3
1
4
Ba1xYxF2+x: Eu3+
BaF2: Eu3+/Eu2+
[196]
[197]
10SiO263B2O313.5Al2O313.5Na2ObNaYF4: Yb3+/Er
b-NaYF4: Yb3+/Er3+
[198]
Ba2GdF7: Eu3+/Tb3+
Ba2GdF7: Er3+/Yb3+ 2535 nm
Ba2GdF7:Eu
BaF2:Yb3+/Ho3+40 nm
[42]
[199]
[200]
[201]
Glass composition
Lit.
58SiO212B2O318Na2O8BaF24GdF3
56SiO212B2O318Na2O8BaF24.5GdF3
60SiO215B2O310Na2O10BaF25GdF30.1EuF3
60SiO212B2O316Na2O8BaF24YbF30.5HoF3
[195]
[45]
50SiO220B2O318Na2O8SrF24GdF30.1EuF30.05TbF3
Sr2GdF7: Eu2+/Tb3+ 32 nm
[43]
64SiO214.5B2O39.5Na2O6NaF6YF30.5ErF31YbF3
66SiO28B2O310Na2O8NaF8GdF3xErF3(x = 0.12.0)
NaYF4:Er3+/Yb3+ 30 nm(cubic)
NaGdF4:Er3+ (hexagonal) 2035 nm
[44]
[202]
65SiO215B2O314Na2O4.5YF31YbF30.5ErF3
63SiO215B2O316Na2O5.5LaF30.5ErF3
YOF: Yb3+/Er3+1023 nm
LaOF: Er3+
[203]
[204]
60SiO215B2O315Na2O8CaF22NaF0.25Eu2O3
(60 + x)SiO2(18.5 x)B2O39.5Na2O8CaF26NaF6GdF3 (x = 010)
1
1
CaF2: Eu3+
Cubic and hexagonal NaGdF4
[205]
[206]
21.1SiO26.5B2O37Al2O321PbF214.3CdF211PbO7.6CdO11.0YbF30.5ErF3
21SiO27Al2O39B2O320PbF220CdF29YbF30.5ErF36PbO5CdO
30SiO220Al2O310B2O34CaO16NaF3NiO0.5ErF3
1
1
1
Pb17Yb17 Er2F64
Pb4Yb3F17:Er3+
CaF2:Er3+
[207]
[23]
[208]
0.94BaB2O40.06Pb4Lu2YbF17
BaF2:Yb3+
[60]
79HBO320BaF21Eu2O3
BaF2: Eu3+
[209]
60B2O332CaF28Bi2O3: 2%R2O3
CaF2:La;Eu, 40 nm
[210]
50BaF225Al2O325B2O3
BaAlBO3F2, 50100 nm
[211]
50BaF225Al2O325B2O3:NiO
25SiO210GeO215AlO1.53TiO237PbF210GdF3
30SiO215GeO215AlO1.53TiO232PbF25YF3
1;3
1
PbF2: Tm3+/Ho3+
PbF2: Tm3+/Ho3+/Eu3+
b-PbF2: Ho3+/Tm3+/Yb3+
[212]
50GeO240PbO10PbF2
PbF2:R3+ R= Er,Yb,Ce, Eu3+

1050 nm
[214]
[55,56]
[215217]
[218]
47.5GeO219Al2O314.25CaF214.25LiF5ErF3
50 x)GeO222Al2O313LaF315LiFxHoF3
1
1
CaF2: Er3+, <20 nm

LaF3: Ho3+, 717 nm
[219]
[220]
45PbF246GeO25Al2O34Yb2O30.05Tm2O3
PbF2
[221]
60GeO220PbO10PbF210CdF2
30TeO230GeO220PbO10PbF210CdF2
Pb1xCdxF2
[57]
45GeO230BaF25B2O315Al2O35R2OxSm2O3 (R = Li,Na,K, x = 1.52.5)
Ba3AlF9
[222]
xBaF2(20 x)BaO15Ga2O365GeO2
BaGa2Ge2O8
[223]
40TeO215SiO225AlF315CaO5KF
30TeO212SiO232AlF318CaO8NaF3RF3
32TeO215SiO228AlF315CaO10NaF1.5ErF3
CaF2
bNaCaAlF6:Er3+/Ho3+
CaF2: Er3+,
[224]
[225]
[226]
64Pb(PO3)216WO320PbF2
PbF2
[61]
40NaPO330YF320BaF210CaF2
Ca1xYxF2+x Yb3+/Er3+
[227]
45P2O513.5Na2HPO425CaF215LiF0.5Ho2O31Nd2O3
CaF2: Nd3+/Ho3+, 10100 nm
[228]
36SiO218BaF218Ba(NO3)215Sr(NO3)22AlF310Yb2O3xEr2O3
BaF2: Yb3+/Er3+
[229]
[213]
Notes:
*
Methods of synthesis: thermal treatment/controlled crystallization of melt-quenched glasses (1), solgel process (2), laser-induced crystallization (3), laser cladding (4),
optical ber preparation (5).
**
We do not use a and/or b designation for PbF2 polymorphs [230], for there are signicant inconsistencies in its use in the modern literature.
28
Fig. 2. Composition tree for SiO2Al2O3 (B) glass-based oxyuoride glassceramics (Table 1).
The simplest way to prepare glass ceramics (method 1)

includes heating the starting glass or amorphous specimens at
temperatures which are close to their crystallization points,
resulting in the formation of crystalline nanoparticles within the
glass matrices. Minimizing the light scattering, including Rayleigh
scattering, is one of the most important requirements for
transparent optical glass ceramics. Rayleigh scattering occurs at
micro-inhomogeneities if their size is close to the wavelength of
the excitation radiation, and this imposes very strict limitations
on the size of the formed nanocrystals and the difference between
refraction coefcients of the crystal and glass phases. Hopper
[235] showed that transparent glass ceramics may contain
nanocrystals up to 30 nm in size, and the difference between
the refraction coefcients of crystalline and glassy phases should
not exceed 0.3.
Optical homogeneity of any glass ceramics (includng oxyuoride ones) may be achieved if their crystalline phases are almost
isotropic. The latter happens only if these formed crystallites have
higher symmetry lattices (e.g., cubic, hexagonal, or tetragonal).
Otherwise, if crystal lattices have lower symmetry and, thus, they
are clearly anisotropic, and/or crystallite sizes exceed the
wavelength of the light, then the prepared glass ceramics will
be optically inhomogeneous due to the anisotropy of refraction
coefcient(s) and translucent. As a result, crystallites in oxyuoride glasses are most frequently chosen from uorite-type
diuorides MF2 (CaF2, SrF2, BaF2, CdF2, PbF2, Pb1xCdxF2; Fm3m
space symmetry group) or solid solutions M1xRxF2+x (Rrare earth
elements). Also oxyuoride glass ceramics frequently contain
nanocrystals with LaF3, NaYF4, LiYF4-structure type compounds
(Table 1). Orthorombic b-YF3-type nanoparticles can be imbedded
in oxide glass matrices of oxyuoride glasses also.
It is worth mentioning that the same glass matrix can be used for
the synthesis of glass ceramics with various crystalline nanophases
in it. For example, SiO2Al2O3NaFRF3 (Rrare earth elements)
alumosilicate glasses are a good starting material for glass ceramics
containing either RF3 or NaRF4 nanophases (Table 1).
Fluoride glasses could have been the major competitors for
oxyuoride glass ceramics. They have much broader transparency
region in their spectra in comparison to quartz glass, from 0.295 to
7.5 mm, i.e., from near UV to mid-IR part of electromagnetic
spectrum [24,231234].
Fluoride nanoparticles are formed at the rst steps of uoride
glass crystallization [27,238240]. At this point, there is not much
difference between the properties of the formed nanophases and

their glass matrices, however, the appearance of crystallization
products in the glass body leads to an increase in optical losses and,
therefore, becomes an undesirable process. Attenuation in uoride
glasses is an order of magnitude lower than in quartz, and
approaches to the theoretical minimum of 0.01 dB/km. This is
why interest in uoride glasses as materials for ber optics originally
was greater than the interest in oxyuoride glass ceramics.
However, in order to achieve ultralow levels of optical losses in
uoride glasses, one has to have concentrations of transitional
metals and OH-groups under 106107 wt.%, for these admixtures
absorb near- and mid-IR radiation. This level of purication provides
the main obstacle to the industrial application of uoride glasses as
optical bers: inorganic uorides react easily with equipment
materials; they are hygroscopic and easily undergo pyrohydrolysis.
Fluoride glasses and their precursors are toxic, unstable and quite
expensive. Their treatment should be done in a vacuum without any
contact with the surrounding air. These factors seriously limit use
and applicability of uoride glasses and all uoride glass ceramics. In
addition, we would like to bring to our readers attention to the
aforementioned very close distribution of dopants-activators in both
crystalline and glassy phases in uoride glass ceramics, when the
latter materials are doped with, for example, rare earth ions. In
contrast, oxide glasses and oxyuoride ceramics do not have such a
drawback. Also they are chemically stable and can be treated at any
step of their manufacturing process under aerobic conditions.
As we have already mentioned, glass ceramics are frequently
doped with one or more (Table 1) rare earth ions in order to obtain
optical materials with properties suitable for different photonic
applications, co-activation allows further tuning of the optical
properties of prepared specimens. Certain advantages of oxyuoride glass ceramics over entirely uoride glass ceramics and uoride
glasses have already been discussed, too, but here, we would like to
mention another preponderance for oxyuoride glass ceramics.
Rare earth dopants and co-dopants can be introduced in the initial
glass batch as oxides, which are more stable and less hygroscopic
than the corresponding uorides [38,72,73,115]. These rare earth
ions will reside in the formed nanocrystal phase(s) of the obtained
glass ceramics anyway. The latter will guarantee that rare earth
ions will be surrounded by the same set of ligands; their inner
coordination polyhedral will be the same as if one have spiked the
initial batch with starting rare earth uorides instead of the
aforementioned oxides.
Oxyuoride glass matrices may not only contain uoride

nanoparticles after crystallization, they may contain nanoparticles
of other compositions as well. Improper choice of the starting
composition may result in the formation of an oxide crystalline
phase. For example, Xiao and Wang [236] obtained nanocrystalline
GaAl6O13 phase after heat treatment of germanate oxyuoride glass
CaF2BaF2AlF3SiO2GeO2; Bagga et al. [356] crystallized nepheline (NaAlSiO4) and oxyapatite (NaY9Si6O26) nanoparticles by
thermal treatment of SiO2Al2O3Na2OYF3B2O3 oxyuoride glass.
Increasing the alkali metal components in (1.79 + 0.018y)Na2O
(14.29 + 0.143y)K2O7.52Al2O3(70.410.161y)SiO26BaF2 glass
resulted in the replacement of primarily crystallizing BaF2
nanoparticles by Al2O3 ones [108].
There are several publications dedicated to the synthesis of
uoroapatite nanoparticles and their analogs that are very hard to
be made as single crystals [180183]. In addition, Kolobkova et al.
described formation of quantum dots of PbS, PbSe, etc., in
uorophosphates glasses [11,241].
Thermal treatment of 20GaF315InF310SnF215ZnF217CdF2(20 x)PbF23P2O5xErF3 glass resulted in the appearance of ZnF2
and cubic ErGa5O12 in the samples [242]. Exposure of similar
composition glass doped with Er/Yb to the constant electrical eld
caused the thermoelectrical crystallization of ZnF2 and a different
Pb5P4O15 phase in it [243]. The authors [242,243] did not report on
the distribution of activating rare earth ions among the phases in
their specimens.
Glass ceramics based on uorogermanate glasses belong to the
same group of materials [223]. Introduction of BaF2 to BaOGa2O3
GeO2 glasses leads to the improvement of their optical transparency
because of decreasing intensity of the absorption band intensity at
about 3 mm (OH concentraton in the glass drops signicantly), and
transformation of the starting glass to glass ceramics (due to the
appearance of BaGa2Ge2O8 crystal phase) which essentially
improves mechanical properties of the latter materials.
Some researchers [237] (see also [231]) have suggested an
iteration strategy for increasing stability of multicomponent
glasses that included analysis of the primary crystallizing phase
followed by changes in the initial batch composition by decreasing
the number of components corresponding to the composition of
these primary crystals. In contrast, in this case of glass ceramics
synthesis, control actions should have been different, and
components of the desired crystalline phase should be introduced
in the batch in excessive amounts. Indeed, the composition of the
starting glass material should be chosen within the close proximity
of the boundaries of the area of glass formation in the
corresponding multicomponent matrix system. Otherwise, one
can obtain just surface crystallization instead of uniformly
distributed crystallization [210].
3. Crystallization and devitrication (devitriheation) of glasses
3.1. Fundamentals of glass crystallization [8]
Glasses are known to be undercooled liquids, existing in
metastable state at ambient temperature. However, they can
undergo transformation to a stable state (devitrication) under the
certain thermal conditions. Crystallization of glasses in the
simplest case occurs in two steps via formation of crystallization
centers and actual crystal growth. In the absence of foreign
crystallization centers introduced into the glass body, crystallization centers form homogeneously as a result of uctuations
[244]. Once their size exceeds a critical limit, they become stable
and can grow spontaneously.
In 1942, Zeldovich formulated a generalized version of the
kinetics for rst order phase transitions [245], considering
nucleation as a process determined by the activated state of the
29
Fig. 3. Rates of homogeneous formation of crystallization centers (Kv) and crystal

growth (Kg) as functions of the degree of overcooling for viscous liquids (Tammans
curves): melting point (1), metastable area of overcooling (2), rate of the crystal
growth (3), rate of the homogeneous formation of crystallization centers (4),
metastable area of the high viscosity (5), ambient (room) temperature (6) [248].
system matrix/nucleus. Since this time, his theory has been

successfully used for the description of nucleation kinetics in glass
[246].
The main laws of crystallization of liquids with lowered ability
to form crystals were established by Tammann [247] (typical
Tammanns curves [248] are presented in Fig. 3). Tammanns
conclusions have been fundamental (and rightfully remain so) for
the analysis of crystallization processes in any glass-forming
liquids or melts. In order to describe glass crystallization,
Tammann used two parameters: rate of formation of new phase
nuclei (number of formed crystallization centers per time unit) and
the growth rate of these nuclei (linear rate of crystallization)
(Fig. 3). If crystallization occurs in an area where the linear rate of
crystallization is high, and the number of formed crystallization
centers per time unit is low, then one will get a relatively small
number of large crystallites. However, if the formation rate of
crystallization nuclei is high, and the rate of their growth is low,
then one will get numerous small crystallites.
The microstructure, size and concentration of crystalline
particles in the glass phase are determined by the rate of creation
of nuclei and their growth rate. These rates depend on temperature
in different manner, and it is obvious that in order to obtain
transparent ceramics one needs to maintain conditions when the
formation rate of crystallization nuclei (centers) is high, but their
rate of growth is low.
Most of the technologically important glasses have multicomponent compositions. As a result, their crystallization includes
complex phase interactions that originate from equilibrium or
quasi-equilibrium (metastable) phase diagrams [231,232]. Thermal treatment of multicomponent glasses may result in the
formation of different crystalline phases of various compositions in
the glass matrix. Crystalline phase formation occurs in many steps;
so by halting its progress at different stages, one can prepare glass
ceramics with different properties, structure and phase compositions. A set of examples is displayed in Section 5. The increase of
the number of the formed crystalline phases associated with
higher temperature thermal treatment of starting glasses does not
30
Fig. 4. Scheme of the nanocrystallization mechanism in homogeneous glasses with

homogeneous nucleation. Reproduced with permission from Ref. [251]. Copyright
The American Ceramic Society and Wiley Periodicals, Inc. 2013.
correspond to the multiplicity of the phases formed under

equilibrium conditions. This set of phases is determined by
Ostwalds step rule, which characterizes the sequence of phase
changes during the transformation from non-equilibrium state to
an equilibrium state [250]. The formation of metastable phases is
quite common for the crystallization of glasses [8]. In general, the
crystalline phase formed via glass thermal treatment should not be
the same as the rst crytallizing phase for melt crystallization.
Nevertheless, literature data unequivocally indicate, that in the
majority of oxyuoride glass ceramics, uoride phases appear at
earlier stages of oxyuoride glass crystallization.
Therefore, primary crystallization of glasses is the most
important process in the preparation of oxyuoride glass ceramics.
In contrast to one-component systems, when multicomponent
glasses undergo crystallization, the composition of the crystallizing phase is different from the composition of the glassy matrix.
During this process, each crystal nucleus is surrounded by the layer
depleted of the components of the forming crystal (Fig. 4). Thus
crystallization process is always accompanied and limited by
diffusion, and because of it, the key target for the preparation of
optical transparent nano glass ceramics is an increase in viscosity
of the residual glassy matrix phase in order to slow down the
diffusion and, therefore, limit the size(s) of the formed crystal
phase inclusion(s) [251].
For example, Bhattacharyya et al. [106] established that BaF2
nanocrystals, formed in SiO2Al2O3K2ONa2OBaF2 system, are
surrounded by a silicon-enriched diffuse layer; and the latter
actually prevents the growth of these BaF2 nanocrystals. The
reason for this is that the above diffuse layer contains 612% more
silicon and, therefore, possesses a higher viscosity than the rest of
the glass matrix and, consequently, acts as a diffusion barrier,
preventing the further growth of BaF2 nanocrystals.
Another case, which is different from homogeneous crystallization, is the heterogeneous formation of crystallization nuclei,
when the latter centers have totally different composition than
crystals (heterogeneous, or catalyzed, crystallization happens
when crystallization centers forms on foreign inclusions or
discontinuities such as surfaces of colloid inclusions, dust particles,
internal surfaces of the containers, etc.). It is accompanied by an
essential lowering of the activation energy barrier for the
formation of the nuclei of the emerging target crystalline phase.
Erystallization in the cases of glass ceramics can be achieved by
the addition of special substances (nucleators and catalytic dopants)
that promote crystallization center formation and creation of the
required material structure [248]. The difference between crystallization catalysts and nucleators is that nucleators, being introduced
in the batch, decrease the stability of glass, ease its crystallization
and become included in the formed crystalline phases. Crystallization catalysts are not included in the formed crystals; therefore, it is
very likely that their action is linked to heterogenenous nucleation.
One such catalytic dopant, which would not get incorporated in the
formed crystalline phases, is NiO [8992].
As an example of nucleators, one may mention the use of
inorganic uorides in the controlled crystallization of oxide
glasses. This approach has been used for decades, since the earlier
experiments of Stookey [3]. Nucleators role of metal uorides was
based on their ability to cause such changes in the original glass
network that the repeated heating of starting uoride materials
produced uoride crystallization centers, which in turn simplied
glass crystallization1.
In particular, rare earth uoride dopants (RF3) decrease the
stability of their glass matrices toward crystallization, acting as
nucleators [39,46,47,56,97,123]. Thermal treatment of such
glasses results in the appearance of these RF3 species as primary
crystalline nanophases [158,159]. However, much more frequently, rare earth triuorides do not appear as a separate nanophase of
this stoichiometric composition. Instead, they appear as a
component of a more complex uorite-type structure and play
crucial roles as activators when they are contained in the materials
used for luminescence.
It is worth noting the importance of the uorite-type
structure clause in the previous sentence. These crystal phases,
primarily M1xRxF2+x (M = Ca, Sr, Ba, Pb; R = rare earth elements)
non-stoichiometric solid-solutions, have many properties similar
to those of glasses (e.g., structural disorder, thermodynamic
instability, low heat conductivity and high ionic conductivity).
However, these solid solutions differ from glasses by their longrange order in the crystal structure (whereas, once again, the short
range order is missing in their lattices). Also, these phases never
exhibit undercooling when their melts crystallize, including
multicomponent systems as well. The latter feature leads to their
primary crystallizations from the melt in all systems, when such
possibility is allowed by the topology of the corresponding phase
diagrams [231,253,254]. Tromel [255] suggested the term antiglasses as a name for these compositions.
3.2. Micro-liquation
Initially, many researchers considered that the rst step of
crystallization center formation in uoride glass ceramics includes
evolution of the forming nanoparticle phase(s) [3744,69,86]. This
suggestion is in agreement with [141], which showed that the
emergence and growth of CaF2, SrF2, BaF2 primary nanoparticles
from SiO2Al2O3ZnF2MF2 glasses could be described by a simple
kinetic equation with a single activation energy parameter (227,
271 and 592 kJ/mol for M = Ca, Sr, Ba, respectively). However, the
nature of nucleation centers in the oxyuoride glass crystallization
has yet to be claried. The phenomenon of micro-liquation is a very
important factor affecting both the formation of initial glass and
the crystallization of glassceramics.
The phenomenon of liquidliquid phase separation (LLPS) is
well-known for silicate glasses, e.g., SiO2Li2O, SiO2Na2O
[8,251,256]. Liquation in these systems is metastable, i.e., melts
can be mixed completely, but separation of amorphous phases
occurs only in undercooled uids, which also includes glasses.
Transition from stable to metastable liquation has been observed
for SiO2-MO systems when ; = Mg, Ca, Sr were replaced by ; = Ba
[256].
Metastable liquation was also observed in uoride glasses. For
example, crystallization of some ourozirconate glasses (such as
1
Conversely, it has been known for a long time that the introduction of uorides
(e.g., cryolite Na3AlF6, uorite CaF2, sodium uoride NaF) to silicate glass batches
increases their transparency [252]. However, usually only small amounts (less than
1%) dopants were used, for this purpose was to decrease the viscosity of the glass
melt with these uoride supplements.
Fig. 5. Scheme of the nanocrystallization mechanism in phase-separated systems.

