ISSN 10637834, Physics of the Solid State, 2012, Vol. 54, No. 8, pp. 1635–1642. © Pleiades Publishing, Ltd.

, 2012.
Original Russian Text © Yu.K. Voron’ko, A.A. Sobol’, V.E. Shukshin, A.I. Zagumennyi, Yu.D. Zavartsev, S.A. Kutovoi, 2012, published in Fizika Tverdogo Tela, 2012, Vol. 54,
No. 8, pp. 1533–1539.

LATTICE
DYNAMICS

Structural Transformations in LiGd9(SiO4)6O2

and Ca2Gd8(SiO4)6O2 Crystals Containing Isolated [SiO4]
Complexes: Raman Spectroscopic Study
Yu. K. Voron’ko, A. A. Sobol’*, V. E. Shukshin**, A. I. Zagumennyi,
Yu. D. Zavartsev, and S. A. Kutovoi
Prokhorov General Physics Institute, Russian Academy of Sciences, ul. Vavilova 38, Moscow, 119991 Russia
* email: [email protected]
** email: [email protected]
Received January 17, 2012

Abstract—The vibrational spectra of single crystals of the LiGd9(SiO4)6O2 and Ca2Gd8(SiO4)6O2 oxyapatites
have been studied using Raman spectroscopy at room and high temperatures. The spectra of internal and
external vibrations in these structures have been resolved. The structural transformation of the
LiGd9(SiO4)6O2 and Ca2Gd8(SiO4)6O2 oxyapatites in the processes of melting and crystallization, as well as
during rapid quenching of the melt, has been investigated. It has been found that the melting of the
LiGd9(SiO4)6O2 compound has an incongruent character and that new metastable disordered phases are
formed during rapid quenching of the Ca2Gd8(SiO4)6O2 melt.
DOI: 10.1134/S106378341208032X

1. INTRODUCTION and Ca2Gd8(SiO4)6O2 [11]. These materials are also

potential objects for the use in ionizing radiation
Single crystals of silicates in which structural units detectors and laser engineering. Furthermore, from
are isolated [SiO4] groups have attracted the particular the scientific point of view, Raman spectra have
attention of researchers as materials for the use in allowed one to reveal specific features in vibrational
quantum electronics, ionizing radiation detectors, spectra of this class of island silicates. Until presently,
and elements of medical engineering [1–4]. Rare these investigations have been hampered because of
earth silicates and alkalineearth metals are of the the lack of LiGd9(SiO4)6O2 and Ca2Gd8(SiO4)6O2 sin
great interest, because it is these compounds that can gle crystals with sizes that would make it possible to
be synthesized in the form of perfect single crystals examined the polarized Raman spectra. The purpose
suitable for technical applications [5–8]. Since the of this work was to investigate the Raman spectra of
synthesis of these crystals has been carried out at high LiGd9(SiO4)6O2 and Ca2Gd8(SiO4)6O2 single crystals
temperatures from the melt (2300 K), it is of interest to with the subsequent identification of the internal
investigate the behavior of their structure in the pro vibrations of the [SiO4] complexes in these structures
cesses of melting and crystallization. The information at room temperature. In addition, the objective of this
obtained from these investigations is useful not only work was to examine the behavior of the spectrum of
for practical application but also for scientific internal vibrations of the [SiO4] complexes during
research. Raman spectroscopy has made it possible to heating of the studied silicates to the melting temper
obtain such information because vibrational spectra of atures, as well as during cooling of their melts.
[SiO4] groups with strong covalent bonds are indica
tors of changes in the structure of the silicates. Owing
to the development of hightemperature Raman spec 2. SAMPLE PREPARATION
troscopy, changes in the structure of refractory sili AND EXPERIMENTAL TECHNIQUE
cates with variations in temperature can be observed
almost up to their melting point [9]. Previously, similar Single crystals of the LiGd9(SiO4)6O2 and
investigations were carried out with Gd2SiO5, Ca2Gd8(SiO4)6O2 oxyapatites were grown by the Czo
Lu2SiO5, and Mg2SiO4 single crystals [8, 10]. Apart chralski method from iridium crucibles 40 mm in
from the aforementioned silicates with a high concen diameter at a pulling rate of 3 mm/h. Attempts to grow
tration of the basic oxide, there is a poorly studied class the single crystals from the stoichiometric melt were
of silicates with the apatite–bertholite structure, not successful. All the crystals were grown from the
which are described by the formulas LiGd9(SiO4)6O2 melts enriched in gadolinium oxide.