Reproduced with permission from Ref. [251]. Copyright The American Ceramic
Society and Wiley Periodicals, Inc 2013.
68.6ZrF4:18.4LaF3:5AlF3:5GaF3:3ErF3 [257,258]) proceeded via

spinodal liquation. After separation of the two liquid phases,
one undergoes spontaneous crystallization, and the crystalline
dendrite phase makes up to 70% of the total material volume.
The formation of three liquid phases of different compositions
instead of two is quite possible in multicomponent systems.
The process of glass crystallization under liquidliquid phase
separation phenomenon (Fig. 5) can not be described by Tammans
model. Berezhnoi [259] and Anlogov et al. [260] described the
long history of theoretical discussion concerning the uoride ions
ability to initiate or amplify micro-liquation of the oxide glass
matrix. Minuscule droplet areas of phase separation are formed in
the thermally treated oxyuoride glass specimen [260]. Quenching
will preserve the homogeneity of such a glass, but new heating will
result in separation of the phases, and the droplet phase will
crystallize via homogeneous nucleation.
This assertion has been supported by the observation of large
areas of separation for oxide and uoride liquid phases in the phase
diagrams of numerous oxyuoride systems, e.g., CaOSiO2CaF2
[261], CaOAl2O3CaF2 [262], Ca5(PO4)3FSiO2NaFAl2O3[263].
Regarding the kinetics of liquid (glass) phase separation, it is
worth noting that its initial step may proceed via two different
mechanisms, spinodal and binodal: the choice between the two
mechanisms depends on the glass composition. The spinodal curve
(surface) corresponds to the transition from metastable (locally
stable) state of homogeneous liquid to an unstable state, where the
further transition from homogeneous unstable state to stable state
of two separate phases occurs without potential barrier (i.e., the
activation energy is zero). The spinodal mechanism is common for
compositions and temperatures for the phase diagram areas
adjacent to the central part of liquation dome. The phase
separation process begins right after the original single-phase
melt reaches the spinodal region (even if phase separation occurs
very slowly). Phase separation proceeds via the formation and
steady increase of concentration uctuations without the formation of new liquid phase nuclei in regions of instability. Spinodal
decomposition results in the formation of the spurious warm-like
two-phase structure with complex topology. Sometimes, however,
spinodal decomposition may also result in the formation of right
spatially modulated structures, leading to the formation of
mutually ordered crystalline objects.
The rst step of phase separation in the binodal area is the
formation of nucleation centers of the new amorphous phase in the
glass. These droplets have phase boundaries from their outset. This
step is controlled by the same laws that govern crystallization
center formation. Binodal liquation proceeds via a nucleation
mechanism, i.e., by crossing the energy barrier for the formation of
nucleation centers of a critical size. Glass can remain for a relatively
31
long time in the binodal area of the liquidity dome without any
indication of phase separation.
There is much evidence conrming that the formation of
oxyuoride ceramics occurs via liquidliquid phase separation
(LLPS). Bocker et al. [100] clearly showed that droplet phase
separation is the initial step of the nano SrF2 crystallization into
silicate glass under thermal treatment. Hemono et al. [159] and de
Pablos-Martin et al. [25,167,264] studied the crystallization
kinetics of LaF3 nanocrystals in oxyuoride SiO2Al2O3Na2OLaF3
glasses and came to the conclusion that phase separation in the
glass body precedes crystallization and quenching of the melt
produces homogeneous glass. Reheating of the aforementioned
SiO2Al2O3Na2OLaF3 samples caused the appearance of the
droplet-like glass surfases, the rst one was enriched in LaF3, and
the second phase contained more SiO2 and Al2O3. Conversion of
such glass to glass nanoceramics by annealing results in the
crystallization of a droplet-like phase with LaF3 nanocrystals
formed inside the droplets. The interphase between the glass
matrix and the crystals in the demixing ranges is enriched in
network formers, namely SiO2, creating a viscous barrier, which
inhibits further crystal growth and limits the crystal size to the
nanometer (1020 nm) range. Similar results have been obtained
by Bhattacharyya et al. [265] on the same objects.
Given the previous discussion, one may conclude that the
preparation of oxyuoride nanoceramics is frequently based on the
metastable liquation of starting glass with mandatory formation of
crystallization centers in it. Time and temperature parameters of
thermal treatment of the starting glass materials is based on the
results of experimental studies of microstructure and phase
composition of glass ceramics prepared under various conditions.
4. Preparation of transparent glass ceramics
Methods to synthesize transparent oxyuoride glass ceramics
can be classied by the use of the following two features (criteria):
(1) preparation techniques to obtain starting glass or amorphous
matrices, and (2) devitrication (annealing and/or laser irradiation) protocols.
A common feature of the rst group protocols is their last step
thermal treatment to perform partial crystallization of the initial
matrices.
One of the most famous methods of this group is the partial
devitrication-controlled crystallization of starting glasses. It
includes two sequential steps, the rst of which is a glass
preparation. This starts with melting of the premixed precursors
(i.e., mixtures of starting oxide and uoride powders) followed by
quenching of the melt. The second step includes glass thermal
treatment at certain temperature. The kinetics of initiation and
growth of the crystals in the glass matrix determines its size and
concentration and, in turn, is dened by the temperature and the
duration of the samples thermal treatment as well as the chemical
composition of the starting glass material. This specimen
treatment temperature is selected using thermal analysis data
for the glass formation (vitrication) temperature (Tg) and the
crystallization temperature (Tc). Thus, the second step is always
carried out at temperatures close to Tc. For example, one can nd a
detailed description of the second step thermal treatment (time
and temperature) in [21], where the authors controlled the
formation of CaF2:Sm nanoparticles with predetermined sizes of
1560 nm.
Usually, thermal treatment is carried out under air at ambient
pressure. This results in signicant (up to dozens percents) losses
of uorine (it has been unequivocally conrmed by chemical
analysis in [167]). Also, Shinozaki et al. [266] have shown that
preparation of 25CaF25CaO20Al2O350SiO2 glass ceramics,
containing 30 nm CaF2 nanoparticles, by batch heating in the
32
electric furnace above the glass transition temperature (500

700 8C) was accompanied by the formation of a ca. 150200 nm
uorine-decient surface layer, where no CaF2 nanocrystals were
formed.
In reality, there are two main mechanisms for uorine depletion
in the course of oxyuoride glass ceramics preparation. The rst
one is pyrohydrolysis [23,267,268], i.e., reaction of uorides with
water vapor:
MF2 H2 O ! MO 2HF " :
(1)
RF3 H2 O ! ROF 2HF " :
(2)
Perhaps, the presence of lead oxyuoride in glass matrix in [61]

was a result of the similar type reaction:
2PbF2 H2 O ! Pb2 OF2 2HF " :
(3)
Domange [269], Warf et al. [270], and Banks et al. [271] have
studied stability of various compounds toward pyrohydrolysis and
found that this process increases in the following series:
the least stable UF4 ThF4 ZnF2 CdF2 PbF2 AlF3 CeF3
MgF2 BeF2 CaF2 SrF2 ; BaF2 NaF the most stable
and
the least stable Sc; Lu Ce Yb Ho Tb Tm Gd Er Dy
Fig. 6. Schematic model for the formation of CaF2 nanocrystals in lines patterned by
laser irradiations and temperature distribution in the laser irradiated region .I and U
are the nucleation and crystal growth rates, respectively. Reproduced with
permission from Ref. [272]. Copyright The American Ceramic Society and Wiley
Periodicals, Inc 2013.
Sm Nd; Y Eu Pr La the most stable for RF3

It is also important to remember that metal uorides usually do
not react with dry oxygen. Use of graphite crucibles (instead of the
regular alundumAl2O3ones) results in the creation of an
anhydrous reducing atmosphere and, therefore, prevents pyrohydrolysis of the specimens.
However, it is the second mechanism that is the chief cause for
the uorine losses, and it is linked to the exchange reactions
resulting in the formation and evaporation of volatile silicon, boron
and aluminum uorides [23]:
2MF2 SiO2 ! SiF4 " 2MO
(4)
3MF2 B2 O3 ! 3MO 2BF3 "
(5)
These processes can be prevented by replacement of alumosilicate glass matrices by uoroposphate ones [227].
Both mechanisms for uorine loss account for the diffusion
processes.
In addition to direct external heating, one can carry out the
thermal treatment of starting glass matrix by other means.
Komatsu et al. [272] used 1.061.08 mm laser irradiation to
crystallize doped CaF2 and LaF3 nanoparticles in uoroalumosilicate glasses spiked with NiO. This laser-induced crystallization
allowed the creation of 0D and 1D structures by local surface
crystallization [8992]. The latter structures are important in
creating prospective planar optical waveguides [272]. NiO addition
is required for accumulating laser irradiation. The patterning of
locally crystallized lines consisted of doped uoride nanocrystals
formed on the glass surface by laser irradiation. The scheme for the
distribution of laser irradiation-formed nanoparticles on the glass
surface is presented in Fig. 6 [221].
The rst step of the 2-step synthesis of transparent glass
ceramics via partial devitrication may include the preparation of
an amorphous matrix instead of the glassy one. Such an
amorphous matrix may be synthesized by so-called soft chemistry
that includes, for example, the solgel synthesis instead of melting/
fusion system components. Fujihara et al. [51] successfully
pursued this venue by preparing initial SiO2:LaF3 gel by reacting
tetramethyl orthosilicate, La(CH3COO)3 and triuoroacetic acid
precursors in aqueous solution. SiOSi bonds were formed during

hydrolysis. The prepared gel was dried at ca. 100 8C in order to
complete the aforementioned hydrolysis and then subjected to the
thermal decomposition at 300800 8C (lanthanum uoroacetate
thermolyzes above 300 8C and forms corresponding triuoride
LaF3). The prepared quartz-based glass ceramics contained 10
30 nm LaF3 crystallites. Similarly, authors [189] synthesized
europium-doped SiO2BaMgF4:Eu2+ glass ceramics in the form
of a thin lm.
Zhou and Chen [184] prepared starting pure sol by mixing
hydrolyzed ethanolic tetraethyl orthosilicate (TEOS) and triuoroacetic acid solutions of calcium and erbium acetates. Then they
converted the obtained sol to gel and, consequently, to xerogel.
Thermal treatment of the latter at 400900 8C produced transparent oxyuoride glass ceramics containing CaF2:Er3+ nanoparticles.
Similar techniques for the thermal treatment of precursor gels
were employed for the synthesis of 0.3Yb3+ and 0.1Er3+doped
90SiO210PbF2 transparent oxyuoride glass nanoceramics [53] as
well as CaF2SiO2 transparent glass ceramics, containing CaF2:Eu3+
nanoparticles [50,185].
Yu et al. [187] discovered an important role for Al2O3
supplement while preparing SiO2Al2O3SrF2:Er3+ glass ceramics
by solgel synthesis: Al2O3 positively affected the stability of oxide
glass matrix and allowed the thermal treatment of intermediate
xerogel at the higher temperature than for the alumina-lacking
SiO2SrF2:Er3+ xerogel. Heating at the higher temperature resulted
in a complete removal of the remaining OH groups from the glass
ceramics specimen and eliminated microporosity of the glassy
matrix. In addition, introduction of Al2O3 supplement in the course
of solgel synthesis caused an intensive up-conversion luminescence in the prepared glass ceramics samples.
The most important advantage of solgel processes is lowering
of the synthetic temperatures by hundreds degrees compared to
the temperatures of glass batch melting: whereas preparation of
germinate and silicate glasses requires heating up to 1,200 8C and
1,600 8C, respectively, synthetic temperatures in solgel protocols
usually do not exceed 800 8C. This signicantly suppresses uorine
losses by pyrohydrolysis and evaporation of volatile uorides from
the starting batches. In addition, solgel techniques allow the

preparation of glass ceramics based on the compositions, for which
synthesis of pure glasses by regular means is obstructed, e.g., rareearth uoride-doped silica, etc. (Table 1).
These methods also avoid undesirable glass microliquation, and
this is a substantial advantage. However, glass ceramics prepared
by solgel protocols frequently contain organic impurities because
of the organic solvents used in the initial steps of their synthesis.
The presence of OH and CH groups in the nal materials could
signicantly decrease their luminescence [48,242]. The latter
factor is a major reason why controlled crystallization (partial
devitrication) methods have become favored for the preparation
of glass ceramics for optical puroposes.
Ding et al. [198] proposed new method of laser cladding for
preparation of luminescent glassceramic. Separately prepared
micron-sized b-NaYF4: Yb3+/Er3+ particles and borosilicate glass
chips were mixed and milled together, placed on a quartz glass
plate and thoroughly melted under CO2 laser irradiation. Solid
uoride particles were absorbed by the bulk melt without loosing
their crystal structure and up-conversion properties.
Similarly, thermoelectric batch treatment (DC current electrolysis) [243] also resulted in crystalline inclusions in the glass matrix.
33
(glass formation) temperature, whereas the rst exo-effect at Tc1

corresponds to CaF2 crystallization, and the second exo-effect at
Tc2to the bulk crystallization of the whole glass sample.
The signicant (more than 200 8C) difference between Tc1 and
Tc2 indicates a relatively easy preparation of CaF2 nanocrystals
from the glass matrix, whereas relatively small (Tc1Tg) value
points out at the high tendency of this glass sample to undergo
devitrication [76].
While dilatometry can be used to determine Tg values
[108,159,166,275], DTA still remains the main method for doing
so. In addition, DTA is widely used for:
For instance, some researchers [36,37,65,74] as well as many

other scientists have used DSC curves to determine glass formation
(vitrication) (Tg) [275] and crystallization (Tc) temperatures
(Fig. 7): the endo-effect at Tg in Fig. 7 corresponds to the vitrication
- nding formation temperatures for various crystalline phases

[135,217,249];
- revealing the correlations between crystallization ability of
glasses and their chemical composition;
- studying the inuence of certain dopants on the manner and type
of crystallization [86,136].
Relocation of the peaks in DTA curves, which correspond to the
maximal glass ceramics crystallization temperatures, is crucially
important for the synthesis of transparent glass ceramic
materials. Thus adding CeF3 dopant to PbF2 shifts the exo-thermic
crystallization effect of the latter component to a higher
temperature [217]. Increasing the YbF3 content in GeO2-PbOPbF2 glass also shifts peaks in DTA curves of this materials
[216]. Luo et al. [97], analyzing DTA curves, established that the
steady increase of Tg, Tc1, and Tc2 temperatures along with the
growth of Eu activator concentration indicated an increase in the
activation energy for the crystallization process. Shinozaki et al.
[75] found that the intensity of crystallization process for SiO2
Al2O3CaOCaF2 glasses depended on the CaF2 content: absence
of CaF2 in this glass increased its vitrication temperature (Tg)
from 590 to 775 8C and caused the disappearance of the exothermic peak in the DTA curve corresponding to this glass
crystallization. The increase in the Tg value when %2?3 was added
to alumosilicate glass resulted in the decrease in the size of CaF2
particles generated under the laser treatment of the sample
surface [208].
Secu [185], who studied xerogels, prepared by the solgel
synthesis with the use of DTA and TGA techniques, determined a
mechanism for and the temperature of organouorine compounds
pyrolysis as well as conditions for CaF2 and EuF3 crystallization,
and thus established proper temperature conditions for xerogel
conversion to glass ceramics. Actually, DTA is quite a good method
for determining crystallization temperature and maximal rate of
crystallization nuclei formation (Fig. 8) [23]: increasing the
duration of the starting glass material thermal treatment results
in a peak intensity decrease for the exo-thermic effect that
corresponds to crystallization at 770 K. This peak becomes smaller
Fig. 7. DSC curve for the glass sample 42SiO223Al2O332CaF23ErF3 Reproduced

with permission from Ref. [65]. Copyright Elsevier 2009.
Fig. 8. DTA curves of original glass 21SiO27Al2O39B2O320PbF220CdF210YbF3

0.5ErF36PbO6.5CdO (upper curve) and the same glass after annealing at 703 K for 31 h
(lower curve). Reproduced with permission from Ref. [23]. Copyright Elsevier 2011.
5. Properties of glass ceramics and methods of their studying

Glass crystallization processes, conditions for nanocrystal
formation in glass matrices, structures and properties of glass
nanoceramics are studied by the following methods:
-
differential thermal analysis (DTA);

differential scanning calorimetry (DSC);
thermogravimetric analysis (TGA);
X-ray diffraction (XRD) phase analysis;
scanning (SEM), transmitting (TEM) and high-resolution transmitting (HRTEM) electron microscopy;
- infrared (IR) and Raman spectroscopy;
- nuclear magnetic resonance spectroscopy (NMR);
- anomalous small-angle X-ray scaterring (ASAXS) [207].
In addition,
- energy dispersion X-ray (EDX) spectroscopy [123,145,199];
- X-ray uorescence analysis and
- ame photometry (FP) [159] are employed to determine
chemical composition of synthesized glasses and glass ceramics.
34
and smaller, totally disappearing once the glass ceramics synthesis

is accomplished (Fig. 8) [23].
However, it is worth noting that all investigations performed to
the present indicate that the introduction of rare earth ions is
mandatory to obtain an exo-thermic effect in the DTA curves at
lower temperatures, which is caused by bulk crystallization.
Because optical, luminescent and other properties of oxyuoride glass ceramics depend on the composition and structure of
imbedded nanocrystals (of course, in addition to the size of these
crystallites), X-ray diffraction (XRD) analysis can be used to
determine the unit cell parameters and particle size of the formed
crystalline particles. The average particle size can be determined
with the use of Scherrers equation [276] by taking into account
widening of the corresponding X-ray diffraction lines and the
estimated size of coherent scattering areas [277] (sizes of
microdeformation areas are seldom estimated [23]).
Some features of the phase composition determination by XRD
technique are discussed in Section 7.
However, a simple identication of the nal crystalline phase
composition in glass ceramics is not sufcient for developing state of
the art synthetic technology for these materials. In order to control
the properties of the formed glass ceramics, it is necessary to control
the whole crystallization sequence from the initial step of nucleation
to the nal step of complete crystallization. Thus, Gomes et al. [61]
observed shifts of the existing peaks and the appearance of new ones
in DTA curves when they studied the effects of increasing the PbF2
content in lead-tungsten glass by differential scanning calorimetry
(DSC). A combination of Raman spectroscopy, thermal analysis and
X-ray diffraction methods produced valuable information for
corresponding thermal treatment required to produce crystallization centers and generate certain crystalline phases in the
aforementioned glass specimens [61]. The annealing of
64Pb(PO3)216WO320PbF2 glass samples at 410 8C for 150 min
produced crystalline cubic-PbF2 phase, while heating similar
specimens at the same temperature for 180 min generated Pb2P2O7
and Pb2OF2 phases (in addition to the rst-crystallized PbF2),
whereas similar exposure to 410 8C just for 75 min was insufcient
to produce any crystallite inclusions (Fig. 9). Further analysis of the
X-ray diffraction data (width of the reection peaks, etc.) conrmed
the size of the b-PbF2 nanocrystals, which were small enough to
guarantee the transparency of synthesized glass nanoceramics.
Thermal treatment of leadgermanate glass produces cubic
PbF2 phase followed by PbGeO4 and PbGe4O9 at higher temperatures [217].
Fig. 9. X-ray diffraction patterns of 64Pb(PO3)216WO320PbF2 glass samples after

the sample thermal treatment at 410 8C for 75, 150 and 180 min. Reproduced with
permission from Ref. [61]. Copyright Elsevier 2011.
In a similar manner, a study of phase transformations during

SiO2Al2O3CdF2PbF2ZnF2ErF3 glass crystallization showed
thataccording to XRD analysis datasamples, annealed at Tg,
were still X-ray amorphous, and no crystalline phase were
observed in them [135]. Sample crystallization was observed in
the specimens annealed at 10 8C higher than the rst exo-thermic
peak temperature (TF1), and the rst phase to crystallize was
uorite-type PbF2. Samples annealed at TF2 also contained CdSiO3,
PbO and ZnF2in addition to the aforementioned PbF2.
Wang et al. [249] showed that increasing the of annealing
temperature for CaF2AlF3SiO2 oxyuoride glass leads to the
formation of CaAl2Si2O8 anortite crystalsin addition to CaF2
uorite microcrystals, that appear as a the only crystalline phase at
lower temperatures. Similarly, reheating of SiO2Al2O3MgF2NaF
alumosilicate glass produced MgF2 phase at 600660 8C and
Al6Si2O13 at higher temperature [113].
X-ray diffraction study of SiO2Al2O3SrF2NaF glasses [97]
showed that the rst crystallization peak at TF1 = 580 8C corresponded to the formation of SrF2 crystalline phase, whereas the
second peak at TF2 = 640 8C corresponded to crystallization of
Sr2Al2Si2O8. Therefore, SrF2 nanocrystals were prepared at temperatures in the TF1TF2 span. Increasing the annealing temperature
from 580 to 640 8C produced narrower X-ray diffraction lines, and
the average size of the formed SrF2 nanocrystals calculated by
Scherrers formula increased from 20 to 37 nm, which was in a good
agreement with independently obtained TEM data (as per [76],
where an increase of 50 8C for the annealing temperature resulted in
the growth of crystallite size from 20 to 40 nm).
In contrast, de Almeida et al. [94] established that the crystal
size depended on the glass chemical composition, but was not
affected by the duration and temperature of annealing: according
to their experiments, the size of the CaF2 crystals grew from 9 to
50 nm with an increase of the Na2O concentration; de Almeida et
al. [94] explained their results by the formation of an extremely
viscous glass layer around the formed CaF2 crystals.
Similarly, Munoz et al. [166] found with the use of X-ray
diffraction analysis that the phase composition of alumosilicatebased glass ceramics varied as a function of SiO2 and Al2O3 content in
the samples: specimens with <55 mol.% SiO2 and >20 mol.%. Al2O3
contained crystalline LaF3, whereas specimens with >55 mol.% SiO2
and <20 mol.%. Al2O3 contained NaLaF4 nanocrystals (we will
further discuss Munoz et al. [166] work below, when we turn to the
use of NMR methods for studying oxyuoride glass ceramics).
Such ability to produce different crystalline phases in glass
matrices of glass nanoceramics is a very important feature of these
materials: because thermal treatment of starting glasses is carried out
at temperatures signicantly lower than glass melting temperatures,
one can produce crystalline phases that would otherwise be
unavailable as single crystals. Moreover, one can synthesize such
metastable phases as orthorhombic BaF2, which otherwise could be
prepared under equilibrium or close to equilibrium conditions only
under high pressure (2.33.0 GPa) [108]. These nanocrystals
because of their small sizes possess very high surface free energy.
The addition of rare earth activators to the forming crystallites is
a very important tool in the creation of glass ceramic materials with
the required properties; however, it too has pros and cons.
Goutaland et al. [163] reported that the LaF3 phase, crystallized
in 16.5Al2O31.6AlF312.7LaF34.3Na2CO364.9SiO2 glass, accommodates quite different amounts of lanthanide dopants, from 2 to 3% of
the total amount of initially introduced ErF3 to 70% of initially added
PrF3. This is in qualitative agreement with other data [278]
concerning the solubility of rare earth uorides in lanthanum
triuoride for voluminous samples. Similarly, activators of the
yttrium subgroup are better incorporated than the other rare earth
elements by forming YF3 nanocrystals. Kanno et al. [92] have
suggested that the crystalline Ca1xRxF2+x (R = Yb, Er) solid solutions
are formed in oxyuoride ceramics after comparing cell parameters

of CaF2 nanocrystals in the glass matrix (a0 = 5.49 A) with similar
data for the intrinsic single crystals of uorite (a0 = 5.46 A).
XRD analysis of SiO2Al2O3NaFTbF3YbF3 glass ceramics
indicated that the only crystalline phase formed was orthorhombic
TbF3 (JCPDS 84-0179) [147]. Quantitative study of these nanocrystals and their glass matrix by erergy dispersion X-ray analysis
(EDX) showed that YbF3 content in the former was 20+ times
higher than in the latter. This was also conrmed by signicant
increase in up- and down-conversion intensity of the prepared
glass ceramics in comparison with the original glass before its
partial crystallization.
EDX study of reheated glass in the SiO2Al2O3B2O3PbF2
CdF2YbF3ErF3 system showed that erbium-activated cubic
Pb4Yb3F17 nanocrystals in the formed glass ceramics do not
contain cadmium [23]. Moreover, melting of the above starting
glass at 1323 K for 30 min leads to a decrease of SiO2, B2O3 uorine
content in the sample in the amount corresponding to a 10% mass
loss according to the following reactions occurring in the melt:
CdF2 H2 O ! CdO 2HF "
(6)
2CdF2 SiO2 ! 2CdO SiF4 "
(7)
3CdF2 B2 O3 ! 3CdO 2BF3 "
(8)
Taking into account the above Eqs. (6)(8), Gugov et al. [23]
suggested that Cd2+ ions were surrounded by the remaining
oxygen atoms, whereas Pb2+, Er3+ and Yb3+ still remained
coordinated by uorine. This was conrmed by the addition of
CdO and PbO instead of the corresponding uorides to the starting
batches: as a result, mass losses at the glass melting step were
lowered to 3 wt.% along with the decrease of initial glass melting
temperature by 150250 K. Luminescence spectra for the initial
glass and obtained glass nanoceramics conrmed their aforementioned structural features [23].
NMR techniques can also be applied for the structural studies of
glass ceramics. Xue [62] used 19F and 27Al NMR techniques to
reveal that CaF2 or SrF2 modiers determined structural features of
50SiO220Al2O330CaF2 (GCa) or 50SiO210Al2O320ZnF2
20SrF2 or 50SiO210Al2O320ZnF216SrF24CaF2 initial glass
and prepared glass ceramics. If Ca cations were used as modiers,
then FCa(n) sites in glass were the precursors of FCa(4) sites in
the nanocrystals of formed glass ceramics. However, in the case of
Sr-modied materials, a large portion of Al-F-Sr(n) sites of starting
glass convertsin addition to FSr(n) sitesto F-Sr(4) sites in
prepared glass ceramics crystallites. The use of both CaF2 and SrF2
modiers resulted in the appearance of CaxSr1xF2 solid solution
nanocrystals with much higher Ca:Sr ratio in the crystalline
35
nanophases than in the starting glass materials. TEM study of

phase separation during crystallization showed the presence of
discrete round-shaped 2027 nm crystalline nanoparticles evenly
distributed in the glass phase (Fig. 10). 19F NMR spectra of the
above composition 50SiO210Al2O318ZnF220SrF22YbF3 and
50SiO210Al2O320ZnF216SrF24CaF22YbF3 glass ceramics unequivocally prove the insertion of Yb3+ ions in the form of a
nanocrystalline lattice.
The NMR method was also crucial in the determination of
important features of LaF3 or NaLaF4 crystallization mechanism in the
Na2OK2OAl2O3SiO2LaF3
system
for
compositions
of
18Na2O30Al2O340SiO212LaF3
(40Si12La
glass),
15Na2O
20Al2O355SiO210-LaF3 (55Si10La) and 8Na2O8 K2O7Al2O3
70SiO27LaF3 (70Si7La) glasses, including an inuence of the
chemical composition of the starting glass materials [166]. Thus,
NMR study of the initial glass precursor showed a signicant amount
of amorphous LaF3 and/or NaLaF4 already present on the glass after its
melting. In addition, as already mentioned above, the SiO2/Al2O3 ratio
in this glass dictates which phase LaF3 or NaLaF4 would crystallize;
so Munoz et al. [166] actually observed diffusion of uorine atoms of
AlFNa groups to corresponding LaF3 or NaLaF4 nanocrystals. Munoz
et al. [166] also mentioned that their results conrmed the presence
of LaF3-enriched areas in the above glass observed by TEM in other
studies [159] (Fig. 11).
Electron microscopy is one of most informative methods for
studying nanoparticles in glass ceramics materials, for it allows direct
observation of the size and shape of individual particles. Transmitting
electron microscopy (TEM) goes even further, for it is based on the
electron diffraction and, therefore, TEM allows one not only to
distinguish crystallized fragments from glass areas, but to identify and
characterize individual nanocrystals with great accuracy, too.
Scanning electron microscopy (SEM) is used, primarily, for the
determination of the particle sizes, similar to what has been already
discussed above for Kishi et al. [74] studies of transparent 45SiO2
20Al2O310CaO22CaF22YbF31ErF3 glass ceramics, where authors
[74] observed increase of Ca1xLnxF2+x crystallite size from 20 to
40 nm with the increase of the annealing temperature from 700 to
750 8C (Fig. 12). The average nanoparticle size was in good agreement
with the X-ray diffraction data (corresponding values were calculated
using Scherrers equation) [74].
The formation of 1015 nm hexagonal LaF3, evenly distributed
in a glass matrix, was proven by a combination of TEM and XRD
analysis methods (Fig. 13) [160]. Additional analysis of the
absorption spectra for initial glass and produced glass ceramics
allowed authors [160] to conclude that Nd3+ dopant ions moved
from the starting glass to the formed LaF3 nanocrystals.
When TEM is used for studying the crystallization processes in
glasses (and, in fact, it is a widely used method for this purpose),
Fig. 10. TEM images of GCa glass (left) and glassceramic after ceramic-forming condition GCa 600 8C 4 h (right). Reproduced with permission from Ref. [62]. Copyright The
American Ceramic Society 2011.
36
Fig. 11. TEM images of 55SiO2-20Al2O3-15Na2O-10LaF3 base glass (a) and glassceramic (b) samples. The latter was obtained by annealing at 700 8C for 20 h. Reproduced with
one should always keep in mind that information obtained using

this method (TEM) is mainly determined by the sample preparation techniques. For example, Bhattacharyya et al. [265] used
different methods to prepare 40SiO230Al2O318Na2O12LaF3
specimens for TEM studies of phase separation in them. One
protocol included treating the fresh glass fracture with an HF and
HNO3 mixture (1:1), followed by thorough rinsing of the surface
with distilled water and covering it with thin PtIrC lm before
taking self-shading replica images (Fig. 14a). Such replicas repeat a
surface microrelief, where 2030 nm pimples represent Laenriched areas. However, an increase in the TEM resolution
(Fig. 14b) did not provide additional information, for the replica
method resolution is limited by the formed lm structure. In other
words, replica method is an indirect technique, so one would
expect more information from direct TEM images.
The other TEM study protocol included cutting the samples and
polishing them down to 1015 nm thickness before Ar+ ionic ray
thinning. Fig. 15a contains dark drop-shaped areas corresponding
to the atoms with the highest atomic number in the sample, i.e.,
La-enriched areas, and amply illustrates the achieved phase
separation. The latter is conrmed by Fig. 15b data, where Laenriched areas are shown as the brightest spots instead of the
darkest in Fig. 15a. Sizes of La-enriched drops in Fig. 14 are twice
as large as those in Fig. 15. Bhattacharyya et al. [265] explained this
by the signicant lm thickness (several nm) in the rst cases.
TEM studies showed that heating SiO2Al2O3SrF2:Er3+ xerogel
at 800 8C led to the creation of a large amount of tiny spherical
particles with ca. 13 nm diameter [187]. Increasing the temperature to 1000 8C caused the growth of diameters of these particles
up to 23 nm (Fig. 16). However, such an increase was accompanied
by a signicant decrease in their surface area, as determined by the
BrunauerEmmettTeller (BET) technique. Yu et
al. [187]
explained it by the elimination of microporosity of the particles
(not the matrix!).
Similarly, del-Castillo et al. [53] observed an increase of
PbF2:Er3+/Er3+ particle size from 10 to 20 nm in thermally treated
10PbF290SiO2 gel with a treatment temperature increase from
300 8C to 400 8C (Fig. 17). HRTEM images of the studied samples
[53] contain clearly visible oriented merging of the defectcontaining nanoparticles (Fig. 17).
Fig. 12. SEM images (at 70,000 magnication) of 45SiO220Al2O310CaO22CaF22YbF31ErF3 glass ceramics fracture after the thermal treatment at 700 8C (a) and 750 8C.
Reproduced with permission from Ref. [74]. Copyright John Wiley and Sons 2005.
Fig. 13. TEM image and the corresponding selected area electron diffraction (SAED)
pattern of 41.2SiO229.4Al2O317.6Na2CO311.8LaF31NdF3 glass ceramics
sample. Reproduced with permission from Ref. [160]. Copyright Elsevier 2007.
37
TEM is also widely used to quantitatively estimate the amount

of crystalline phases as well as nanocrystal sizes and their
distributions. Thus, authors [266] synthesized transparent glass
nanoceramics by heating 25CaF25CaO20Al2O350SiO2 glass at
700 8C for 3 h. TEM picture of the sample obtained by focused ion
beam (FIB) technique contains images of ca. 30 nm CaF2
nanocrystals formed in the bulk of glass nanoceramics, but absent
in its surface layer (Fig. 18). Thermal treatment of the starting glass
was accompanied by 1.56 wt.% losses of the sample mass. At the
same time, EDX studies conrmed formation of the 150200 nm
surface layer with extremely low uorine concentration. This was
the main reason for the absence of the nanoparticles in the
aforementioned surface layer: one cannot form CaF2 nanocrystals
if no uorine is available.
Lin et
al. [87] studied glass ceramics containing CaF2
nanocrystals by X-ray diffraction (data [87] were erroneously
interpreted as orthorhombic modication of CaF2 instead of the
actually observed real cubic modication), TEM, HRTEM and EDX
methods (Fig. 19). The size of nanocrystals, calculated by Scherrers
equation (10 nm) from X-ray diffraction patterns, was in a good
agreement with TEM data (912 nm). As usual, EDX data indicated
that Eu2+ and Yb3+ dopant ions accumulated primarily in the
aforementioned CaF2 nanocrystals.
HRTEM, in contrast with its regular TEM analog, allows
visualization of the structure of nanocrystals imbedded in the
Fig. 14. (a) Bright-eld TEM image of the replica lm of the glass sample recorded using a Hitachi H-8100 microscope operated at 200 kV. (b) High-resolution TEM image of
the replica lm of the glass sample recorded using a JEOL JEM 4010 microscope operated at 400 kV. Reproduced with permission from Ref. [265]. Copyright Elsevier 2009.
Fig. 15. (a) Bright-eld TEM image of the glass sample recorded using a Hitachi H-8100 microscope operated at 200 kV. (b) Elemental mapping of La of the glass sample
recorded using a Zeiss 912 microscope operated at 120 kV. Reproduced with permission from Ref. [265]. Copyright Elsevier 2009.
38
Fig. 16. TEM images of 97.5(90SiO210SrF2)2.5Al2O30.5ErF3 heated at 800 8C (a) and 1000 8C (b). The insets are the corresponding SAED patterns. Reproduced with
Fig. 17. (a) TEM bright-eld image of 90(SiO2)10(PbF2) NGC co-doped with 0.1 Er3+ and 0.3 Yb3+ (mol.%), which was treated at 400 8C, shows the presence of PbF2
nanoparticles (dark spots). (b) HRTEM micrograph of the similar composition sample, where PbF2 nanocrystals are observed. The right-top side inset corresponds to the
power spectrum obtained from the region zoomed in white. The right-bottom inset corresponds to magnied detail of the same zoomed region showing the crystalline
pattern of PbF2 nanoparticle. Reproduced with permission from Ref. [53]. Copyright Elsevier 2009.
Fig. 18. TEM image of the edge part of 25CaF25CaO20Al2O350SiO2 glass nanoceramics in a thin foil (heat-treated at700 8C for 3 h), prepared by a FIB method (a). High
resolution TEM images of the surface (b) and a thin foil particle (c), respectively. Reproduced with permission from Ref. [266]. Copyright Elsevier 2012.
glass matrix and, at the present time, appears to be the only

method that is capable of producing such information at the
atomic level or at the level of the crystalline unit cells. In addition,
HRTEM allows one to obtain electron diffraction patterns that
allow determination of the crystal structure of nanoobjects and
measurement of their unit cell parameters.
Results of HRTEM study of real structure of SrF2 nanocrystals in
glass matrix are presented in Fig. 20 [143,144]: crystals are
oriented in (1 1 1) plane in Fig. 20a, and in Fig. 20b orientation was
carried out in two different directions. Interplane distances in
these samples were determined using the Fast Fourier Transformation (FFT) technique.
39
Similarly, results of the HRTEM study of SrF2 nanocrystals [143]

coincided with Fourier-transformed data of X-ray diffraction
analysis of the same material (Fig. 21) and indicated that Yb3+,
Tb3+ and/or Er3+-doped SrF2 nanocrystals had smaller crystal
lattice parameters and, therefore, contained the aforementioned
rare earth dopants in uorite-type SrF2 nanophase.
Several researchers used Raman spectroscopy to study oxyuoride glass ceramics (e.g., [167,273,354359]). Tikhomirov et al.
[357,358] assigned two lines, observed in Raman spectra at
relatively low vibrational frequencies, to spheroidal and torsional
vibrations of PbF2 spheric nanoparticles in the glass matrix and
calculated diameters of the latter to be ca. 13 nm. This estimate
Fig. 19. XRD patterns of precursor glass (PG) and corresponding glass ceramics (GC) (a). TEM micrograph of glass ceramics containing 0.5Eu2+/0.2Yb3+:CaF2 (inset shows the
selected area electron diffraction pattern) (b). HRTEM image of an individual 0.5Eu2+/0.2Yb3+:CaF2 nanocrystal (c). EDS spectra taken from an individual nanocrystal (d) and
from glass matrix in glass ceramics containing 0.5Eu2+/0.2Yb3+:CaF2 nanocrystals (e). Reproduced with permission from Ref. [87]. Copyright Elsevier 2011.
40
Fig. 20. HRTEM images of SrF2 nanocrystals formed in 50SiO210Al2O320ZnF220SrF24YbF31TbF3 glass ceramics: nanocrystalline phase exhibiting crystal planes going in
the same direction (a) and nanocrystalline phase exhibiting two overlapping crystal planes (b). Reproduced with permission from Ref. [144]. Copyright Elsevier 2011.
correlated very well with electron microscopy results. However, the

main goal of the Raman spectroscopy use in studying of oxyuoride
glass ceramics has been monitoring the changes in the glass matrix
ne structure after formation of the uoride nanoparticles:
sometimes, analyzing changes in the Raman spectra of the glass
precursors during their thermal treatment can detect the beginning
of the destruction of oxyuoride framework at the initial stage of
crystallization, when the XRD methods dont work yet.
6. Oriented attachment of nanoparticles
Recent HRTEM studies of crystalline nanoparticle formation
within glass phases during oxyuoride glass ceramics synthesis
revealed the unusual features of the latter process. Neighboring
nanoparticles were found to be coherently oriented from a
crystallographic point of view. This was repeatedly observed for
various crystal phases, such as hexagonal LaF3 [25,164] and
NaGdF4 [279], cubic NaLuF4 [191] PbF2 [53] (Fig. 17), CaF2:R3+
[67,87], (Fig. 19) and SrF2 [143] (Fig. 21), etc. The formed
nanoparticles eventually merge with each other and form
monocrystalline aggregates of very complex shape. The same

observations were reported in [29] for other nanoparticle
ensembles generated by different techniques. Such phenomena
have been described as non-classical micro-block crystal growth
mechanism more than one hundred years ago [280,281], and
rediscovered and renamed as oriented attachment growth
recently [282]. It is worth noting that the aforementioned hill-drop
allocation of the formed nanoparticles probably indicated a latent
liquation of starting glass phase and, namely, spatial modulation of
the glass composition during spinodal glass phase decomposition.
There are two known mechanisms by which nanoparticles
coherently merge [281]: (a) trial and error (hit-and-miss) approach,
when correct mutual orientation is found after the numerous
attempts of nanoparticles to join (dance of nanoparticles), and
(b) recrystallization of erroneously merged nanoparticle. The
rst mechanism is impossible for glass ceramics due to the
high viscosity of this medium, and there is no experimental proof
for recrystallization of the in-grown nanoparticles to support
the second mechanism. Thus, we suggest that there should be the
third mechanism based on the long-range forces by which an
Fig. 21. HRTEM image of the domain centered at the single nanocrystal in 50SiO210Al2O315.95ZnF220SrF23.99YbF30.05TbF3-0.01ErF3 sample (a) and the corresponding
reciprocal diffraction lattice pattern obtained by Fast Fourier Transformation (FFT) (b). Reproduced with permission from Ref. [143]. Copyright Elsevier 2011.
already-formed nanoparticle affects an adjoining part of the nonordered amorphous matrix and thus causes preferable (re)orientation of the other secondary forming crystalline nanoparticle.
Such long-range effects were described by Distler and Vlasov [283].
Shinozaki et al. [211] generated a directed crystallization of
BaF2Al2O3B2O3 glass under laser irradiation that resulted in the
formation of coherent-oriented merged BaAlBO3F nanoparticles in
the upper layer of material. Orientation of crystallites in this case
was caused by an applied thermal eld generated by a moving
laser beam.
7. Phase and chemical composition of the nanocrystals
Interpreting the natures of crystalline phases formed in
oxyuoride glass ceramics still remains a serious problem. X-ray
diffraction data are normally used for this purpose; however, the
results of this approach are often unsatisfactory.
First, erroneous results may arise from incorrect interpretation
of the obtained X-ray diffraction patterns. For example, Mallik et
al. [165] assigned their results as the formation of orthorhombic
ErF3. However, their published data [165] correspond to another
crystal structure, namely, hexagonal LaF3-type tysonite, and
erbium triuoride does not have such a stable modication
[278,284,285]. The appearance of tysonite-type structure may be
related to the partial contamination of the formed ErF3 nanoparticles by calcium and/or oxygen traces that can stabilize an
otherwise unstable tysonite-type crystal lattice for ErF3 [286,287].
Lin et al. [87] mistakenly interpreted synthesized cubic phase
as orthorhombic CaF2 nanocrystals [JCPDS 65-0535]. They
followed quite common path of errors when they used only part
of the aforementioned JCPDS data and did not consider the absence
of a signicant number of reections in the experimental X-ray
diffraction pattern in comparison with the X-ray diffraction
pattern of the suggested prototype. Similarly, Zheng et al. [203]
and Chen et al. [204] wrongfully assigned indexes of some
reections corresponding to trigonal YOF [203] and LaOF [204]
modications to peaks of relatively simple X-ray diffraction
patterns of cubic uorite-type phases. Errors in research papers,
caused by unscrupulous use of JCPDS database information, are not
limited to the aforementioned types of misinterpretation data for
polycrystalline specimens. JCPDS contains data for the certain set
of chemical compounds, but in practice, for example, while
studying glass ceramics, researchers have to deal with phases of
variable compositions that would have, in turn, variable lattice
parameters and, thus, variable angles for the observed reection
lines. Very frequently, according to the X-ray diffraction analysis
data, nanoparticles formed in the glass matrices belong to the facecentered cubic uorite-type structure [69,77,80,88,138,143145],
and one of the simplest examples could be the cubic M1xRxF2+x
(M = Ca, Sr, Ba, Pb; R = rare earth element) solid solutions that have
their crystal lattice parameters changing over quite broad
intervals.
In order to understand the formation of rare earth-activated
nanouoride crystals in the glass matrices of oxouoride glass
ceramics, one needs to consider the physical and chemical
processes that are occurring in these systems.
MF2-RF3 (M = Ca, Sr, Ba, Pb; R = rare earth element) systems are
prone to heterovalent isomorphism and formation of M1xRxF2+x
solid solutions [230,253,288,289]. Area of homogeneity for these
solid solutions can achieve up to 50 mol.% under equilibrium at
high temperatures [278].
It has been unequivocally established in [253,290296] that the
formation of the aforementioned solid solutions is accompanied by
the replacement of cations in certain crystal lattice positions of
uorite lattice (space symmetry group Fm3m). The cationic
sublattice remains completely lled, and only insignicant local
41
displacement of some cations is possible in it. However, in order to

compensate for the excessive positive charge of trivalent lanthanide cations, the insertion of additional interstitial anions becomes
necessary. Interaction of the latter interstitial uoride anions with
rare earth cations results in the formation of cluster defects.
Several dozens of cluster models, based on experimental results
and theoretical calculations, have been suggested in [253,290
296]. Such dominant defects for yttrium group rare earth MF2based concentrated solid solutions can be described as so-called
R6F37 hexamer clusters. The latter is formed by six rare earth ions,
each of them having Thompon antiprism coordination polyhedral
formed by uoride ligands (coordination number = 8). The internal
cavity of the R6F37 cluster has cubooctahedral shape, and may
contain an additional uoride ion. Such R6F37 cluster can be
seamlessly built in uorite-type crystal lattice (Fig. 22), and
isomorphous substitution in the formed solid state solutions can
be presented as follows:
M6 F32 20 $ R6 F37 19 Fint ;
(9)
The difference between the formal charges of the hexameric