1635
1636 VORON’KO et al.

ν1 + ν3 tra. For the investigation of the melt, the Raman spec

ν3
ν2 ν4 tra were excited and recorded through its upper
boundary. This design made it possible to perform a
νext + ν2 ν1 + ν3 5 rapid quenching of the melt (at a rate of higher than
Intensity, arb. units

400 K/s in the temperature range 2270–900 K) by

ν4 ν3 turning off the heating source of the iridium strip.
4

3. EXPERIMENTAL RESULTS
3 AND DISCUSSION
ν2 ν4 ν1 ν3
2
The main representatives of the apatite–bertholite
structure in the class of island silicates are the com
1 pounds Re9.33䊐0.67(SiO4)6O2, where Re is an element of
the beginning of the lanthanide series and 䊐 is a cation
0 400 800 1200 vacancy [11]. The composition corresponds to the
Δν, cm−1 concentration ratio of the oxides Re2O3/SiO2, which is
equal to 7/9. The unit cell of the hexagonal symmetry
Fig. 1. Raman spectra of the (1) LiGd9(SiO4)6O2 poly 2
crystals, (2) Ca2Gd8(SiO4)6O2 polycrystals, (3) P63/m ( C 6h ) contains one formula unit. Cations and
Lu2(SiO4)O oxyorthosilicate, (4) Gd2(SiO4)O oxyortho cation vacancies are located in two nonequivalent
silicate, and (5) Mg2SiO4 orthosilicate with the structure positions with symmetries Cs(h) and C3( f ). The ratio
containing the isolated [SiO4] complexes. Notation: νext of the number of positions h to the number of positions
stands for “external vibrations” of these complexes. The f is equal to 3/2. The specific feature of the oxyapatite
spectra were recorded at the temperature T = 300 K.
structures is the presence of additional oxygen atoms
that are not included in the composition of the isolated
The oriented samples of good optical quality had tetrahedra [SiO4]. These oxygen atoms O(4) form
dimensions of 8 × 8 × 3 mm. The Raman spectra at chains parallel to the hexagonal axis of the crystal [11].
room temperature were recorded on a Spex–Ramalog The structures of the double oxyapatites
1403 spectrometer with a resolution of 2 cm–1 under LiGd9(SiO4)6O2 and Ca2Gd8(SiO4)6O2 are distin
excitation with radiation from an argon laser operating guished by the absence of cation vacancies; moreover,
at wavelengths of 488.0 and 514.5 nm. The hightem the systems of lattice sites h and f in these structures
perature investigations of the Raman spectra up to can be statistically occupied by two types of cations.
2270 K were performed with the use of specially Therefore, the aforementioned double oxyapatites
designed equipment [9]. The Raman spectra were have disordered structures.
recorded with a resolution of 3 cm–1. In this case, the According to the grouptheoretical analysis, the
spectra were excited with radiation from a copper vibrations in the apatite structure with space group
vapor laser operating at a wavelength of 510.6 nm in 2
C 6h , taking into account the positional symmetry of
the pulsedperiodic mode at a pulserepetition rate of
15 kHz and an average power of 3 W. In the tempera the structural elements, can be represented as [12]
ture range from 300 to 1900 K, the heating of the sam R IR
ples was carried out in a vertical tubular resistance fur Γ = ( 12A g + 8E 1g + 13E 2g ) + ( 8A u + 12E 1u )
nace with a Pt–30%Rh resistance wire used as a heat + ( A u + E 1u )
AC S
+ ( 9B g + 8E 2u + 12B u ) .
ing element. The temperature was measured using a
Pt–6%Rh–Pt–30%Rh thermocouple with an accu The vibrations of the symmetries Ag, E1g, and E2g are
racy of 5 K. At temperatures in the range from 1500 to active in the Raman spectra (superscript R). Among
2180 K, the heating of the sample up to the melting them, 6Ag + 3E1g + 6E2g are internal vibrations of the
was performed in an inert gas atmosphere. The heating tetrahedral anion [SiO4]4–. Twenty antisymmetric
element was prepared from iridium in the form of a vibrations are active in the IR spectra (superscript IR).
strip with a thickness of 0.1 mm and dimensions of In addition, we should note two (Au + E1u) modes of
8 × 35 mm, through which the electric current was
acoustic vibrations (superscript AC) and 29 vibrations
passed. The temperature in this case was measured that are inactive in both the Raman and IR spectra
using an optical pyrometer with an accuracy of 50 K. (S modes).
A sample weighing from 5 to 7 mg was placed directly
on the iridium strip whose ends were fixed on water Table 1 shows the correlation of vibrations of the
cooled contacts. The screening of radiation from the free [SiO4]4– anion, the cation positions f and h, and
heating element was achieved using a cylinder fabri the O2–(4) oxygen ion with due regard for the posi
cated from a tungsten foil with a hole 5 mm in diame tional symmetry of the oxyapatite lattice and the influ
ter for the excitation and detection of the Raman spec ence of the correlation field.

PHYSICS OF THE SOLID STATE Vol. 54 No. 8 2012

 STRUCTURAL TRANSFORMATIONS 1637

Table 1. Correlation of the vibrational representations of the structural units in Gd31/3䊐2/3Gd6[SiO4]6O2

Vibrational representation for the factor group of the
Structural unit Free state symmetry Positional symmetry C6h structure

[SiO4]4– Td Cs
A1(ν1) A' Ag + E2g + Bu + E1u
E(ν2) A' + A'' (Ag + E2g + Bu + E1u) + (Bg + E1g + Au + E2u)
F2(ν3) 2A' + A'' 2(Ag + E2g + Bu + E1u) + (Bg + E1g + Au + E2u)
F2(ν4) 2A' + A'' 2(Ag + E2g + Bu + E1u) + (Bg + E1g + Au + E2u)
F1(νrot) A' + 2A'' (Ag + E2g + Bu + E1u) + 2(Bg + E1g + Au + E2u)
F2(νtr) 2A' + A'' 2(Ag + E2g + Bu + E1u) + (Bg + E1g + Au + E2u)
Gd3+(h) – 2A' + A'' 2(Ag + E2g + Bu + E1u) + (Bg + E1g + Au + E2u)
Gd 3+(f) – C3
A+E (Ag + Bg + Au + Bu) + (E2g + E1g + E1u + E2u)
O2–(4) – C3h
A'' + E' (Bg + Au) + (E2g + E1u)
Note: νrot and νtr are the rotational and translational modes of the external vibrations of the [SiO4]4– complex.

Figure 1 illustrates the Raman spectra measured at vibration ν4, only one line of the two presumed lines
300 K for the LiGd9(SiO4)6O2 and Ca2Gd8(SiO4)6O2 with the symmetry E2g was not identified. The differ
polycrystals in comparison with the spectra of the ence revealed in the frequencies of identical vibrations
Lu2(SiO4)O and Gd2(SiO4)O oxyorthosilicates and from the comparison of the Raman spectra of the
the Mg2SiO4 orthosilicate, whose structures also con Ca2Gd8(SiO4)6O2 and LiGd9(SiO4)6O2 compounds
tain the isolated [SiO4] complexes. varied in the range from 0 to 19 cm–1. The same corre
spondence was observed in the Raman spectrum of
The Raman spectra of the LiGd9(SiO4)6O2 and lowfrequency external vibrations. In this case, among
Ca2Gd8(SiO4)6O2 polycrystals are similar to each the lines of the six modes Ag predicted by the theory,
other not only in frequency of the recorded lines but five lines were identified, and, among the seven lines of
also in the distribution of their intensities. The vibrations with the symmetry E2g, two lines were not
observed difference in the Raman spectra of these observed. In the spectrum of each of the two com
compounds is associated with some broadening of the pounds, among the expected five lines with the sym
Raman lines in the spectrum of the LiGd9(SiO4)6O2 metry E1g, five lines were observed. Therefore, the
oxyapatite as compared to the Ca2Gd8(SiO4)6O2 oxya identification of lines in the polarized Raman spectra
patite. This fact indicates a higher degree of disorder of the Ca2Gd8(SiO4)6O2 and LiGd9(SiO4)6O2 single
ing of the structure of the lithium gadolinium oxyapa crystals is in satisfactory agreement with the symmetry
tite as compared to the calcium gadolinium oxyapa of the unit cell of the oxyapatite.
tite. It should be noted that previous Xray diffraction
investigations of these compounds, on the contrary, The analysis of the Raman spectra of the com
suggested a more disordered structure for pounds considered in our work with the oxyapatite
Ca2Gd8(SiO4)6O2 as compared to LiGd9(SiO4)6O2 structure in the highfrequency region, which corre
[11]. The polarized Raman spectra measured in the sponds to the internal vibrations of the anion [SiO4]4–
scattering geometries x(zz) x , x(zy) x , and z(xy) z , revealed that these spectra differ from the previously
allowed us to resolve the lines corresponding to vibra studied spectra of other silicates containing the island
tions of the symmetries Ag, E1g, and E2g in [SiO4] fragments, such as lutetium and gadolinium
Ca2Gd8(SiO4)6O2 and LiGd9(SiO4)6O2 (Fig. 2). The oxyorthosilicates and Mg2SiO4 [8, 13, 14].
z axis corresponded to the hexagonal axis of the apatite It can be seen from Fig. 2 that, in the Raman spec
structure. The frequencies of the identified lines are tra of the silicates with the oxyapatite structure, the
presented in Table 2. Based on the analysis of the frequency ranges, in which there are groups of lines
polarized Raman spectra, we identified all the compo whose origin is associated with the vibrations ν1, ν2, ν3,
nents presented in Table 2, whose origin is associated and ν4 of the free [SiO4]4– anion, are well separated.
with the internal vibrations ν1, ν2, and ν3 of the free By contrast, in the Raman spectra of the Gd2SiO5,
[SiO4]4– anion. Among the five components of the Lu2SiO5, and Mg2SiO4 crystals, there are overlapping