R6F37 cluster and replaced block of the intrinsic uorite matrix
requires the introduction of an additional interstitial uoride ion.
Correlation between crystal lattice parameters and chemical
composition of M1xRxF2+x solid solutions is determined by the
aforementioned heterovalent cationic isomorphism. This process
is inuenced by two different effects: replacement of relatively
large M2+ cations by smaller R3+ cations as well as insertion of
additional uoride ions in the crystal lattice cavities. These effects
have opposite inuence on the crystal lattice parameters that could
vary over a 5.466.2 A range for the aforementioned rare earth
alkaline earth metal uoride systems. Fedorov and Sobolev [297]
published empirical equations describing changes in these crystal
lattice parameters of M1xRxF2+x solid solutions as functions of
compositions for all possible M2+ and R3+ combinations.
According to the existing MF2RF3 phase diagrams
[233,278,288,289], decreasing the temperature under equilibrium
conditions leads to the decomposition of M1xRxF2+x solid solutions
and the formation of a series of ordered uorite-like phases in
some systems (predominantly rare earth elements of the yttrium
subgroup), such as M2RF7, M9R5F33, M8R5F31, M4R3F17, etc.
Formation of these compounds is caused by ordering of R6F37
clusters, which are statistically distributed in their crystalline
lattices at high temperature. A typical example of the PbF2-YF3
phase diagram (according to different authors) [298301] is
presented in Fig. 23.
Each compound (phase) has a corresponding split of the main
lines in the X-ray diffraction pattern which is determined by its
crystal lattice symmetry (except the ordered cubic Sr17R10F64
phase, which has an increased lattice parameter that can be
produced by multiplication of the uorite lattice parameter by an
integer number). Also, one can see additional superstructure lines
in the X-ray diffraction patterns of such phases.
It is worth mentioning, that literature data in addition to
characterization of well-established ordered phases contains
descriptions of ctitious phases (phantom phases) caused by
errors in the experiments. Unfortunately, such numerous errors
have been incorporated in JCPDS, e.g., BaYF5 (JCPDS code
46-0039) and BaGdF5 (JCPDS code 24-0098). A detailed account
of BaYF5 has been reported in [302], while BaGdF5 was
chronicled in [278], respectively.
In addition, there are some phases, described in JCPDS, that
actually exist, but their X-ray diffraction data have been
interpreted erroneously, e.g., lower temperature Ba2RF7 phases
([303]; JSPDS No. 41-0823). The latter cases are important, for one
should always keep in mind that the formation of nanoparticles in
42
Fig. 22. R6F37 cluster built in the uorite matrix.
glass ceramics occurs at relatively low temperatures (even if they

are still much above ambient temperature). These phases, formed
under these conditions, are formed in accordance with Ostwalds
step rule and, therefore, belong to the corresponding usually hightemperature non-equilibrium modications. This is quite a typical
situation for nanotechnology, and it also includes formation of
phases of various compositions [29]. Liu et al. [174] observed
initial formation of cubic NaYF4 nanophase in glass ceramic (which
is really a high-temperature phase), which started to transform to
equilibrium low-temperature hexagonal phase after increasing the
treatment temperature to 650 8C. A similar cubic-to-hexagonal
phase evolution was observed for NaGdF4 nanocrystals [206].
Fig. 23. Combined phase diagram of the PbF2YF3 system [298] according to DTA
data obtained in the hermetically sealed platinum crucibles (1) and in opened
graphite crucibles (1, 6) (correction for PbF2 evaporation has been accounted for)
and according to X-ray diffraction data (25, 78) (single phase specimens (2, 4, 7)
and two-phase specimens after annealing in gold (3), platinum (5) and copper (8)
crucibles, respectively).
Experimental studies of BaF2YF3 [302] and SrF2YF3 [304] model

systems demonstrated that ordered phases did not form at lowtemperature conditions, and composition areas of non-ordered
uorite-type solid solutions were broader than the similar
composition intervals for high-temperature equilibrium conditions. Heating of such non-equilibrium phases may cause their
transformation to equilibrium low-temperature phases that
would be stable under these conditions, in accordance with the
corresponding phase diagrams.
The same picture has been observed by Hu et al. [125], who
used corrosive treatment of glass ceramics for separation of the
imbedded nanoparticles and unhindered studying their chemical
composition. As a result, this study revealed that nanoparticles
formed at 460500 8C are cubic PbF2:Yb3+/Er3+, but the nanophase
formed at 520560 8C is tetragonal (Fig. 24) [125].
X-Ray diffraction data look similar to that of the PbRF5
approximate composition [299], but tetragonal distortion of the
initial cubic lattice is unequivocally the rst step in the ordering of
a solid solution. At the same time, the aforementioned X-ray
diffraction pattern lacks superstructure reections that should
indicate the increase of unit cell parameters. Similar results with
tetragonal nanophase Pb0.55Er0.45F2.45 were reported in
[116]. Therefore, in order to determine the real crystal lattice
parameters of such nanoparticles, one needs to study them using
electron diffraction, as was done previously [300].
Nan et al. [125] and Ge et al. [305] offered some models for the
structure of the aforementioned tetragonal phases, but because
their suggestions do not include the existing defect clusters, they
can not be considered as correct and acceptable explanations.
In general, the information discussed above shows that the use
of the JCPDS database information to identify crystalline phases in
oxyuoride glass ceramics is not the most efcient strategy when
one deals with phases of variable compositions, and the main
reason for such failures lies (as previously mentioned) in the
difference between actual lattice parameters of the solid solutions
and lattice parameters of the intrinsic MF2 matrices. The latter
causes shifting of the reection angles in the observed X-ray
diffraction patterns. Calculation of the actual parameters for the
crystal lattices and their comparison with the literature data with
the use of known a(x) concentration dependencies could be of
great help, but most authors dont even attempt to index their Xray diffraction patterns. Description of Ea1xLaxF2+x solid solution
in [68] represents a rare exception to that trend.
Further, the assignment of specic stoichiometric formulas or
structures of ordered phases to the synthesized cubic solid
solutions of varied composition, such as Pb4Yb3F17:R3+ [23],
tweittite [306], BaYF5 [101,102,109] or Ba2RF7 [42,199,200], is
not accurate. For example, Xin et al. [43] and Bai et al. [201]
frivolously and arbitrarily assigned to the peaks of cubic phases,
that correspond to M1xRxF2+x solid solutions, some awkward
Fig. 24. X-ray diffraction patterns of the nanoparticle samples obtained from glass
ceramics, synthesized by oxyuoride glass annealing at different temperature.
Reproduced with permission from Ref. [125]. Copyright The Royal Society of
Chemistry 2011.
Miller indexes taken from Sr2GdF7 [43] and Ba2YbF7 [201] X-ray
diffraction patterns.
Biswas et al. [196] interpreted formation of two nanophases of
cubic Ba1xYxF2+x solid solution with different lattice parameters as
formation of Ba4Y3F17 (compound of this formula is real, it actually
crystallizes in slightly trigonal-distorted uorite system) or
phantom-phase BaYF5 [196], and assigned peculiar Miller
indexes to the diffraction peaks in very simple X-ray diffraction
patterns in both cases.
Polyshchuk et al. [307] grounlessly interpreted the uorite
phase obtained by the thermal treatment of MnNbOF5BaF2BiF3
glass as Ba0.55Bi0.45F2.45, despite the fact that their X-ray diffraction
pattern did not have any traces of crystal lattice distortion or
ordering.
It is also worth noting that if authors postulate the existence of
uorite-type phases with distorted cubic lattices, then it would be
incorrect to use Scherers equation to estimate sizes of the formed
nanoparticles: splitting of the main peaks should cause additional
line broadening, and this would have no relation to the size of small
particles.
The third potential cause of interpretation errors lies in making
conclusions about the phase composition using only X-ray
diffraction data. The most common crystalline phases in oxyuoride ceramics are uorite-based phases. However, these phases are
prone to both isovalent and heterovalent isomorphism. MF2 phases
can dissolve up to dozens percents rare earth uorides as well as
alkali metal uorides and oxygen (dissolving of the latter results in
formation of oxyuorides).
Heterovalent replacement of uorine by oxygen is known to
cause formation of the relatively broad areas of homogeneity for
the uorite-type solid solutions based on Ca, Sr, Ba, Pb diuorides;
and this is especially common for the systems that also contain
rare earth cations (MF2-ROF systems) [230,308310] and/or NaRF4
[311]. Substitution of uorine of oxygen in the crystal lattices of
these phases results in essential variations of the unit cell
parameters.
Failure to account for the latter phenomenon may cause serious
errors in the interpretation of the obtained results. For example,
Qian et al. [70] erroneously assigned CeOF (a = 5.697 A, JCPDS No
22-0618) composition to the face-centered cubic nanophases with
a = 5.6965.598 A, that were prepared by crystallization of Ca, Ce
and Dy uoride-containing alumosilicate glasses.
This is not the only paper, where authors never considered that
oxygen may be included in the compositions of the formed
nanophases and interpreted their X-ray diffraction data as formation
of Ca1xRxF2+x-type solid solutions only [69,77,80,87,88,93,94]. For
43
example, Ca1xCexF2+x solid solution, formed in the CaF2-CeF3

system, has its lattice parameter vary from 5.463 to 5.67 A, when
CeF3 content changes within 045 mol.% range [288]. Qian et al. [70]
suggested Ca1xCexF2+x solid solution composition with cerium
content way above the limit possible for the equilibrium phase, but
at the same time they completely ignored the idea that the formed
phase may contain oxygen.
Omitting the role of oxygen is not the only aberration in such
phase composition interpretation. Aseev et al. [133] explained
their low values of unit cell parameters for uorite-type PbF2based phases by inclusion of oxygen in the formed PbROF3 phases,
but they didnt consider that these phases may also contain
relatively small cadmium ions [230,312].
Zhou et al. [129] studied the formation of glass ceramics from
multicomponent glasses, containing Ba, Pb, Al and several rare
earth metal uorides, and assigned the PbF2 formula to the
crystallized face-centered uorite-type phase using only the
similarity between the calculated lattice parameter and the one
known for the pure PbF2 phase. However, there is no obvious
reason why their synthesized phase may not contain rare earth
uorides, BaF2 (BaF2PbF2 system contains continuous solid
solutions) and/or AlF3. Addition of BaF2 to the solid solution
increases its cubic lattice parameter [313], but the addition of AlF3
decreases the sze of the solid solution unit cell [230], thus making
the outcome for the formed composition quite different and
dependent on the actual chemical composition. Replacement of
uoride-ions by hydroxyls is quite probable, too, especially if one
uses Al(OH)3 instead of Al2O3 [128] as starting material for the
preparation of PbF2-based nanophase [128].
Another example includes the study of crystallites formed in
the SiO2-Al2O3-PbF2-CdF2-RF3 (R = Y, Yb, Tb, Er, Eu, Pr) glass
ceramics, where authors suggested different compositions for the
formed nanoparticles [19,20,124,136]. They considered the formed
crystallites to be face-centered cubic PbxCd1xF2:RF3 nanocrystals
(X-ray diffraction data), but Tikhomirov et al. [123] indicated that
the corresponding nanoparticles did not contain cadmium. Instead,
they were actually cubic PbF2:RF3 solid solutions.
Therefore, chemical analysis of the crystallized nanophases in
glass ceramics is necessary to determine what actually undergoes
crystallization.
Whereas classic-type chemical analysis is seldomly used for the
determination of nanophase chemical composition, the aforementioned EDX [110,145,199], X-ray uorescence analysis and ame
photometry [159] are widely implemented for nding the content
of nanocrystals in glass ceramics. An EDX study unequivocally
conrmed that nanocrystals formed in the 32SiO29AlO1.5
31.5CdF218.5PbF25.5ZnF2:3.5ErF3 system were, in fact, cubic
PbF2:RF3 solid solutions [132]. Therefore, practically all later
publications [115,117,120,126,130,131] considered cubic PbF2:RF3
nanocrystals as the crystalline phase of the aforementioned
system.
EDX-analyzed nanocrystal samples always contain traces of
their glass matrix materials due to the very small sizes of the
analyzed nanoparticles. In order to avoid this problem, the
detrmination of nanoparticle composition (e.g., their chemical
analysis) sould be done separately after their separation from the
glass matrix as was done by Hu et al. [125].
Regarding other type of crystalline inclusions in oxyuoride
glass ceramics, rst of all, it is necessary to mention tysonite
LaF3-type nanocrystals. This structural type is common for
cerium subgroup of the rare earth elements and includes two
different modications: ordered low-temperature (P3c1 space
symmetry group, Z = 6) and disordered high-temperature (P63/
mmc space symmetry group, Z = 2) [278]. Conversion between
these two polymorphs in glass ceramics is possible, and Zhang
et al. [220] have observed such transition from disordered
44
LaF3:Ho tysonite-type nanoparticles to ordered ones with

superstructure reections under increasing temperature during
the thermal treatment of samples.
Similar to the above discussed uorite-type crystals, tysonite
structural type objects are also prone to isomorphic substitutions
with creation of vacancies in the anionic sublattice. Such phases
are capable of accommodating large amounts of Ca, Sr, Ba, Pb
[230,278,286,314], Na [315,316] cations as well as oxygen atoms
[287], while forming the corresponding solid solutions. As was
already mentioned above, such formed crustalline inclusions can
not be reliably characterized only by X-ray diffraction data, and
their chemical analysis is a must for the unequivocal determination of their compositions.
Decrease of rare earth element ionic radii leads to the
morphotropic transition from hexagonal to orthorhombic b-YF3type [285] structure, which in contrast with tysonite is
characterized by strict stoichiometry. Growth of the latter type
crystals is a complicated technical problem, so glass ceramics
opens a unique opportunity to produce optical materials that
contain such unusual phases (Table 1) as a-YF3 [317], which can
not be easily stabilized at room temperature [318] and thus has
poorly documented spectral features.
NaFRF3 systems also have a similar feature of polymorphism
because of the competition between variable-composition cubic
uorite-type Na0.5xR0.5+xF2+2x phases and low-temperature hexagonal gagarinite-type NaRF4 phases [315]. The latter phases are
typical non-stoichiometric phases with structures similar to that of
UCl3. Their general formulas can be presented as Na3xR2xF6. One
should expect quite broad variations of compositions of both type
phases in the nanosystems, including oxyuoride glass ceramics.
For example, non-equilibrium cubic nanophase of NaLuF4
nominal composition has been described in [96]. Zhao et al.
[206] observed the transition from a metastable cubic to stable
hexagonal polymorphs of NaGdF4 while varying the composition of
starting glass materials. Hexagonal NaGdF4 was also prepared in
[202], and similar transition from metastable cubic NaYF4 to stable
hexagonal polymorph was observed [172]. However, authors of the
aforementioned publications did not question the actual composition of the uoride phases they have studied. They even did not
apply quite useful correlation [319] between lattice parameters of
uorite-type Na0.5xR0.5+xF2+2x phases, rare earth element (R) ionic
radii and phase composition to estimate the stoichiometry of the
obtained uorides.
Crystallization of nanophases in LiF-containing glass ceramics
systems leads to the preparation of specimens containing
tetragonal nanophases of LiYF4-type structure (I41/a space
symmetry group) [320,321]. Such type single crystals are
important optical materials, and thus, are glass ceramics with
LiYF4-type nano-inclusions. Deviation from stoichiometry in 3D
samples is insignicant and appears to be a matter of the ongoing
discussion [322,323].
Distribution of activators between glass and crystal phases
needs further study. Originally, researchers considered that rare
earth activators are almost completely extracted by forming
uoride nanocrystals, i.e., distribution coefcients of rare earth
ions between formed nanocrystals and their glass matrixes were
very high. Moreover, R/M ratio in these uorite-type nanophases in
regard to the same R/M ratio in the initial glass (so-called
segregation coefcient k) very frequently exceeds 1 (like in [41]): k
is about 1.52.0 in [55,131,132,142]. However, de Pablos-Martin
et al. [25] found that for alumosilicate glasses thulium was present
in both glass matrix and nanocrystalline LaF3. Also, other data [26]
indicate that neodymium ions are practically absent in nanocrystaline PbF2 phase distributed in the glass matrix. In [210], europium
was not extracted by CaF2, for its (Eu) luminescence spectra did not
change after the partial glass crystallization. However, the latter
fact may be explained by the specic glass composition that