PHYSICS OF THE SOLID STATE Vol. 54 No. 8 2012

1638 VORON’KO et al.

(a) toward the lowenergy range and a broadening of the

highest frequency line E2g (321 and 323 cm–1 at 300 K)
ν2 ν4 ν1 ν3 in the family of external vibrations. Other lines also
demonstrated a frequency shift and a broadening
Intensity, arb. units

within considerably narrower ranges, and the frequen

cies of some lines remained unchanged with an
increase in the temperature up to the melting point.
The specific behavior of the E2g line can be supposedly
x(zz)x explained by the activation of the reorientational
*
* * motion of the [SiO4]4– anions with an increase in the
x(zy)x
temperature due to a decrease in the force constant of
the E2g component of the F1 libration vibration of the
* * z(xy)z free silicon–oxygen complex.
0 400 800 1200 After the melting temperature was reached, the
intensity of the Raman spectrum of the
ν2 ν4 ν1 ν3 (b) Ca2Gd8(SiO4)6O2 oxyapatite was significantly
decreased and the spectrum itself became almost
Intensity, arb. units

structureless in shape, which made it impossible to

obtain a reliable information about the structure of the
silicon–oxygen anions in the molten state (Fig. 3a).
The observed change in the Raman spectrum of the
Ca2Gd8(SiO4)6O2 melt with a decrease in the temper
x(zz)x ature demonstrated that the melt underwent crystalli
*
x(zy)x zation; moreover, at a temperature of 300 K, the spec
trum contained only the lines that were observed in the
spectrum of this oxyapatite before the melting
* z(xy)z
(Fig. 3b). Since, before the melting, we dealt with the
transparent single crystal of the Ca2Gd8(SiO4)6O2
0 400 800 1200
Δν, cm−1 oxyapatite and, after the crystallization of the melt, we
dealt with the polycrystalline sample of this com
Fig. 2. Polarized Raman spectra of (a) Ca2Gd8(SiO4)6O2 pound, the Raman spectra of these objects measured
and (b) LiGd9(SiO4)6O2 singlecrystal samples at a tem at 300 K before and after the melting exhibited a redis
perature of 300 K in the scattering geometries x(zz) x (Ag),
tribution of the intensities of the lines (Figs. 3a, 3b). In
the process of melting and crystallization, we did not
x(zy) x (E1g), and z(xy) z (E2g). Asterisks indicate vibra
reveal additional lines in the Raman spectra of the
tions that are forbidden in the given scattering geometry.
Ca2Gd8(SiO4)6O2 oxyapatite which would belong to
other crystal structures. Therefore, we can conclude
frequency ranges of groups of the lines corresponding that, during our investigation, the composition of the
to the vibrations ν1 and ν3, as well as the group of the material changed only slightly.
lines attributed to the ν2 vibrations and the lines of The variation in the character of the Raman spectra
external vibrations [8, 14]. This indicated a strong during the heating of the LiGd9(SiO4)6O2 single crys
influence of both the crystal field and the correlation tals was similar to that observed in the spectra of the
field on the vibrational spectra of the free [SiO4]4– Ca2Gd8(SiO4)6O2 oxyapatite up to the temperature of
anions in the Gd2SiO5, Lu2SiO5, and Mg2SiO4 crys 2053 K. The intensity of the Raman spectrum of the
tals, which resulted in the mixing of different types of LiGd9(SiO4)6O2 oxyapatite substantially decreased
vibrations. Our investigations revealed that the effects during the subsequent heating to 2073 K; moreover, we
of mixing appeared to be less significant in the struc observed a significant transformation of this spectrum
tures of the silicate oxyapatites studied in this work, in comparison with the spectrum at a temperature of
and they fairly well satisfy the conditions of the molec 2053 K (Fig. 4a). It was found that the Raman spec
ular approximation used in the analysis of the internal trum of the studied sample during cooling to room
vibrations of the isolated [SiO4]4– anions. temperature was completely different from the Raman
spectrum of the LiGd9(SiO4)6O2 crystal before the
The examination of the behavior of the Raman heating (Fig. 4b). A comparison of the Raman spec
spectra of both structures in the range from room tem trum at 300 K for the sample with the initial structure
perature to the melting point revealed interesting spe of LiGd9(SiO4)6O2 after the heating to 2073 K and the
cific features (Figs. 3a and 4a). An increase in the tem subsequent cooling with the Raman spectrum of the
perature to the melting point led to a significant shift polycrystalline gadolinium oxyorthosilicate