includes bismuth in its matrix, and rare earth ions could have
occupied bismuth positions in the glass.
8. Spectral and luminescent properties of glass ceramics
Studying of oxyuoride glass ceramics materials is one very
important area of modern nanophotonics. New glassceramic
materials, containing nonlinear optical BaAlBO3F2 oxyuoride
nanocrystals, have been developed recently [211]. Surface crystallization under laser irradiation leads to a high degree of
orientation of BaAlBO3F2 nanocrystals, so it becomes very close to
the orientation of the structural blocks in the single crystals. As a
result, authors [211] were able to generate the second harmonic
irradiation.
Nevertheless, most papers dedicated to oxyuoride glass
ceramics are focused primarily on the spectral and luminescent
properties of these materials rather than their other properties.
The reason for such interest lies in the fact that, in general, glass
ceramics exhibit luminescence of higher intensity than other
materials, and the lifetimes of rare earth ions in their excited states
are longer in comparison to regular glasses, for multi-phonon
relaxation effect in uorides is smaller than in an oxide
environment [77].
The complexity of single crystal growth for some phases leads
to the viewing of glass ceramics as potential laser materials.
For example, glass ceramics with Ca5(PO4)3F:Nd3+ apatite [180] or
its Sr5(PO4)3F:Nd3+ strontium analog [183] nanoparticles are
quite useful as materials capable of generating 1.06 mm laser
radiation, especially in view of spectroscopic studies of Ca5(PO4)3F:Eu3+ model glass ceramics [325]. Glass ceramics containing
nano LaF3:Nd was considered as potential laser material for
1.06 mm emission [160]. Similarly, glass ceramics with Er-doped
crystallites (CaF2:Er3+ [88]; LaF3:Er3+ [240,242]; PbF2:Er3+[123];
NaYF4:Er3+[173];
LiYF4:Er3+[177];
PbF2:
Er3+,Yb3+[122];
3+
3+
3+
PbF2:Er ,Yb ,Ce
[217]; erbium uorosilicates or Pb5Al3F19:Er3+,Yb3+[119]) have been tested as quantum ampliers for
optical communication purposes at 1.54 mm wavelength (both
ber and planar implementation). Similarly, Pr3+-doped oxouoride glass ceramics was developed for 1.30 mm spectral range
[20], and transparent Ho3+ [134], Ho3+/Tm3+ and Ho3+/Tm3+/Eu3+
[212] doped nanoglass oxiuoride ceramics have been found to be
quite promising for application to optical amplication in the 1.2
1.7 and 1.4 mm spectrum range, respectively. The opportunity to
design a ber laser operating at approximately 2 mm wavelength
caused studying of luminescence properties of nanouorides
codoped with Ho3+,Tm3+ [82,140] and Ho3+,Yb3+ [201].
Luminescence intensity at the 2.06 mm range for glass ceramics
is higher than for the similar type glasses [126,201], and such
ceramic materials have potential applications in eye-safe laser
radar, laser medical surgery, combustion monitoring and atmosphere transmission of electromagnetic signals. Glass ceramics
with nano-CaF2: Er3+ were used for far-infrared emission generation at 2.7 mm (980 nm laser excitation) [79].
The infrared to ultraviolet emissions of Tm3+, originating from
the ve- and four-phonon upcoversition processes, were observed
in the Tm3+,Yb3+ codoped oxouoride glass ceramics. It is
interesting for the elaboration of short-wavelength solid-state
laser in the UV to green spectral range [40,156].
The above results are impressive, but complexity of achieveing
the appropriate optical quality of glass ceramic materials, which is
required for lasing, makes specialists considering glass ceramics to
be a luminescence material only, i.e., like traditional luminnophores. Thus, many authors noted the enhanced luminescence
properties of Eu [21,36,43,51,52,97,178,185,200,205,206,218], Er3+
[45,47,56,57,91,184,187,219,355], Tb3+ [43,72,111,178], Sm3+
[63,222], Tm3+ [178], Dy3+ [273], Pr3+ [41], and pair Eu2+/Mn2+
[113] in oxiuoride glass ceramic in comparison with their glass
precursors. Scintillation intensity of CaF2:Eu2+ under X-ray
exitation is weaker in glass ceramics compared to single crystal,
alhough stronger than Eu2+-doped glass [71]. The new areas of
glass ceramics research are relatively scarce (like laser cooling with
Tm3+-doped oxy-uoride glass ceramics [324]).
UV-luminescence of Ce3+ [59], thermoluminescence of
CaF2:Eu3+ and CaF2:Sm3+ [50], X-ray luminescence of CaF2:Tb3+,
Gd3+ [38] were also observed in oxyuoride glass ceramics.
However, it is worth noting that major efforts have been made
in the following areas: development of white-light-emitting
devices [194,326] and enhancing solar cell photovoltaic efciency
[80,202,327,328,354].
Both applications are based on complex processes of energy
transfer between different rare earth ions during their coactivation, and this includes the changes in the irradiation
wavelengths. Up conversion (UC) is the energy transfer from
low energy photons to high energy photons. This process has
relatively low efciency coefcients. The reverse process has been
termed as down conversion (DC). In particular, down conversion
includes so-called quantum cutting (QC). QC phosphors convert
one higher energy photon into two lower energy photons, and
thus, theoretically, QC efciency coefcients may reach 200%.
White-light-emitting diode (LED) technology has attracted
much attention because of advantages such as high luminous
efciency and long lifetime. Until recently, the most efcient way
to produce commercial white LEDs is a combination of the yellowemitting YAG:Ce3+ phosphor with the blue GaN or GaInN LED.
However, this component combination has a poor color rendering
index, and the latter stimulates searches for the other means of
down conversion of UV irradiation to visible light.
In order to increase solar panel efciency, one needs to increase
the efciency of converting both UV and visible light to nearinfrared (NIR) photons, for this is the part of spectrum, where
modern solar batteries have the best conversion coefcients and
the highest reliability. For DC mechanism, one UV-blue solar
photon (300500 nm) dissipating as heat in the solar cell (so-called
carrier thermalization) can be absorbed by the donor ions, i.e., Tb3+,
Pr3+, Nd3+, Tm3+, Ho3+, Er3+ or Tm3+ and then simultaneously
converted into two Yb3+ NIR photons above the c-Si energy gap
[105,130,149,354]. On the other hand, the NIR-QC system also may
be implemented in R3+ (R = Dy, Er, Ho and Tm) singly doped
luminophores [353]. Trupke et al. [327] calculated the theoretical
energy efciency of such c-Si cell coupled with an ideal DC layer to
be equal to 38.6%.
Enhancement of silicon solar cell efciency may be done with
the use of both down- and up-conversion processes
[274,352,353]. Up-conversion luminescence of Er-doped glass
ceramics containing NaGdF4 nanocrystals for silicon solar cells was
studied in [44,202]. Using excitation by 1530 nm diode laser, Xin
et al. [202] observed emission lines at 527, 540 and 653 nm.
Intensities of these lines for glassceramics were greatly enhanced
by heat treatment in comparison with starting entirely glass
specimens. Under similar excitation, luminescence was observed
at 410, 525, 550, 650, and 850 nm for nano (Pb,Cd)F2:Er3+ in [54].
In addition to the above matters, we would like to mention the
following publications that were specically focused at the
application of nanophase oxyuoride vitroceramics to enhance
silicon solar cell efciency, namely: infrared quantum cutting
luminescence phenomena of Ho3+/Yb3+ couple were studied in
[231,328,330], and efcient down conversion by near-infrared
quantum cutting was studied for glass ceramics containing Pr3+/
Yb3+ co-doped CaF2 [78,81,331], b-YF3 [152], or SrF2 [98],
respectively. Tb3+/Yb3+ visible to near infrared down conversion
luminescence was investigated in [147,170], when Tb3+ions were
45
initially excited by 488 nm irradiation to the 5D4 level in order to

stimulate the subsequent 2F5/2- 2F7/2 transition in Yb3+ ions in
infrared part of the spectrum (977 nm) [170].
Plasmonic resonance could be a venue for increasing the
luminescence in glass ceramics, and can be carried out by including
silver and/or gold nanoparticles, such as 14 nm molecular-like
silver clusters, that act as sensitizers for Tb3+Yb3+ near-infrared
down-conversion [105], and infrared-to-visible upconversion in
Er3+-doped glass ceramics [65].
Studies, dedicated to the development of white light emission
devices, include investigations of UV-driven emission by glass
ceramics, containing Ba2LaF7:Eu2+/Tb3+/Sm3+ [104] or YF3:Ho3+/Yb
3+
/Ce3+ [154] nanocrystals and oxyuoride glas ceramics co-doped
with Tb 3+/Sm3+ [73] or Tm3+, Tb3+, Eu3+ [70]. Also, photoluminescence properties of glass ceramics, containing CeF3:Dy3+ nanocrystals, were studied in [112].
Bae et al. [161] studied the behavior of rare earth-doped LaF3
nanocrystals incorporated in glass ceramics matrices for their
potential use in UVLED color convension devices. They tested
numerous dopants and found that Dy3+ and Eu3+ ions showed
practically utilizable visible emissions under UVLED excitation at
365 nm [161]. This is in agreement with other data [76,148].
Transparent glass ceramics (TGC) may be a candidate as a
warm-white LED materials pumped by a UV InGaN chip, so
borosilicate glass, containing Sr2GdF7 nanoparticles, was investigated [43,326]. The luminescence spectrum of Dy3+-doped TGC
exhibited white light emission under 382 nm UV excitation. The
emission color of Dy3+-Tb3+ co-doped TGC turned from green to
white via energy transfer from Dy3+ to Tb3+, and the emission color
of Dy3+-Eu3+ co-doped TGC turned from white to yellow through
energy transfer from Eu3+ to Dy3+ [326].
Glass ceramics white light sources are of separate interest for
the developers of computer displays, for they are based on
luminophores emitting white light by up-conversion. Such
luminophores possess low efciency coefcients, but their light
does not contain UV-component and, therefore, they are totally
harmless for human eyes [332]. They also can be used for the threedimensional displays (e.g., SiO2Al2O3NaFRF3 (R = Nd, Yb, Tm,
Ho) glass ceramics [334]). For such purposes, the up-conversion
luminescence glass ceramics, co-activated by Yb3+/Ho3+/Tm3+, was
studied in [49,107,118,120,129,151,155,176,213,333].
Oxyuoride glass ceramics opens tremendous opportunities for
these and other technical solutions by combining different ionsactivators in various uoride nanocrystals and glass matrices.
Thus, Sontakke and Annapurna [172] studied energy transfer
kinetics for combinations of different donor-acceptor ions (e.g., Nd
3+
/Yb3+; Yb 3+/Dy3+; Nd 3+/Dy3+) in cubic NaYF4 nanoparticles; Lin
et al. [150] and Yu et al. [95] studied Tm3+ ions up- and downconversion luminescence; and Wang and Ohwaki [19] were the
rst ones who achieved an up-conversion luminescence for Yb3+/
Er3+ ionic pair in uoride glass ceramics (Pb1xCdxF2-based
nanoparticles) with energy transformation from the near-infrared
to the visible part of the spectrum. Later, the same activator couple
was used in nanoparticles of different chemical compositions, such
as PbF2 [53,115,193], Pb4Yb3F17 [23], CaF2 [74,86,89,329],
Ca1xLaxF2+x [68], SrF2 [142], BaF2 [229], Ba2GdF7 [42,199],
NaYF4 [44], YOF [203], b-NaCaAlF6 [96] and other [58] surrounded
by oxide glass matrixes. The up-conversion luminescence for
Yb3+/Tm3+ ion pair in oxiuoride glass ceramics has been studied
for PbF2 [117,221], SrF2 [138], Ba2GdF7 [42], b-YF3 [190]
nanocrystals. Other achievements in this area include: an upconversion luminescence of CaF2:Er3+, enhanced by plasmon
resonance on gold nanoparticles, observed in [65]; an enhanced
luminescence of nano-LaOF:Er3+ observed in [204]; interaction of
Tb3+Yb3+ co-activator couple in various uoride nanoceramics
[96,128,164].
46
9. Conclusions
Oxyuoride glass ceramics studies are represented in both
regular scientic papers as well as in a large body of patent
literature, see, for example [334345].
Despite the plethora of papers published about uoride glass
ceramics, it is necessary to admit that the main goal of creation of
the novel materials for photonics obtaining laser generation has
yet to be achieved for glass ceramics. Such achievement requires
signicant improvements in the optical transparency of the
synthesized media. Many glasses, used for the preparation of
oxyuoride glass ceramics, are subjected to micro-liquation; and
as a result, inclusions with refraction coefcients different from
that of the glass matrix have much larger sizes than the
nanoparticles formed within such inclusions (drops). In turn,
these drops are much larger than the wavelength of emitted or
absorbed light, and this factor causes unacceptably high optical
losses and makes it impossible to achieve laser generation.
Therefore, in order to resolve that latter lasing problem, one has
to nd the new glass compositions that would not have areas of
phase separation (aliquation) with uorides. Already, there are
numerous classes of oxyuoride glasses that should be thoroughly
investigated from this point of view [346349,355] in order to
develop new types of oxyuoride glass ceramics.
The majority of published oxyuoride glass ceramics studies
lacks clearly determined areas of glass formation for multicomponent systems, which is in contrast to entirely uoride glasses,
where such determinations (of glass formation areas) are the
regular beginning of the investigation.
Researchers should pay more attention to glass ceramics with
nanophases, that usually do not easily produce single crystals (e.g.,
uoride garnets), or to ceramics containing non-equilibrium
phases, that emerge during glass crystallization (e.g., nanophases
of a-YF3 stuctural type, that can not be stabilized as large
voluminous objects under ambient conditions [317,318]).
One may expect further progress in the creation of novel
optically active nano-glassceramics [272], containing inclusions
of segnetoelectric or non-linear optical uoride nanoparticles, and/
or development of highly promising optical ceramics containing
non-linear potassium beryllium uoroborate (KBBF) nanoparticles
(preparation of KBBF single crystals is a highly challenging task
[350]).
The further investigations are warranted for:
- the phase and chemical compositions of crystalline nano-phases
in oxyuoride glass ceramics, the structure of the transitional
border layer separating the uoride nanoparticles and the oxide
glassy matrix, and
- for the disctribution of activators between crystal and glass
phases in various oxyuoride glass ceramics.
Such information about the real composition of crystalline
inclusions is critically important for controlling the properties of
synthesized materials. Also it is necessary to investigate oxygen
incorporation into uoride nanoparticles.
In the course of the aforementioned studies, it is always
necessary to follow certain experimental rules, such as using inert
[355] or reducing atmosphere [104] and/or introduce self-uorinating agents in the starting batches (e.g., BaF2.HF [351],
Sr1xRxF2+x:NH4F [332], etc.) in order to minimize uorine losses,
and so on.
The above-mentioned materials are not the only promising
objects for studies in the area of oxyuoride glass ceramics. One
should not discount an alternative type of these substances, i.e.,
composites formed by oxide nano- and/or submicro-particles
(SiO2, Al2O3) imbedded in the uoride glass matrices. Such
inversed ceramics, well-known for the polycrystalline uoride
matrices, are of high interest for cases when the increase of

uoride-ion conductivity is required.
Finally, one should not overlook a very special and highly useful
class of oxide glass ceramics that contains inclusions of the other
halide nanoparticles (chlorides, bromides, iodides): such halides
are highly hygroscopic, and their particles require special
protecting layers to avoid their degradation, but their properties
may be the solution for the aforementioned problems in design
and synthesis of the novel materials for photonics.
Acknowledgements
Authors thank S. V. Kuznetsov and V. V. Osiko for their valuable
discussions and Elena Chernova and Richard Simoneaux for their
help in the preparation of this manuscript. This work was
supported by Russian Foundation for Basic Research grant number
15-08-02481.
References
[1] S.D. Stookey, Ind. Eng. Chem. 45 (1953) 115118.
[2] (a) S.D. Stookey, Ind. Eng. Chem. 46 (1954) 174176;
(b) S.D. Stookey, Res. Manage. 1 (1958) 155163.
[3] S.D. Stookey, Ind. Eng. Chem. 51 (1959) 805808.
[4] W. Pannhorst, J. Non-Cryst. Solids 219 (1997) 198204.
[5] P.W. McMillan, Glass Ceram., second ed., Academic Press, London, New York,
1979, 285 pp..
[6] I.I. Kitaigorodskii (Ed.), Tekhnologiya Stekla (Glass Technology), fourth ed.,
Izdatelstvo Literatury po Stroitelstvu, Moscow, 1967 (564 pp.).
[7] G.H. Beall, D.A. Duke, J. Mater. Sci. 4 (1969) 340352.
[8] E.T. Zanotto, Int. J. Appl. Glass Sci. 4 (2013) 105116.
[9] L.R. Pinckney, Glass ceramics, in: Encyclopedia of Materials: Science and Technology, second ed., Elsevier Ltd., Amsterdam, 2001, , pp. 35353540ISBN 978-008-043152-9.
[10] G.H. Beall, L.R. Pinckney, J. Am. Ceram. Soc. 82 (1999) 516.
[11] A. Lipovskii, E. Kolobkova, V. Petrikov, I. Kang, A. Olkhovets, N. Krauss, M.
Thomas, J. Silcox, F. Wise, Q. Chen, S. Kycia, Appl. Phys. Lett. 71 (1997) 3406
3408.
[12] Yu Teng, K. Sharafudeen, S. Zhou, J. Qiu, J. Ceram. Soc. Japan 120 (2012) 458466.
[13] D. Ehrt, IOP Conf. Ser.: Mater. Sci. Eng. 2 (2009) 012001, http://dx.doi.org/
10.1088/1757-899X/2/1/012001.
[14] D. Ehrt, IOP Conf. Series: Mater. Sci. Eng. 21 (2011) 012001, http://dx.doi.org/
10.1088/1757-899X/21/1/012001.
[15] F. Auzel, Chem. Rev. 104 (2004) 139173.
[16] S.D. Stookey, US Patent 2,921,860 (1960).
[19] Y. Wang, J. Ohwaki, Appl. Phys. Lett. 63 (1993) 32683270.
[20] P.A. Tick, N.F. Borrelli, L.K. Cornelius, M.A. Newhouse, J. Appl. Phys. 78 (1995)
63676375.
[21] M.J. Dejneka, J. Non-Cryst. Solids 239 (1998) 149155.
[22] T. Suzuki, S. Masaki, K. Mizuno, Y. Ohishi, Proc. SPIE 7721 (2010) 77210T, http://
dx.doi.org/10.1117/12.854090.
[23] I. Gugov, M. Mueller, C. Ruessel, J. Solid State Chem. 184 (2011) 10011007.
[24] A.J. Stevenson, H. Serier-Blrault, P. Gredin, M. Mortier, J. Fluorine Chem. 132
(2011) 11651173.
[25] A. de Pablos-Martin, C. Patzig, T. Hoeche, A. Duran, M.J. Pascual, CrystEngComm
15 (35) (2013) 69796985.
[26] H. Yu, H. Guo, M. Zhang, Y. Liu, M. Liu, L.J. Zhao, Nanoscale Res. Lett. 7 (2012) 275.
[27] B. Dieudonne, B. Boulard, G. Alombert-Goget, A. Chiasera, Y. Gao, S. Kodjikian, M.
Ferrari, J. Non-Cryst. Solids 377 (2013) 105109.
[28] R. Lisiecki, E. Augustyn, W. Ryba-Romanowski, M. Zelechower, Opt. Mater. 33
(11) (2011) 16301637, http://dx.doi.org/10.1016/j.optmat.2011.04.027.
[29] P.P. Fedorov, A.A. Luginina, S.V. Kuznetsov, V.V. Osiko, J. Fluorine Chem. 132 (2011)
10121039.
[30] M. Mortier, G. Dantelle, in: A. Tressaud (Ed.), Functionalized Inorganic Fluorides:
Synthesis, Characterization & Properties of Nanostructured Solids, John Wiley &
Sons, Ltd., Chichester, West Sussex, UK, 2010, pp. 273303.
[31] Pablos-Martin, A. Duran, M.J. Pascual, Int. Mater. Rev. 57 (2012) 165186.
[32] M.M. Shul0 ; O.V. Mazurin, Sovremennye predstavleni o stroenii stekol i ikh
svostvakh, Leningrad: Nauka," Leningradskoe otd-nie, 1988. 197 pp.
[33] V. K. Leko, O. V. Mazurin, Svoistva kvar evogo stekla, Ed. B. G. Varshal,
Leningrad: Izd-vo Nauka," Leningradskoe otd-nie, 1985. 164 pp.
[34] V. Fay, Tooley (Eds.), The Handbook of Glass Manufacture, third ed., Books for the
Glass Industry Division, Ashlee Pub. Co, New York, NY, 1984 (2 volumes, set).
0911993223.
[35] C. Russel, Chem. Mater. 17 (2005) 58435847.
[36] J. Fu, J.M. Parker, P.S. Flower, R.M. Brown, Mater. Res. Bull. 37 (2002) 18431849.
[37] G. Aldica, M. Secu, J. Non-Cryst. Solids 356 (3334) (2010) 16311636.

[38] X.-Y. Sun, S.-M. Huang, Nucl. Instrum. Methods Phys. Res. A 621 (2010) 322325,
http://dx.doi.org/10.1016/j.nima.2010.04.032.
[39] D.Q. Chen, Y.S. Wang, Y.L. Yu, E. Ma, F. Bao, Z.J. Hu, Y. Cheng, Mater. Chem. Phys
95 (23) (2006) 264269, http://dx.doi.org/10.1016/j.matcehmphys.2005.06.
017.
[40] D.Q. Chen, Y.S. Wang, Y.L. Yu, Ping Huang, Appl. Phys. Lett. 91 (2007) 051920,
http://dx.doi.org/10.1063/1.2767988.
[41] K. Biswas, A.D. Sontakke, J. Ghosh, K. Annapurna, J. Am. Ceram. Soc. 93 (2010)
10101017.
[42] S.L. Zhao, S.Q. Xu, D.G. Deng, H.P. Wang, L.H. Huang, X.P. Fan, Chem. Phys. Lett.
494 (2010) 202205, http://dx.doi.org/10.1016/j.cplett.2010.06.012.
[43] F. Xin, S. Zhao, S. Xu, L. Huang, G. Jia, D. Deng, H. Wang, Opt. Mater. 34 (2011)
8588.
[44] S. Zhao, S. Xu, G. Jia, D. Deng, L. Huang, H. Wang, Mater. Lett. 65 (2011)
24072409.
[45] L.J. Lin, G.Z. Ren, M.P. Chen, Y. Liu, Spectrosc. Spectral Anal. 29 (12) (2009) 3212
3215, http://dx.doi.org/10.3964/j.issn.1000-0593(2009)12-3212-04.
[46] V.A. Aseev, V.V. Golubkov, A.V. Klementeva, E.V. Kolobkova, N.V. Nikonorov, Opt.
Spectrosc. 106 (2009) 691696.
[47] V.A. Aseev, Yu.A. Varaksa, A.V. Klementeva, E.V. Kolobkova, N.V. Nikonorov, G.V.
Sinitsyn, M.A. Khodasevich, Opt. Spectrosc. 108 (2010) 720727.
[48] D.Q. Chen, Y.S. Wang, Y.L. Yu, E. Ma, L.H. Zhou, J. Solid State Chem. 179 (2) (2006)
532537, http://dx.doi.org/10.1016/j.jssc.2005.11.010.
[49] J. del-Castillo, A.C. Yanes, J. Mendez-Ramos, V.K. Tikhomirov, V.V. Moshchalkov,
V.D. Rodriguez, J. Sol-Gel Sci. Technol. 53 (2010) 509514.
[50] M. Secu, C.E. Secu, C. Ghica, Opt. Mater. 33 (2010) 613617.
[51] S. Fujihara, T. Kato, T. Kimura, J. Am. Ceram. Soc. 84 (2001) 27162718.
[52] A. Santana-Alonso, A.C. Yanes, J. Mendez-Ramos, J. del-Castillo, V.D. Rodrguez, J.
Non-Cryst. Solids 356 (2010) 933936.
[53] J. del-Castillo, A.C. Yanes, J. Mendez-Ramos, V.K. Tikhomirov, V.D. Rodrguez,
Opt. Mater. 32 (2009) 104107.
[54] A.S. Gouveia-Neto, L.A. Bueno, R.F. do Nascimento, E.A. da Silva, E.B. da Costa, J.
Non-Cryst. Solids 355 (2009) 488491.
[55] M. Mortie, A. Bensalah, G. Dantelle, G. Patriarche, D. Vivien, Opt. Mater. 29 (2007)
12631270.
[56] M. Mortier, P. Goldner, C. Chateau, M. Genotelle, J. Alloys Compd. 323324
(2001) 245249.
[57] Z. Pan, A. Ueda, M. Hays, R. Mu, S.H. Morgan, J. Non-Cryst. Solids 352 (2006)
801806.
[58] C. Yu, D. He, G. Wang, J. Zhang, L. Hu, Eighth Pacic Rim Conference on Lasers and
Electro-Optics. CLEO/PACIFIC RIM, 2009, 12, http://dx.doi.org/10.110/
CLEOPR.2009.5292452.
[59] L. Dimitrocenko, U. Rogulis, A. Veispals, M. Springis, P. Kulis, A. Fedotovs, A.
Mishnev, Phys. Status Solidi C 4 (2007) 753756, http://dx.doi.org/10.1002/
pssc.200673827.
[60] O.B. Petrova, L.N. Dmitruk, A.V. Popov, V.E. Shukshin, Opt. Spectrosc. 107 (2009)
347352.
[61] Fernandes Roger Gomes, Pereira Camila, Bertholdo Roberto, Fabia Castro Cassanjes, Gael Poirier, J. Non-Cryst. Solids 357 (2011) 33453350.
[62] Z. Xue, T.G. Edwards, S. Sen, J. Am. Ceram. Soc. 94 (2011) 20922098, http://
dx.doi.org/10.1111/j.1551-2916.2011.04480.x.
[63] M. Secu, J. Nanopart. Res. 13 (7) (2010) 27272732, http://dx.doi.org/10.1007/
s11051-010-0181-2.
[64] M. Secu, C.E. Secu, S. Polosan, G. Aldica, C. Ghica, J. Non-Cryst. Solids 355 (2009)
18691872.
[65] Jumpei Ueda, Setsuhisa Tanabe, Akito Ishida, J. Non-Cryst. Solids 355 (2009)
19121915.
[66] M.H. Imanieh, I.R. Martin, B.E. Yekta, V.K. Marghussian, S. Shakhesi, J. Am. Ceram.
Soc. 95 (2012) 38273833, http://dx.doi.org/10.1111/jace.12012.
[67] M.-Y. Yoo, J.-H. Lee, H.-M. Jeong, K.S. Lim, P. Babu, Opt. Mater. 35 (2013) 1922
1926, http://dx.doi.org/10.1016/j.optmat.2012.12.020.
[68] M.H. Imanieh, I.R. Martin, B.E. Yekta, J. Gonzalez-Platas, A.H. Creus, J. Am. Ceram.
Soc. 97 (2014) 782788, http://dx.doi.org/10.1111/jace.12816.
[69] J.H. Xie, Q.A. Zhang, Y.X. Zhuang, X.F. Liu, M.J. Guan, B. Zhu, R. Yang, J.R. Qiu, J.
Alloys Compd. 509 (2011) 30323037, http://dx.doi.org/10.1016/j.jallcom.2010.11.192.
[70] J.Y. Qian, Q. Luo, D.L. Zhao, S.O. Cui, X.S. Qiao, X.P. Fan, X.H. Zhang, Opt. Mater. 34
(2012) 700704, http://dx.doi.org/10.1016/j.optmat.2011.10.003.
[71] J. Fu, M. Kobayashi, S. Sugimoto, J.M. Parker, J. Am. Ceram. Soc. 92 (2009) 2119
2121.
[72] X.-Y. Sun, M. Gu, S.-M. Huang, X.-J. Jin, X.-L. Liu, B. Liu, C. Ni, J. Lumin. 129 (2009)
773777, http://dx.doi.org/10.1016/j.jlumin.2009.02.017.
[73] Z.Y. Lin, X.L. Liang, Y.W. Ou, C.X. Fan, S.L. Yuan, H.D. Zeng, G.R. Chen, J. Alloys
Compd. 496 (2010) L33L37, http://dx.doi.org/10.1016/j.jallcom.2010.02.155.
[74] Y. Kishi, S. Tanabe, S. Tochino, G. Pezzotti, J. Am. Ceram. Soc. 88 (2005) 3423
3426, http://dx.doi.org/10.1111/j.1551-2916.2005.00614.x.
[75] K. Shinozaki, T. Honma, K. Oh-ishi, T. Komatsu, Opt. Mater. 33 (2011) 13501356,
http://dx.doi.org/10.1016/j.optmat.2011.03.037.
[76] P. Babu, K.H. Jang, C.S. Rao, L.A. Shi, C.K. Jayasankar, V. Lavin, H.J. Seo, Opt. Express
19 (2011) 18361841, http://dx.doi.org/10.1364/OE.19.001836.
[77] G. Lakshminarayana, R. Yang, M.F. Mao, J.R. Qiu, I.V. Kityk, J. Non-Cryst. Solids
355 (2009) 26682673, http://dx.doi.org/10.1016/j.jnoncrysol.2009.08.029.
[78] L. Zhang, J. Xu, Y. Hu, G. Chen, Z. Wang, J. Wuhan Univ. Technol.-Mater. Sci. 28
(2013) 455459.
[79] G.B. Wu, S.H. Fan, Y.H. Zhang, G.Q. Chai, Z.J. Ma, M.Y. Peng, J.R. Qui, G.P. Dong, Opt.
Lett. 38 (2013) 30713074 http://dx.doi.org/10.1364/OL.38.003071.
47
[80] Q.J. Chen, W.J. Zhang, X.Y. Huang, G.P. Dong, M.Y. Peng, Q.Y. Zhang, J. Alloys
Compd. 513 (2012) 139144.
[81] Y. Kishi, S. Tanabe, J. Alloys Compd. 408412 (2006) 842844.
[82] W.J. Zhang, Q.J. Chen, Q.Y. Zhang, Z.H. Jiang, J. Non-Cryst. Solids 357 (2011)
22782281.
[83] D.Q. Chen, Y.S. Wang, Y.L. Yu, E. Ma, F. Bao, Z.J. Hu, Y. Cheng, Mater. Res. Bull. 41
(2006) 11121117, http://dx.doi.org/10.1016/j.materresbull.2005.11.009.
[84] D.Q. Chen, Y.S. Wang, Y.L. Yu, E. Ma, F. Liu, J. Phys. Chem. Solids 68 (2007) 193
200, http://dx.doi.org/10.1016/j.jpcs.2006.10.009.
[85] D.Q. Chen, Y.S. Wang, E. Ma, Y.L. Yu, F. Liu, Opt. Mater. 29 (2007) 16931699,
http://dx.doi.org/10.1016/j.optmat.2006.09.002.
[86] Z.J. Hu, Y.S. Wang, E. Ma, D.Q. Chen, F. Bao, Mat. Chem. Phys. 101 (2007) 234237,
http://dx.doi.org/10.1016/j.matchemphys.2006.04.001.
[87] H. Lin, D.Q. Chen, Y.L. Yu, Z.F. Shan, P. Huang, A.P. Yang, Y.S. Wang, J. Alloys
Compd.
509
(2011)
33633366,
http://dx.doi.org/10.1016/j.jallcom.2010.12.066.
[88] D.Q. Chen, Y.S. Wang, Y.L. Yu, E. Ma, J. Solid State Chem. 179 (2006) 14451452,
http://dx.doi.org/10.1016/j.jssc.2006.01.056.
[89] T. Honma, M. Kanno, T. Komatsu, Mater. Sci. Eng. B 171 (2010) 2530, http://
dx.doi.org/10.1016/j.mseb.2010.03.049.
[90] M. Kusatsugu, M. Kanno, T. Honma, T. Komatsu, J. Solid State Chem. 181 (2008)
11761183.
[91] M. Kanno, T. Honma, T. Komatsu, J. Am. Ceram. Soc. 92 (2009) 825829.
[92] M. Kanno, T. Honma, T. Komatsu, Mater. Res. Bull. 44 (2009) 21432146.
[93] K. Ritter, S. Gerlach, C. Ruessel, J. Non-Cryst. Solids 356 (5254) (2010) 3090
3094, http://dx.doi.org/10.1016/j.jnoncrysol.2010.04.056, SI.
[94] R.P.F. de Almeida, C. Bocker, C. Russel, Chem. Mater. 20 (2008) 59165921,
http://dx.doi.org/10.1021/cm801426u.
[95] D.C. Yu, J.P. Zhang, Q.J. Chen, W.J. Zhang, Z.M. Yang, Q.Y. Zhang, Appl. Phys. Lett.
101 (17) (2012) 171108, http://dx.doi.org/10.1063/1.4764005.
[96] Y.L. Wei, X.Y. Liu, X.N. Chi, R.F. Wei, H. Guo, J. Alloys Compd. 578 (2013) 385388,
http://dx.doi.org/10.1016/j.jallcom.2013.06.014.
[97] Q. Luo, X.S. Qiao, X.P. Fan, X.H. Zhang, J. Am. Ceram. Soc 93 (2010) 26842688,
http://dx.doi.org/10.1111/j.1551-2916.2010.03756.x.
[98] Y. Katayama, S. Tanabe, J. Lumin. 134 (2013) 825829.
[99] M. Reben, J. Non-Cryst. Solids 357 (2011) 26532657.
[100] C. Bocker, J. Wiemert, C. Ruessel, J. Eur. Ceram. Soc. 33 (2013) 17371745.
[101] S.-M. Huang, Q.-C. Gao, M. Gu, J. Lumin. 132 (2012) 750754, http://dx.doi.org/
10.1016/j.jlumin.2011.11.002.
[102] M. Gu, Q.-C. Gao, S.-M. Huang, X.-L. Liu, B. Liu, C. Ni, J. Lumin. 132 (2012) 2531
[103] X.Y. Liu, Y.L. Wei, R.F. Wei, J.W. Yang, H. Guo, J. Am. Ceram. Soc. 96 (2013) 798
800, http://dx.doi.org/10.1111/jace.12086.
[104] Y. Xu, S. Cui, H.Y. Fu, J.Y. Qian, Q. Luo, X.S. Qiao, X.P. Fan, X.H. Zhang, Chin. Opt.
Lett. 10 (2012) 031602, http://dx.doi.org/10.3788/COL201210.031602.
[105] H. Lin, D.Q. Chen, Y.L. Yu, R. Zhang, Y.S. Wang, Appl. Phys. Lett. 103 (2013)
091902, http://dx.doi.org/10.1063/1.4819951.
[106] S. Bhattacharyya, C. Bocker, T. Heil, J.R. Jinschek, T. Hoche, C. Russel, H. Kohl,
Nano Lett. 9 (2009) 24932496.
[107] C.X. Li, S.Q. Xu, R.G. Ye, D.G. Deng, Y.J. Hua, S.L. Zhao, S.L. Zhuang, Physica B 406
(2011) 16981701, http://dx.doi.org/10.1016/j.physb.2011.01.073.
[108] L.F. Vendramim, K. Zorn, C. Bocker, C. Russel, J. Non-Cryst. Solids 356 (2010)
29993003, http://dx.doi.org/10.1016/j.jnoncryso1.2010.02.024.
[109] F. Liu, Y.S. Wang, D.Q. Chen, Y.L. Yu, E. Ma, L.H. Zhou, P. Huang, Mater. Lett. 61
(2007) 50225025, http://dx.doi.org/10.1016/j.matlet.2007.03.089.
[110] Z. Shan, D. Chen, Y. Yu, P. Huang, F. Weng, H. Lin, Y. Wang, Mater. Res. Bull. 45
(2010) 10171020.
[111] S. Huang, M. Gu, J. Non-Cryst. Solids 358 (2012) 7780.
[112] L.A. Wu, H.Y. Fu, J.Y. Qian, D.L. Zhao, Q. Luo, X.S. Qiao, X.P. Fan, X.H. Zhang, Chin.
Phys. Lett. 29 (2012) 017802, http://dx.doi.org/10.1088/0256-307X/29/1/
017802.
[113] Q. Luo, X.S. Qiao, X.P. Fan, B. Fan, X.H. Zhang, J. Am. Ceram. Soc. 94 (2011) 1670
1674, http://dx.doi.org/10.1111/j.1551-2916.2011.04554.x.
[114] A.F. Lahoz, I.R. Martin, J.M. Calvilla-Quintero, Appl. Phys. Lett. 86 (2005) 0511061051106-3.
[115] Wei Xu, Cheng-Ren Li, Bao-Sheng Cao, Bin Dong, Chin. Phys. B 19 (12) (2010)
127804.
[116] C. Liu, X. Zhao, J. Heo, J. Non-Cryst. Solids 365 (2013) 15.
[117] J.B. Qiu, Z.G. Song, J. Rare Earths 26 (2008) 919923.
[118] Z.C. Duan, J.J. Zhang, W.D. Xiang, H.T. Sun, L.L. Hu, Mater. Lett. 61 (2007) 2200
2203, http://dx.doi.org/10.1016/j.matlet.2006.08.049.
[119] E. Augustyn, M. Zelechower, D. Stroz, J. Chraponski, Opt. Mater. 34 (2012) 944
[120] S.F. Leon-Luis, J. Abreu-Afonso, J. Pena-Martinez, J. Mendez-Ramos, A.C. Yanes, J.
del-Castillo, V.D. Rodriguez, J. Alloys Compd. 479 (2009) 557560, http://
dx.doi.org/10.1016/j.jallcom.2008.12.136.
[121] A.S. Kuznetsov, A. Nikitin, V.K. Tikhomirov, M.V. Shestakov, V.V. Moshchalkov,
Appl. Phys. Lett. 102 (2013) 161916, http://dx.doi.org/10.1063/1.4803448.
[122] S.-Q. Luo, L.-J. Zhao, N. Hu, M. Zhang, P. Zhang, Y.-Z. Wang, H. Yu, Chin. Phys. Lett.
28 (2011) 034207, http://dx.doi.org/10.1088/0256-307X/28/3/034207.
[123] V.K. Tikhomirov, D. Furniss, A.B. Seddon, I.M. Reaney, M. Beggiora, M. Ferrari, M.
Montagna, R. Rolli, Appl. Phys. Lett. 81 (2002) 19371939.
[124] H. Yu, K.D. Zhou, K. Chen, J. Song, C.X. Hou, L.J. Zhao, J. Non-Cryst. Solids 354 (30)
(2008) 36493652, http://dx.doi.org/10.1016/j.jnoncrysol.2008.03.015.
[125] Nan Hu, Hua Yu, Ming Zhang, Pan Zhang, Yazhou Wang, Lijuan Zhao, Phys. Chem.
Chem. Phys. 13 (2011) 14991505, http://dx.doi.org/10.1039/c0cp00903b.
48
[126] J.J. Pan, R.R. Xu, Y. Tian, K.F. Li, L.L. Hu, J.J. Zhang, Opt. Mater. 32 (2010) 1451
[127] M. Liu, H. Yu, P. Zhang, M. Zhang, Y. Liu, L.J. Zhao, Acta Phys. Sin. 61 (2012) 118102.
[128] X. Chen, S. Li, G.J. Salamo, et al. Opt. Lett. 38 (2013) 15301532, http://
dx.doi.org/10.1364/OL.38.001530.
[129] D. Zhou, R. Wang, Z. Song, Z. Yang, X. Yu, D. Yan, C. Li, J. Qiu, IEEE (2012), ISBN
978-1-4577-0911.
[130] V.D. Rodrguez, V.K. Tikhomirov, J. Mendez-Ramos, A.C. Yanes, V.V. Moshchalkov, Sol. Energy Mater. Sol. Cells 94 (2010) 16121617.
[131] V.K. Tikhomirov, M. Mortier, P. Gredin, G. Patriarche, C. Gorller-Walrand, V.V.
Moshchalkov, Opt. Express 16 (2008) 1454414549.
[132] W. Van den Heuvel, V.K. Tikhomirov, D. Kirilenko, N. Schildermans, L.F. Chibotaru, J. Vanacken, P. Gredin, M. Mortier, G. Van Tendeloo, V.V. Moshchalkov,
Phys. Rev. B: Condens. Matter 82 (2010) 094421, http://dx.doi.org/10.1103/
PhysRevB.82.094421.
[133] V.A. Aseev, V.V. Golubkov, E.V. Kolobkova, N.V. Nikonorov, Glass Phys. Chem. 38
(2012) 212217, http://dx.doi.org/10.1134/S1087659612020010.
[134] K. Driesen, V.K. Tikhomirov, C. Gorller-Walrand, Appl. Phys. Lett. 88 (2006)
073111, http://dx.doi.org/10.1063/1.2174829.
[135] A.M. Beggiora, I.M. Reaney, A.B. Seddon, D. Furniss, S.A. Tikhomirova, J. NonCryst. Solids 326327 (2003) 476483.
[136] E.V. Kolobkova, N.O. Tagiltseva, P.A. Lesnikov, Glass Phys. Chem. 36 (2010) 317324.
[137] E.V. Kolobkova, V.G. Melekhin, A.N. Penigin, Glass Phys. Chem. 33 (2007) 813.
[138] X.S. Qiao, X.P. Fan, Z. Xue, X.H. Xu, J. Non-Cryst. Solids 357 (2011) 8387, http://
dx.doi.org/10.1016/j.jnoncrysol.2010.09.008.
[139] W.-J. Zhang, Q.-J. Chen, Q. Qian, Q.-Y. Zhang, J. Am. Ceram. Soc. 95 (2011) 663
669, http://dx.doi.org/10.1111/j.1551-2916.2011.04809.x.
[140] W.J. Zhang, Q.Y. Zhang, Q.J. Chen, Q. Qian, Z.M. Yang, J.R. Qiu, P. Huang, Y.S. Wang,
Opt. Express 17 (2009) 2095220958.
[141] Y.-M. Sung, J. Non-Cryst. Solids 358 (2012) 3639.
[142] X.S. Qiao, X.P. Fan, M.Q. Wang, X.H. Zhang, J. Phys. D: Appl. Phys. 42 (2009)
055103, http://dx.doi.org/10.1088/0022-3727/42/5/055103.
[143] X.S. Qiao, X.P. Fan, Z. Xue, X.H. Xu, Q. Luo, J. Alloys Compd. 509 (2011) 4714
4721, http://dx.doi.org/10.1016/j.jallcom.2011.01.099.
[144] X.S. Qiao, X.P. Fan, Z. Xue, X.H. Xu, Q. Luo, J. Lumin. 131 (2011) 20362041,
http://dx.doi.org/10.1016/j.jlumin.2011.05.012.
[145] X.S. Qiao, X.P. Fan, Y. Pan, A. Lotnyk, L. Kienle, Mater. Res. Bull. 47 (2012) 2934,
http://dx.doi.org/10.1016/j.materresbull.2011.10.014.
[146] G. Lakshminarayana, E.M. Weis, B.L. Bennett, A. Labouriau, D.J. Williams, J.G.
Duque, M. Sheik-Bahae, M.P. Hehlen, Opt. Mater. 35 (2012) 117125, http://
dx.doi.org/10.1016/j.optmat.2012.07.022.
[147] D.Q. Chen, Y.L. Yu, Y.S. Wang, P. Huang, F.Y. Weng, J. Phys. Chem. C 113 (2009)
64066410, http://dx.doi.org/10.1021/jp809995f.
[148] D.Q. Chen, Y.L. Yu, P. Huang, H. Lin, Z.F. Shan, Y.S. Wang, Acta Mater. 58 (2010)
30353041, http://dx.doi.org/10.1016/j.actamat.2010.01.035.
[149] D.Q. Chen, Y.L. Yu, H. Lin, P. Huang, Z.F. Shan, Y.S. Wang, Opt. Lett. 35 (2010) 220
222.
[150] H. Lin, J. Marques-Hueso, D.Q. Chen, Y.S. Wang, B.S. Richards, Mater. Res. Bull. 47
[151] D.Q. Chen, Y.S. Wang, K.L. Zheng, T.L. Guo, Y.L. Yu, P. Huang, Appl. Phys. Lett. 91
(2007) 251903, http://dx.doi.org/10.1063/1.2825285.
[152] D.Q. Chen, Y.S. Wang, Y.L. Yu, P. Huang, F.Y. Weng, Opt. Lett. 33 (2008) 1884
1886, http://dx.doi.org/10.1364/OL.33.001884.
[153] D.Q. Chen, Y.S. Wang, Y.L. Yu, F. Liu, P. Huang, Opt. Lett. 32 (2007) 30683070,
http://dx.doi.org/10.1364/OL.32.003068.
[154] F.G. Yang, G.T. Chen, Z.Y. You, C.Y. Tu, Mater. Lett. 64 (2010) 824826, http://
dx.doi.org/10.1016/j.matlet.2010.01.026.
[155] D.Q. Chen, Y.S. Wang, Y.L. Yu, P. Huang, F.Y. Weng, J. Solid State Chem. 181 (2008)
27632767, http://dx.doi.org/10.1016/j.jssc.2008.07.003.
[156] H. Lin, D.Q. Chen, Y.L. Yu, A.P. Yang, R. Zhang, Y.S. Wang, Mater. Res. Bull. 47
[157] D.Q. Chen, Y.L. Yu, P. Huang, Y.S. Wang, CrystEngComm 11 (2009) 16861690,
http://dx.doi.org/10.1039/b904169a.
[158] D.Q. Chen, Y.L. Yu, H. Lin, P. Huang, F.Y. Weng, Z.F. Shan, Y.S. Wang, Opt. Lett. 34
(2009) 28822884.
[159] N. Hemono, G. Pierre, F. Munoz, A. de Pablos-Martin, M.J. Pascual, A. Duran, J. Eur.
Ceram. Soc. 29 (2009) 29152920.
[160] Y.L. Yu, D.Q. Chen, E. Ma, Y.S. Wang, Z.J. Hu, Spectrochim. Acta, A 67 (2007) 709
713, http://dx.doi.org/10.1016/j.saa.2006.08.028.
[161] S.R. Bae, Y.G. Choi, W. Bin Im, K.S. Lee, Ji W. Chung, Opt. Mater. 35 (2013) 2034
[162] R.E. Youngman, M.J. Dejneka, J. Am. Ceram. Soc. 85 (2002) 10771082.
[163] F. Goutaland, P. Jander, W.S. Brocklesby, G.J. Dai, Opt. Mater. 22 (2003)
383390.
[164] Y.L. Wei, J.J. Li, J.W. Yang, X.N. Chi, H. Guo, J. Lumin. 137 (2013) 7072, http://
dx.doi.org/10.1016/j.jlumin.2012.11.017.
[165] A. Mallik, B. Pal, P. Kundu, A. Basu Majumdar, Ceram. Int. 39 (2013) 61076112,
http://dx.doi.org/10.1016/j.ceramint.2013.01.028.
[166] F. Munoz, A. de Pablos-Martin, N. Hemono, M.J. Pascual, A. Duran, L. Delevoye, L.
Montagne, J. Non-Cryst. Solids 357 (5) (2011) 14631468.
[167] A. de Pablos-Martin, D. Ristic, S. Bhattacharyya, T. Hoeche, G.C. Mather, M.O.
Ramirez, S. Soria, M. Ferrari, G.C. Righini, L.E. Bausa, A. Duran, M.J. Pascual, J. Am.
Ceram. Soc. 96 (2013) 447457, http://dx.doi.org/10.1111/jace.12120.
[168] A. de Pablos-Martn, G.C. Mather, F. Munoz, S. Bhattacharyya, Th. Hoche, J.R.
Jinschek, T. Heil, A. Duran, M.J. Pascual, J. Non-Cryst. Solids 356 (2010) 3071
3079.
[169] A. de Pablos-Martin, M.O. Ramirez, A. Duran, L.E. Bausa, M.J. Pascual, Opt. Mater.
33 (2010) 180185.
[170] Z. Pan, G. Sekar, R. Akrobetu, R. Mu, S.H. Morgan, J. Non-Cryst. Solids 358 (2012)
18141817, http://dx.doi.org/10.1016/j.jnoncrysol.2012.05.028.
[171] G. Domoniak-Dzik, R. Lisiecki, W. Ryba-Romanowski, L. Krajczyk, J. Alloys
Compd. 511 (2012) 189194, http://dx.doi.org/10.1016/j.jallcom.2011.09.026.
[172] A.D. Sontakke, K. Annapurna, J. Appl. Phys. 112 (2012) 013510.
[173] F. Liu, E. Ma, D.Q. Chen, Y.S. Wang, Y.L. Yu, P. Huang, J. Alloys Compd. 467 (2009)
317321, http://dx.doi.org/10.1016/j.jallcom.2007.11.109.
[174] F. Liu, E. Ma, D.Q. Chen, Y.L. Yu, Y.S. Wang, J. Phys. Chem. (B) 110 (2006) 20843
20846, http://dx.doi.org/10.1021/jp063145m.
[175] D.Q. Chen, Y.L. Yu, P. Huang, F.Y. Weng, H. Lin, Y.S. Wang, Appl. Phys. Lett. 94
(2009) 041909, http://dx.doi.org/10.1063/1.3076111.
[176] D.G. Deng, S.Q. Xu, S.L. Zhao, C.X. Li, H.P. Wang, H.D. Ju, J. Lumin. 129 (2009)
[177] T. Suzuki Takenobu, S.I. Masaki, K. Mizuno, Y. Ohishi, Appl. Phys. Express 3
(2010) 072601, http://dx.doi.org/10.1143/APEX.3.072601.
[178] G. Lakshminarayana, J.R. Qiu, J. Alloys Compd. 476 (2009) 720727, http://
[179] C.R. Kesavulu, M-Y. Yoo, J-H. Lee, K.S. Lim, P. Dharmaiah, C.K. Jayasankar, P. Babu,
J. Mater. Res. 28 (2013) 14811489 http://dx.doi.org/10.1557/jmr.2013.128.
[180] S.N. Zhang, J.H. Huang, Y.J. Chen, X.H. Gong, Y.F. Lin, Z.D. Luo, Y.D. Huang, J. NonCryst. Solids 358 (2012) 28352840, http://dx.doi.org/10.1016/j.jnoncrysol.2012.07.005.
[181] J.-H. Zhang, Q. Jiao, R.-F. Wang, D.-C. Zhou, X. YU, J.-B. Qiu, J. Kunming Univ. Sci.
Technol.
37
(2012)
2629,
http://dx.doi.org/10.3969/j.issn.1007855x.2012.01.006.
[182] S.N. Zhang, J.H. Huang, Y.J. Chen, X.H. Gong, Y.F. Lin, Z.D. Luo, Y.D. Huang, Opt.
Mater. Express 3 (2013) 868874, http://dx.doi.org/10.1364/OME.3.000868.
[183] S.N. Zhang, J.H. Huang, Y.J. Chen, X.H. Gong, Y.F. Lin, Z.D. Luo, Y.D. Huang, J. NonCryst. Solids 366 (2013) 3541, http://dx.doi.org/10.1016/j.jnoncrysol.2013.01.048.
[184] L.H. Zhou, D.Q. Chen, W.Q. Luo, Y.S. Wang, Y.L. Yu, F. Liu, Mater. Lett. 61 (2007)
39883990, http://dx.doi.org/10.1016/j.matlet.2007.01.001.
[185] C.E. Secu, D. Predoi, M. Secu, M. Cernea, G. Aldica, Opt. Mater. 31 (2009) 17451748.
[186] S. Georgescu, A.M. Voiculescu, C. Matei, J. Lumin. 143 (2013) 150156.
[187] Y.L. Yu, Y.S. Wang, D.Q. Chen, F. Liu, Ceram. Int. 34 (2008) 21432146, http://
dx.doi.org/10.1016/j.ceramint.2007.08.001.
[188] E.E. Secu, M. Secu, C. Ghica, L. Mihut, Opt. Mater. 33 (2011) 17701774.
[189] S. Fujihara, S. Kitta, T. Kimura, Chem. Lett. 32 (2003) 928929.
[190] A.C. Yanes, A. Santana-Alonso, J. Mendez-Ramos, J. del-Castillo, V.D. Rodrguez,
Adv. Funct. Mater. 21 (2011) 31363142, http://dx.doi.org/10.1002/
adfm.201100146.
[191] G. Kawamura, R. Yoshimura, K. Ota, S.Y. Oh, N. Hakiri, H. Muto, T. Hayakawa, A.
Matsuda, J. Am. Ceram. Soc. 96 (2013) 476480, http://dx.doi.org/10.1111/
jace.12053.
[192] G. Kawamura, R. Yoshimura, K. Ota, S.Y. Oh, H. Muto, T. Hayakawa, A. Matsuda, Opt.
Mater. 35 (2013) 18791881, http://dx.doi.org/10.1016/j.optmat.2013.07.015.
[193] L.A. Bueno, A. da S. Gouveia-Neto, A.F. da Silva, D.S. Moura, E.A. da Silva, E.B.
Costa, Nonlinear frequency generation and conversion: materials, devices, and
applications IX, Proc. SPIE 7582 (2010) 75821H, http://dx.doi.org/10.1117/
12.840406.
[194] A.S. Gouveia-Neto, A.F. da Silva, L.A. Bueno, E.B. da Costa, J. Lumin. 132 (2012)
299304.
[195] M. Reben, M. Sroda, J. Therm. Anal. Calorim. 113 (2013) 7781.
[196] K. Biswas, A.D. Sontakke, K. Annapurna, Int. J. Appl. Glass Sci. 3 (2012) 154162,
http://dx.doi.org/10.1111/j.2041-1294.2012.00087.x.
[197] K. Biswas, A.D. Sontakke, R. Sen, K. Annapurna, J. Fluoresc. 22 (2012) 745752,
http://dx.doi.org/10.1007/s10895-011-1010-4.
[198] M.Y. Ding, C.H. Lu, L.H. Cao, W.J. Huang, Y.R. Ni, Z.Z. Xu, Appl. Surf. Sci. 277 (2013)
176181, http://dx.doi.org/10.1016/j.apsusc.2013.04.019.
[199] S.L. Zhao, S.Q. Xu, D.G. Deng, X.P. Fan, J. Rare Earths 28 (2010) 903906, http://
dx.doi.org/10.1016/S1002-0721(09)60220-9.
[200] F.X. Xin, S.L. Zhao, S.Q. Xu, G.H. Gia, D.G. Deng, H.P. Wang, L.H. Huang, J. Rare
Earths 30 (2012) 69, http://dx.doi.org/10.1016/S1002-0721(10)60628-X.
[201] G.X. Bai, L.L. Tao, K.F. Li, L.L. Hu, Y.H. Tsang, J. Non-Cryst. Solids 361 (2013) 1316,
http://dx.doi.org/10.1016/j.jnoncrysol.2012.10.012.
[202] F.X. Xin, S.L. Zhao, L.H. Huang, D.G. Deng, G.H. Jia, H.P. Wang, S.Q. Xu, Mater. Lett.
78 (2012) 7577, http://dx.doi.org/10.1016/j.matlet.2012.03.037.
[203] F. Zheng, S.Q. Xu, S.L. Zhao, D.G. Deng, Y.J. Hua, H.P. Wang, J. Rare Earths 30
(2012) 137141, http://dx.doi.org/10.1016/S1002-0721(12)60010-6.
[204] S.L. Chen, S.L. Zhao, F. Zheng, C. Zhang, L.H. Huang, S.Q. Xu, Ceram. Int. 39 (2013)
29092913, http://dx.doi.org/10.1016/j.ceramint.2012.09.065.
[205] Y.H. Li, L. Zhao, Y.M. Zhang, J. Ma, J. Rare Earths 30 (2012) 11951198, http://
dx.doi.org/10.1016/S1002-0721(12)60204-X.
[206] S.L. Zhao, X.L. Wang, X. Sun, G.H. Jia, L.H. Huang, D.G. Deng, F.X. Xin, S.Q. Xu,
CrystEngComm 15 (2013) 73467353, http://dx.doi.org/10.1039/c3ce40629f.
[207] S. Haas, A. Hoell, R. Wurth, C. Russel, P. Boesecke, U. Vainio, Phys. Rev. B:
Condens. Matter 81 (2010) 184207, http://dx.doi.org/10.1103/PhysRevB.81.184207.
[208] K. Shinozaki, A. Noji, T. Honma, T. Komatsu, J. Fluor. Chem. 145 (2013) 8187,
http://dx.doi.org/10.1016/j.juchem.2012.10.007.
[209] Y. Dwivedi, S.B. Rai, Opt. Mater. 31 (2008) 8793.
[210] A.V. Egorysheva, A.P. Melekhov, V.D. Volodin, I.A. Gerasimov, T.B. Kuvshinova,
G.S. Bogdanov, I.P. Sipailo, T.D. Dudkina, D.V. Lavrukhin, Inorg. Mater. 49 (2013)
10611065, http://dx.doi.org/10.1134/S0020168513100026.