PHYSICS OF THE SOLID STATE Vol. 54 No. 8 2012

 STRUCTURAL TRANSFORMATIONS 1639

(Gd2SiO5) demonstrated that these spectra are com Table 2. Frequencies (in cm–1) and the symmetry of vibra
pletely identical to each other (Fig. 4b). Previously, tions in the Raman spectra of Ca2Gd8(SiO4)6O2 and
the Raman spectra of the Gd2SiO5 oxyorthosilicate LiGd9(SiO4)6O2 at 300 K
were investigated in detail in our work [8]. The Ca2Gd8(SiO4)6O2 LiGd9(SiO4)6O2
observed phenomenon can be explained by the incon Assignment
gruent character of the melting of the LiGd9(SiO4)6O2 Ag E1g E2g Ag E1g E2g
crystal according to the reaction 46 45
(LiGd9(SiO4)6O2)cryst = 9/2(Gd2SiO5)cryst 78 74
+ 1/2(Li2O · 3SiO2)melt. 103 96
– 100
In this case, the main result should be the formation of
polycrystalline Gd2SiO5 with a small fraction of the 107 104
melt with the Li2O · 3SiO2 composition. 161 164
After cooling, the Li2O · 3SiO2 composition at 178 –
room temperature should form a silicate glass with a 180 F1(νrot) + (νtr) 175
higher SiO2 content. However, the Raman spectrum of 207 205
this glass was not observed in our work. This is proba 228 –
bly associated with the fact that the intense Raman 236 236
spectrum of polycrystalline Gd2SiO5 hindered the
manifestation of the weak broadband Raman spec 250 255
trum of the vitreous phase. Furthermore, it should also 277 273
be taken into consideration that the melting tempera 286 285
ture of the Li2O · 3SiO2 composition does not exceed 321 323
1300–1500 K [15], whereas the temperature of the
393 400
incongruent melting of the LiGd9(SiO4)6O2 oxyapa
tite, according to our estimates, is equal to 2073 K. In 418 E(ν2) 406
this case, the Li2O · 3SiO2 composition is overheated 442 423
by almost 600–700 K, which, quite possibly, caused a 532 535
significant evaporation of this melt. 535 F2(ν4) 536
As was mentioned above, the slow cooling of the 562 584
Ca2Gd8(SiO4)6O2 melt leads to the crystallization of 588 590
the compound of the same composition and structure
as those before the melting. At the same time, the 870 A1(ν1) 870
Raman spectrum at 300 K for the sample prepared by 889 890
rapid quenching of the Ca2Gd8(SiO4)6O2 melt demon 940 952
strated the formation of a structure different from the 957 F2(ν3) 958
structure of the initial oxyapatite Ca2Gd8(SiO4)6O2.
962 979
The Raman spectra of the rapidly quenched melt and
the polycrystalline sample of the Ca2Gd8(SiO4)6O2 981 987
oxyapatite at 300 K are shown in Fig. 5 (curves 2, 3). 1031 1036
The location of the bands in the Raman spectrum of
the rapidly quenched melt at 300 K indicates that this
sample predominantly contains the isolated [SiO4] condensation of [SiO4] tetrahedra than those of the
groups. At the same time, the appearance of bands in initial interacting fragments [18]. For silicates with
the Raman spectrum at frequencies in the range of isolated [SiO4] groups, this implies the formation of
700 cm–1 (G band) counts in favor of the formation of oxygen ions that are not included in the composition
polymerized silicon–oxygen fragments in the sample. of the silicon–oxygen tetrahedra, which is caused by
It is this G band of the bridging Si–O–Si bonds in the the presence of cations capable of binding oxygen
frequency range 600–700 cm–1 which is an indicator through partially covalent bonds. Experimentally, this
of the occurrence of the processes of polymerization phenomenon was demonstrated in the Raman and
[16, 17]. This band should be absent in the structures NMR investigations of the melts and glasses with the
with isolated [SiO4] fragments. composition of crystalline Mg2SiO4 [10, 19–21]. It
The effect of polymerization in silicate melts was can be seen from Fig. 5 (curves 1) that the Raman
explained by the transformation of the anionic motif, spectrum of the transparent glass prepared by rapid
which resulted in the formation of silicon–oxygen quenching of the Mg2SiO4 melt contains the G band.
complexes with both the higher and lower degrees of The Re cations, which participate in the formation of