[211] K. Shinozaki, T. Honma, T. Komatsu, J. Appl. Phys. 112 (2012) 093506.
[212] S. Tanabe, H. Hayashi, T. Hanada, J. Am. Ceram. Soc. 85 (2002) 839843.
[213] C. Liu, J. Heo, Mater. Lett. 61 (2007) 37513754, http://dx.doi.org/10.1016/
j.matlet.2006.12.042.
[214] G. Dantelle, M. Mortier, G. Patriarche, D. Vivien, J. Solid State Chem. 179 (2006)
19952003.
[215] M. Mortier, G. Patriarche, Opt. Mater. 28 (2006) 14011404.
[216] G. Dantelle, M. Mortier, D. Vivien, J. Mater. Res. 20 (2005) 472480.
[217] G. Dantelle, M. Mortier, D. Vivien, G. Patriarche, Opt. Mater. 28 (2006) 638642.
[218] C. Bensalem, M. Mortier, D. Vivien, M. Diaf, Opt. Mater. 33 (2011) 791798.
[219] D. Wu, B. Tang, L. Calvez, X.H. Zhang, L. Zhang, Chin. Phys. Lett. 27 (2010) 067804,
http://dx.doi.org/10.1088/0256-307X/27/6/067804.
[220] W.J. Zhang, Q.J. Chen, J.P. Zhang, Q. Qian, Q.Y. Zhang, L. Wondraczek, J. Alloys
Compd. 541 (2012) 323327, http://dx.doi.org/10.1016/j.jallcom.2012.06.092.
[221] F.C. Guinhos, P.C. Nobrega, P.A. Santa-Cruz, J. Alloys Compd. 323324 (2001)
358361.
[222] G.L. Zhao, H.D. Xi, X.M. Li, J.X. Wang, G.R. Han, J. Noncrystalline Solids 357 (2011)
23322335, http://dx.doi.org/10.1016/j.jnoncrysol.2010.11.087.
[223] S.Q. Zhang, M.X. Xu, X. Chen, Y.L. Zhang, L. Calvez, X.H. Zhang, Y.S. Xu, Y. Huai,
Y.Q. Jin, J. Am. Ceram. Soc. 96 (2013) 24612466, http://dx.doi.org/10.1111/
jace.12477.
[224] Z.X. Hou, Z.L. Xue, S.H. Wang, X.D. Hu, H.R. Lu, C.L. Niu, H. Wang, C. Wang, Y.
Zhou, Key Eng. Mater. 512515 (2012) 10151018, http://dx.doi.org/10.4028/
www.scientic.net/KEM.512-515.1015.
[225] Z.X. Hou, Z.L. Xue, F. Li, M.H. Wang, X.D. Hu, S.H. Wang, J. Alloys Compd. 577
(2013) 523527, http://dx.doi.org/10.1016/j.jallcom.2013.06.178.
[226] Z.X. Hou, Z.L. Xue, S.H. Wang, J. Alloys Compd. 514 (2012) 109112, http://
[227] Y. Ledemi, M. El Amraoui, J.L. Ferrari, P.L. Fortin, S.J.L. Ribeiro, Y. Messaddeq, J.
Am. Ceram. Soc. 96 (2013) 825832, http://dx.doi.org/10.1111/jace.12109.
[228] A. Zohreh, V. Mehdi, P. Aboozar, Chin. J. Phys. 51 (2) (2013) 224229.
[229] Shengchun Xiao, Jingwen Lu, Tao Zheng, Qi Sang, Chin. J. Lasers 39 (2012)
0206002-10206002-7.
[230] I.I. Buchinskaya, P.P. Fedorov, Uspekhi Khimii 73 (2004) 404434 (Russ. Chem.
Rev. 73 (2004) 371400).
[231] P.P. Fedorov, Crystallogr. Rep. 42 (1997) 10641075.
[232] P.P. Fedorov, Inorg. Mater. 33 (1997) 11971205.
[233] P.P. Fedorov, R.M. Zakaliukin, L.N. Ignatieva, V.M. Bouznik, Uspekhi Khimii 69
(2000) 767779 (Russ. Chem. Rev. 69(8) (2000) 705716).
[234] R.M. Zakalyukin, P.P. Fedorov, Inorg. Mater. 39 (2003) 640644.
[235] R.W. Hopper, J. Non-Cryst. Solids 70 (1985) 111142.
[236] Zhuohao Xiao, Shenglong Wang, Mat. Sci. Forum 663665 (2011) 12851288,
http://dx.doi.org/10.4028/www.scientic.net/MSF.663-665.1285.
[237] E.Ia. Mukhin, N.G. Gutkina, Crystallization of glasses and methods of its prevention, Moscow: Izdatelstvo Oboronnoi Promyhlennosti (1960) 128 pp (in Russian) QD548.M8 LANDOVR.
[238] D. Esser, D. Wortmann, J. Gottmann, Advanced fabrication technologies for
micro/nano optics and photonics, Proc. SPIE 7205 (2009) 720510, http://
dx.doi.org/10.1117/12.808736.
[239] C.L. Yu, J.J. Zhang, Z.H. Jiang, J. Non-Cryst. Solids 353 (2007) 26542658, http://
dx.doi.org/10.1016/j.jnoncrysol.2007.05.005.
[240] O. Peron, C. Duverger-Arfuso, Y. Jestin, B. Boulard, M. Ferrari, Opt. Mater. 31
(2009) 12881291.
[241] E.V. Kolobkova, A.A. Lipovskii, V.D. Petrikov, V.G. Melekhin, Glass Phys. Chem. 28
(2002) 251255, http://dx.doi.org/10.1023/A:1019918530283.
[242] K. Zhou, J.Q. Zhu, J. Zeng, J.F. Liu, Rare Metals 30 (2011) 121125, http://
dx.doi.org/10.1007/s12598-011-0252-2.
[243] J. Zeng, J. Zhu, J. Liu, Opt. Mater. 35 (2012) 5055.
[244] M. Volmer, Kinetik der phasenbildung,(Kinetics of the phase formation), T.
Steinkopff, Dresden und Leipzig, 1939, 220 pp.
[245] Ya.B. Zeldovich, J. Techn. Phys. (USSR) 12 (1942) 525 (in Russian); Acta Phys.
(USSR) 18(1943)1.
[246] I. Gutzow, J. Schmelzer, A. Dobreva, J. Non-Crystalline Solids 219 (1997) 116.
[247] G. Tammann, Der Glaszustand,(The Glassy State), L. Voss, Leipzig, 1933p. 123 pp
(in German).
[248] P.D. Sarkisov, Targeted Crystallization of Glass - The Basis For Production Of
Multifunctional GlassCeramics, ;.: RKhTU., 1997p. 218 (in Russian).
[249] R. Wang, J. Zhou, B. Li, L.T. Li, J. Alloys Compd. 490 (2010) 204207, http://
[250] W. Ostwald, Zeitschrift fur Physikalische Chemie 22 (1897) 289330 (in German).
[251] Ch. Bocker, Ch. Russel, I. Avramov, Int. J. Appl. Glass Sci. 4 (2013) 174181.
[252] E. Zschimmer, Chemische technologie des glases, in: ALS Manuskript Gedruckt.,
1913, p. 556 pp.
[253] P.P. Fedorov, Russ. J. Inorg. Chem 45 (Suppl. 3) (2000) S268S291.
[254] P.P. Fedorov, P.A. Popov, Nanosystems: Phys. Chem. Math. 4 (2013) 148159.
[255] M. Tromel, Z. Kristallogr. 183 (1988) 1526.
[256] W. Eitel, Physical Chemistry of the Silicates, The University of Chicago Press,
Chicago, IL, 1954p. 1592 pp.
[257] M. Mortier, A. Monteville, G. Patriarche, G. Maze, F. Auzel, Opt. Mater. 16 (2001)
255267.
[258] M. Mortier, A. Monteville, G. Patriarche, J. Non-Cryst. Solids 284 (2001) 8590.
[259] A.I. Berezhnoi, in: I.V. Tananaev (Ed.), Sitally i fotositally, second ed., Mashinostroenie, Moscow, 1981, , 463 pp.
[260] V.N. Anlogov, I.B. Bobylev, G.I. Anlogova, N.A. Zuzeva, Stroenie i svoistva
silikatno-galogenidnykh rasplavov,(Structure and Properties Of Silicato-Halogenide Melts), Nauka (Science), Moscow, 1990, p. 107 ppISBN 5020027189.
49
[261] J. Mukerji, J. Am. Ceram. Soc. 48 (1965) 210213.

[262] A.K. Chatterjee, G.I. Zhmoidin, J. Mater. Sci. 7 (1972) 9397.
[263] L.V. Delitsyna, L.M. Delitsyn, Doklady Akademii Nauk SSSR 317 (1991) 963
967.
[264] A. de Pablo-Martin, N. Hemono, G.C. Mather, S. Bhattacharyya, T. Hoche, H.
Bornhoft, J. Deubener, F. Munos, A. Duran, M.J. Pascual, J. Am. Ceram. Soc. 94
(2011) 24202428.
[265] S. Bhattacharyya, Th. Hoche, K. Hahn, P.A. van Aken, J. Non-Cryst. Solids 355
(2009) 393396.
[266] K. Shinozaki, T. Honma, K. Oh-ishi, T. Komatsu, J. Phys. Chem. Solids 73 (2012)
683687, http://dx.doi.org/10.1016/j.jpcs.2012.01.010.
[267] P.P. Fedorov, V.V. Osiko, Crystal growth of uorides, in: P. Capper (Ed.), Bulk
Crystal Growth of Electronic, Optical and Optoelectronic Materials., Wiley Series
in Materials for Electronic and Optoelectronic Applications, John Wiley & Son,
Ltd, 2005, pp. 339356, http://dx.doi.org/10.1002/9780470012086, ISBN 978-0470-85142-5.
[268] S.V. Kuznetzov, V.V. Osiko, E.A. Tkatchenko, P.P. Fedorov, Russ. Chem. Rev. 75
(2006) 10651082.
[269] L. Domange, Ann. Chim. 7 (1937) 225297.
[270] J.C. Warf, W.D. Cline, R.D. Tevebaugh, Anal. Chem. 26 (1954) 342346, http://
dx.doi.org/10.1021/ac60086a019.
[271] C.V. Banks, K.E. Burke, J.W. OLaughlin, Anal. Chim. Acta 19 (1958) 239243,
http://dx.doi.org/10.1016/S0003-2670(00)88149-0.
[272] T. Komatsu, T. Honma, Int. J. Appl. Glass Sci. 4 (2013) 125135, http://dx.doi.org/
10.1111/ijag.12023.
[273] K.H. Kim 327a., Y.G. Choi, W.B. Im, W.J. Chung, Met. Mater. Int. 19 (2013) 347352.
[274] S. Fischer, J.C. Goldschmidt, P. Loper, G.H. Bauer, R. Bruggemann, K. Kramer, D.
Biner, M. Hermie, S.W. Glunz, J. Appl. Phys. 108 (2010) 044912.
[275] O.V. Mazurin, Glass Phys. Chem. 33 (2007) 2236, http://dx.doi.org/10.1134/
S108765960701004X.
[276] P. Scherrer, Gotting. Nachrichten Gesell 2 (1918) 98.
[277] V.K. Pecharsky, P.Y. Zavalij, Fundamentals of Powder Diffraction and Structural
Characterization of Materials, second ed., Springer Science + Business Media
LLC, New York, NY, 2009,
p. 744 ppISBN 10: 0387095780 ISBN-13: 9780387095783.
[278] B.P. Sobolev, The Rare Earth Triuorides. Part 1. The High-temperature Chemistry of the Rare Earth Triuorides, Institut dEstudis Catalans, Barcelona, 2000p.
520pp (pt. 1).ISBN 8472835189.
[279] A. Herrmann, M. Tylkowski, C. Bocker, C. Ruessel, J. Mater. Sci. 48 (2013) 6262
6268, http://dx.doi.org/10.1007/s10853-013-7423-5.
[280] P.P. Fedorov, V.V. Osiko, S.V. Kuznetsov, O.V. Uvarov, M.N. Mayakova, D.S.
Yasirkina, A.A. Ovsyannikova, V.V. Voronov, V.K. Ivanov, J. Cryst. Growth 401
(2014) 6366.
[281] V.K. Ivanov, P.P. Fedorov, A.E. Baranchikov, V.V. Osiko, Russian Chem. Rev. 83
(12) (2014) 12041222.
[282] R.L. Penn, J.F. Baneld, Science 281 (1998) 969971.
[283] G.I. Distler, V.P. Vlasov, Thin Solid Films 3 (1969) 333339.
[284] B.P. Sobolev, L.S. Garashina, P.P. Fedorov, N.L. Tkachenko, K.B. Seiranyan, Kristallograya 18 (1973) 751758.
[285] P.P. Fedorov, B.P. Sobolev, Kristallograya 40 (1995) 315321.
[286] B.P. Sobolev, V.B. Aleksandrov, P.P. Fedorov, K.B. Seiranyan, N.L. Tkachenko,
Kristallograya 21 (1976) 96105.
[287] B.P. Sobolev, P.P. Fedorov, D.B. Steynberg, B.V. Sinitsyn, G.S. Shakhkalanian, J.
Solid State Chem. 17 (1976) 191199, http://dx.doi.org/10.1016/00224596(76)90220-6.
[288] B.P. Sobolev, P.P. Fedorov, J. Less-Common Metals 60 (1978) 3346, http://
dx.doi.org/10.1016/0022-5088(78)90087-5.
[289] B.P. Sobolev, K.B. Seiranian, L.S. Garashina, P.P. Fedorov, J. Solid State Chem. 28
(1979) 5158, http://dx.doi.org/10.1016/0022-4596(79)90057-4.
[290] O. Greis, J.M. Haschke, Rare earth uorides, Handbook on the Physics and
Chemistry of Rare Earths, 5, North-Holland Publ. Co., Amsterdam et ?al.,
1982, , pp. 387460ISBN 0-444-86375-3.
[291] P.J. Bendall, C.R.A. Catlow, J. Corish, P.W.M. Jacobs, J. Solis State Chem. 51 (1984)
159168.
[292] L.A. Muradyan, B.A. Maksimov, V.I. Simonov, Koordinatsionnaya Khimiya 12
(1986) 13981403.
[293] A.M. Golubev, V.I. Simonov, Kristallograya 31 (1986) 478487.
[294] S.A. Kazanskii, A.I. Ryskin, A.E. Nikiforov, A.Yu. Zaharov, M.Yu. Ougrumov, G.S.
Shakurov, Phys. Rev. B: Condens. Matter 72 (2005) 014127.
[295] E.A. Sulyanova, V.N. Molchanov, I.A. Verin, S.N. Sulyanov, B.P. Sobolev, Crystallogr. Rep. 54 (2009) 516525, http://dx.doi.org/10.1134/S1063774509030249.
[296] E.A. Sulyanova, I.A. Verin, B.P. Sobolev, Crystallogr. Rep. 57 (2012) 7384, http://
dx.doi.org/10.1134/S1063774512010130.
[297] P.P. Fedorov, B.P. Sobolev, Kristallograya 37 (1992) 12101219.
[298] P.P. Fedorov, The Ninth All-Russian Meeting on Fluorine Chemistry, October 22
26, 2012, Moscow, 2012, hwww.pavel-fedorov.sitecity.rui Abstract P-57.
[299] J.M. Reau, P.P. Fedorov, L. Rabardel, S.F. Matar, P. Hagenmuller, Mat. Res. Bull. 18
(1983) 12351246, http://dx.doi.org/10.1016/0025-5408(83)90027-2.
[300] A. Dib, S. Aleonard, M.Th. Roux, J. Solid State Chem. 52 (1984) 292301.
[301] A.K. Tyagi, S.J. Patwe, S.N. Achary, M.B. Mallia, J. Solid State Chem. 177 (2004)
17461757.
[302] C.P. Fedorov, M.N. Mayakova, S.V. Kuznetsov, V.V. Voronov, R.P. Ermakov, K.S.
Samarina, A.I. Popov, V.V. Osiko, Mater. Res. Bull. 47 (2012) 17941799, http://
dx.doi.org/10.1016/j.materresbull.2012.03.027.
[303] U.R.K. Rao, A.K. Tyagi, K.V. Muralidharan, R.M. Iyer, J. Mat. Sci. Lett. 11 (1992)
435436.
50
[304] M.N. Mayakova, A.A. Luginina, S.V. Kuznetsov, V. Voronov, R.P. Ermakov, A.E.
Baranchikov, V.K. Ivanov, O.V. Karban, P.P. Fedorov, Mendeleev Commun. 24 (6)
(2014) 360362.
[305] J. Ge, L.J. Zhao, H. Guo, Z.J. Lan, L.F. Chang, Y.M. Li, H. Yu, Phys. Chem. Chem. Phys.
15 (2013) 1728117286, http://dx.doi.org/10.1039/c3cp53073f.
[306] V.K. Tikhomirov, G. Adamo, A.E. Nikolaenko, V.D. Rodriguez, P. Gredin, M.
Mortier, N.I. Zheludev, V.V. Moshchalkov, Opt. Express 18 (2010) 88368846.
[307] S.A. Polyshchuk, L.N. Ignateva, S.L. Sinebryukhov, S.V. Gnedenkov, A.B. Podgorbunsky, N.N. Savchenko, A.B. Slobodyuk, V.M. Bouznik, Russ. J. Inorg. Chem. 58
(2013) 387391, http://dx.doi.org/10.1134/S003602361304013X.
[308] V.A. Gorbulev, P.P. Fedorov, B.P. Sobolev, J. Less-Common Metals 76 (1980) 55
62, http://dx.doi.org/10.1016/0022-5088(80)90009-0.
[309] P.P. Fedorov, V.A. Gorbulev, E. Mariani, M. Svantner, A.M. Aronova, B.P. Sobolev,
Cryst. Res. Technol. 16 (1981) k75k78.
[310] J.-H. Muller, T. Petzel, B. Hormann, O. Andersen, J. Alloys Compd. 259 (1997)
208211.
[311] P.P. Fedorov, B.P. Sobolev, S.F. Belov, Inorg. Mater. 15 (1979) 640643.
[312] P.P. Fedorov, I.I. Buczinskaya, V.A. Stasyuk, O.S. Bondareva, Zhurnal Neorganicheskoi Khimii 41 (1996) 464468 (Russ. J. Inorg. Chem. 41 (1996) 445449).
[313] I.I. Buchinskaya, P.P. Fedorov, O.L. Evdokimova, B.P. Sobolev, Kristallograya 39
(1994) 539543 (Crystallogr. Rep. 39(3) (1994) 480484).
[314] B.P. Sobolev, P.P. Fedorov, K.B. Seiranyan, N.L. Tkachenko, J. Solid State Chem. 17
(1976) 201212, http://dx.doi.org/10.1016/0022-4596(76)90221-8.
[315] P.P. Fedorov, Russ. J. Inorg. Chem. 44 (1999) 17031727.
[316] P.P. Fedorov, S.V. Kuznetsov, M.N. Mayakova, V.V. Voronov, R.P. Ermakov, A.E.
Baranchikov, V.V. Osiko, Russ. J. Inorg. Chem. 56 (2011) 15251531, http://
dx.doi.org/10.1134/S003602361110007X.
[317] B.P. Sobolev, P.P. Fedorov, Kristallograya 18 (1973) 624625.
[318] P.P. Fedorov, Russ. J. Inorg. Chem. 59 (2014) 595599, http://dx.doi.org/10.1134/
S0036023614060072.
[319] P.P. Fedorov, V.B. Aleksandrov, O.S. Bondareva, I.I. Buchinskaya, M.D. Valkovskii,
B.P. Sobolev, Crystallogr. Rep. 46 (2001) 239245, http://dx.doi.org/10.1134/
1.1358401.
[320] A.V. Goryunov, A.I. Popov, N.M. Khajdukov, P.P. Fedorov, Mater. Res. Bull. 27
(1992) 213220, http://dx.doi.org/10.1016/0025-5408(92)90215-L.
[321] A.V. Goryunov, A.I. Popov, Zhurnal Neorganicheskoi Khimii 37 (1992) 276279
(Russ. J. Inorg. Chem. 37 (1992) 126128).
[322] P.P. Fedorov, L.V. Medvedeva, B.P. Sobolev, Russ. J. Phys. Chem. 76 (2002) 337
342.
[323] M.V. Zamoryanskaya, M.A. Petrova, V.Y. Egorov, Russ. J. Inorg. Chem. 48 (2003)
12441251.
[324] G. Nemova, R. Kashyap, J. Opt. Soc. Am. (B) 29 (2012) 30343038.
[325] S.N. Zhang, J.H. Huang, Y.J. Chen, X.H. Gong, Y.F. Lin, Z.D. Luo, Y.D. Huang, Opt.
Mater. Express 3 (2013) 868874.
[326] X.F. Wang, X.H. Yan, Y. Xuan, J. Zheng, W.Y. He, Appl. Phys. A 113 (2013) 4146.
[327] T. Trupke, M.A. Green, P. Wurfel, J. Appl. Phys. 92 (2002) 16681674, http://
dx.doi.org/10.1063/1.1492021.
[328] X. Chen, G. Yang, S. Li, M. Ohtsuka, S. Naruhito, J.Y. Liu, L. Chen, G.J. Salamo, Opt.
Commun. 285 (2012) 52475253, http://dx.doi.org/10.1016/j.optcom.2012.08.035.
[329] Y. Kishi, S. Tanabe, J. Alloys Compd. 408412 (2006) 842844, http://dx.doi.org/
10.1016/j.jallcom.2005.01.096.
View publication stats
[330] X.B. Chen, G.J. Yang, S. Li Song, N. Sawanobori, Y.Z. Xu, X.D. Chen, G. Zhou, Acta
Phys. Sin. 61 (2012) 227803, http://dx.doi.org/10.7498/aps.61.227803.
[331] Jie Xu, Yi-chen Hu, Zhong-jian Wang, Miao-hong Ye, Fei Xiang, J. East China Univ.
Sci. Technol. 37 (2011) 6570.
[332] Yu.A. Rozhnova, A.A. Luginina, V.V. Voronov, R.P. Ermakov, S.V. Kuznetsov, A.V.
Ryabova, D.V. Pominova, V.V. Arbenina, V.V. Osiko, P.P. Fedorov, Mat. Chem. Phys.
148 (2014) 201207, http://dx.doi.org/10.1016/j.matchemphys.2014.07.032.
[333] Wanlei Han, Yutao Jia, Yinglin Song, Acta Opt. Sin. 31 (2011) 161165, Article
Number:0253-2239(2011)31:2<161:TEYGCD>2.0.TX;2-E.
[334] D.Q. Chen, Y.S. Wang, Y.L. Yu, H. Lin, China Patent CN102,491,642 (2011).
[335] X.-Y Mi, H. Shi, N. Wang, X. Zhang, Chinese Patent CN201210296877A (2012).
[336] D. Chen, Y. Wang, Z. Hu, Chinese Patent CN1, 955,129 (2007).
[337] M. Koch, German Patent GE102007046925 (2009).
[338] Y.H. Wang, J.C. Ohwaki, European Patent EP0640571 (1995).
[339] N.F. Borrelli, M.A. Newhouse, L.K. Cornelius, P.A. Tick, European Patent
EP0716050 (1996).
[340] N.F. Borrelli, L.K. Cornelius, M.A. Newhouse, P.A. Tick, European Patent EP0739863
(1996).
[341] N.F. Borrelli, L.K. Cornelius, M.A. Newhouse, P.A. Tick, US Patent 5,483628
(1996).
[342] G.W. Billings, US Patent US2007007897 (2007).
[343] P. Egger, E. Muller, PCT Patent WO0151571 (2001).
[344] M.J. Dejneka, PCT Patent WO9829351 (1998).
[345] M. Koch, G. Wubbeling, PCT Patent WO2007121898 (2007).
[346] N.I. Sorokin, Uspekhi Khimii 70 (2001) 901908.
[347] L. Ignatieva, N. Savchenko, S. Polyshchuk, Yu. Marchenko, V. Kuriaviy, T. Antokhina, V. Bouznik, J. Non-Crystalline Solids 356 (2010) 26452650.
[348] S.A. Polishchuk, L.N. Ignateva, Y.V. Marchenko, V.M. Bouznik, Glass Phys. Chem.
37 (2011) 120, http://dx.doi.org/10.1134/S108765961101010X.
[349] N.M. Laptash, I.G. Maslennikova, A.B. Slobodyuk, V.Ya. Kavun, V.K. Goncharuk,
Inorg. Chem. 52 (2013) 57225728.
[350] Chuangtian Chen, Takatomo Sasaki, Rukang Li, et al., Nonlinear Optical Borate
Crystals, Viley-VCH, Weinheim, 2012p. 387 pp.
[351] A.A. Luginina, A.E. Baranchikov, A.I. Popov, P.P. Fedorov, Mater. Res. Bull. 49 (1)
[352] Q.Y. Zhang, X.Y. Huang, Prog. Mater Sci. 55 (2010) 353427.
[353] X. Huang, S. San, W. Huang, X. Liu, Chem. Soc. Rev. 42 (1) (2013) 173201.
[354] J.P. Zhang, D.C. Yu, F.F. Zhang, M.Y. Peng, Q.Y. Zhang, Opt. Mater. Express 4 (2014)
111120, http://dx.doi.org/10.1364/OME.4.0111.
[355] W.A. Pisarski, T. Goryczka, J. Pisarska, W. Ryba-Romanowski, J. Phys. Chem. B 111
(2007) 24272430.
[356] R. Bagga, V.G. Achanta, A. Goel, J.M.F. Ferreira, N.P. Singh, D.P. Singh, M.
Falconieri, G. Sharma, Mater. Sci. Eng. B 178 (2013) 218224.
[357] V.K. Tikhomirov, A.B. Seddon, M. Ferrari, M. Montagna, L.F. Santos, R.M. Almeida,
J. Non-Cryst. Solids 337 (2004) 191195.
[358] M. Mattarelli, V.K. Tikhomirov, A.B. Seddon, M. Montagna, E. Moser, A. Chiasera,
S. Chaussedent, G. Nunzi Conti, S. Pelli, G.C. Righini, L. Zamperdi, M. Ferrari, J.
Non-Cryst. Solids 345346 (2004) 354358.
[359] M. Sroda, C. Paluszkiewicz, M. Reben, B. Handke, J. Mol. Structure 744747
(2005) 647651.

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Transparent Oxyfluoride Glass Ceramics

Russian Academy of Sciences

Russian Academy of Sciences

379 PUBLICATIONS 3,028 CITATIONS

19 PUBLICATIONS 158 CITATIONS

Journal of Fluorine Chemistry 172 (2015) 2250

Contents lists available at ScienceDirect

Journal of Fluorine Chemistry

Review, Review Article

Transparent oxyuoride glass ceramics

General Physics Institute RAS, 38 Vavilov Street, Moscow 119991, Russia

Natural and man-made glass ceramic materials, i.e., materials

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

1.2. History of oxyuoride glass ceramics

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

unusual and unexpected effects of stabilizing otherwise unstable

Fig. 1. Annual numbers of publications on oxyuoride* + transparent +

nanocrystals responsible for control of the spectral properties of

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

CaF2 (2027 nm)

CaF2:R3+ (R = Tb/Gd) 24 nm

CaF2:Er3+/Yb3+ (1719 nm)

50SiO220Al2O320SrF2(10 x)NaFxEuF3 (x = 05)

SrF2:Eu2+ (2037 nm)

BaYF5:Yb3+/Ho3+ (1525 nm)

Pb5Al3F19:Er; Er3Si3O10F; Er4Si3O11F2

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

CaF2, SrF2, BaF2; ZnF2

50SiO215Al2O3(35 x)LaF3xCeF3 (x = 017.5): Sb2O3

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

(SiO2BaF2):R3+ (R = Eu, Sm, Dy, Ho, Pr)

90SiO2(10 x)LaF3xEuF3 and SiO2LaOF

(90SiO210YF3): xYb3+/0.1Tm3+ (x = 0.5; 1; 1.5)

90SiO210PbF2:RF3 (R = 0.3Yb and 0.1Er)

PbF2:R3+ R= Er,Yb,Ce, Eu3+

CaF2: Er3+, <20 nm

45GeO230BaF25B2O315Al2O35R2OxSm2O3 (R = Li,Na,K, x = 1.52.5)

CaF2: Nd3+/Ho3+, 10100 nm

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

The simplest way to prepare glass ceramics (method 1)

difference between the properties of the formed nanophases and

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

Oxyuoride glass matrices may not only contain uoride

Fig. 3. Rates of homogeneous formation of crystallization centers (Kv) and crystal

system matrix/nucleus. Since this time, his theory has been

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

Fig. 4. Scheme of the nanocrystallization mechanism in homogeneous glasses with

correspond to the multiplicity of the phases formed under

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

Fig. 5. Scheme of the nanocrystallization mechanism in phase-separated systems.

68.6ZrF4:18.4LaF3:5AlF3:5GaF3:3ErF3 [257,258]) proceeded via

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

electric furnace above the glass transition temperature (500

RF3 H2 O ! ROF 2HF " :

Perhaps, the presence of lead oxyuoride in glass matrix in [61]

Sm Nd; Y Eu Pr La the most stable for RF3

3MF2 B2 O3 ! 3MO 2BF3 "

precursors in aqueous solution. SiOSi bonds were formed during

P.P. Fedorov et al. / Journal of Fluorine Chemistry 172 (2015) 2250

the starting batches. In addition, solgel techniques allow the

(glass formation) temperature, whereas the rst exo-effect at Tc1

For instance, some researchers [36,37,65,74] as well as many