PHYSICS OF THE SOLID STATE Vol. 54 No. 8 2012

1640 VORON’KO et al.

(a) (b)

2273 K
2273 K
Intensity, arb. units

E2g

2073 K

2073 K
1673 K

1373 K 1900 K

973 K

573 K

300 K 300 K
0 400 800 1200 0 400 800 1200
Δν, cm−1 Δν, cm−1
Fig. 3. Change of the Raman spectra of Ca2Gd8(SiO4)6O2 (a) during heating from 300 K to the melting and (b) during crystalli
zation.

(a) (b)

2073 K
E2g 2073 K
Intensity, arb. units

2053 K

1673 K 1923 K

1373 K

1473 K
973 K

573 K 300 K

300 K Gd2SiO5

0 400 800 1200 0 400 800 1200

Δν, cm−1 Δν, cm−1
Fig. 4. Change of the Raman spectra of LiGd9(SiO4)6O2 (a) during heating from 300 K to the incongruent melting and (b) during
cooling with the crystallization of the gadolinium oxyorthosilicate. For comparison, the reference spectrum of crystalline
Gd2SiO5 at 300 K is shown in panel (b).

PHYSICS OF THE SOLID STATE Vol. 54 No. 8 2012

 STRUCTURAL TRANSFORMATIONS 1641

4. CONCLUSIONS
167
Thus, the Raman spectra of internal and external
vibrations in the Ca2Gd8(SiO4)6O2 and
LiGd9(SiO4)6O2 single crystals with the oxyapatite
237 G 870
structure have been resolved. It has been shown that
409 730 the frequency ranges of internal vibrations ν1–ν4 of the
isolated [SiO4] tetrahedra do not overlap, which indi
330 516
561 1 cates a weak influence of the crystal and correlation
Intensity, arb. units

606 759
878 fields in the structure of the silicate oxyapatites. The
698 978 hightemperature Raman spectroscopic investigation
2 has revealed that the LiGd9(SiO4)6O2 crystals undergo
870
646 incongruent melting at a temperature of 2073 K with
the precipitation of the crystalline phase of the
3 Gd2SiO5 oxyorthosilicate. The rapid quenching of the
Ca2Gd8(SiO4)6O2 oxyapatite leads to the formation of
previously unknown highly disordered metastable
structures containing both the isolated [SiO4] anions
and the polymerized silicon–oxygen complexes.
4
ACKNOWLEDGMENTS
5
This study was supported by the Council on Grants
ν2 ν4 ν1 ν3 from the President of the Russian Federation for the
0 400 800 1200 State Support of Young Russian Scientists (grant no.
Δν, cm−1 MK816.2010.2).

Fig. 5. Raman spectra of (1) vitreous magnesium orthosil

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