Journal of Non-Crystalline Solids 362 (2013) 20–24

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Journal of Non-Crystalline Solids

journal homepage: www.elsevier.com/ locate/ jnoncrysol

Raman and IR investigation of silica nanoparticles structure

A. Alessi ⁎, S. Agnello, G. Buscarino, F.M. Gelardi
Dipartimento di Fisica Università degli Studi di Palermo, Via Archirafi 36, I-90123 Palermo, Italy

a r t i c l e i n f o a b s t r a c t

Article history: In the present investigation we report experimental data regarding the Raman and Infra-Red (IR) absorption
Received 15 September 2012 activities of commercial silica nanoparticles. We compared the data of the nanoparticles with the ones ac-
Received in revised form 5 November 2012 quired in the same experimental conditions for commercial bulk silica. By this comparison we highlighted
Available online 14 December 2012
that the variability of the spectral features of the matrix related Raman and IR bands in the nanoparticles is
above the one observed for the bulk systems before any treatments. Furthermore, by studying nanoparticles
Keywords:
Raman spectroscopy;
with different sizes (diameters from 40 to 7 nm) and applying the shell-model we can suggest that the core
IR absorption; network of the nanoparticles is close to the one encountered in the bulk materials. By contrast for the surface
Silica nanoparticles shell, having a thickness of about 1 nm, as suggested by previous investigations, the structure is strongly
modified. In fact, from Raman and IR data it appears that the Si–O–Si angle has a lower main value than
those encountered in bulk systems and that the ring statistic is shifted towards lower member rings.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
In the last decades the fumed silica has attracted an increasing atten-
tion [1–5]. The fumed silica materials are amorphous silicon dioxide
(a-SiO2) nanoparticles obtained by reacting silicon tetrachloride in an
O2/H2 flame [6,7]. The generated primary particles, having diameters
from few to tens of nanometres, tend to aggregate forming larger sys-
tems that can be linked generating agglomerates [7]. These nanoparticles
are employed in different applications [6,8–11] and now they have
attracted the interest as they are promising materials to meet the mod-
ern tendency towards the device's miniaturization. The relevant role of
the fumed silica is due to the accessibility of the raw material, to the
chemical and physical properties of the SiO2 and to its sufficiently simple
preparation. In addition this material covers a fundamental function for
the basic research since it gives the possibility to investigate the amor-
phous state in the nanoscale range.
Studying the fumed silica nanoparticles several differences with
respect to the bulk silica were highlighted [3,4,12–14].
In the Raman spectra the peak position (ωR) of the R band at
about 440 cm − 1 (mainly generated by the oxygen atom bending in
the Si–O–Si linkages [15]) is observed at higher energies with respect
to the bulk [3,12]. The relative amplitudes (with respect to the signal
amplitude recorded at 800 cm−1) of the D1 (breathing vibration
mode of the 4-member rings [15]) and D2 (breathing vibration mode
of the 3-member ring [15]) bands, at about 495 and 605 cm−1, respec-
tively, appear more intense in the smaller nanoparticles than in the bulk
[3,12]. These differences have a great relevance since, for example, the R
band peak is related to the maximum of the distribution of the Si–O–Si
⁎ Corresponding author.
E-mail address: antonino.alessi@unipa.it (A. Alessi).
angle [15–17], whereas the D1 and the D2 bands are very useful for the
study of the ring statistic. Significant differences between fumed silica
nanoparticles, having different sizes, and bulk systems were observed
in the IR spectra too [3,12]. In this context, it is important to remember
that the fundamental network related IR bands of the silica are located
at about 1100 cm−1, 800 cm−1 and 480 cm−1[18].
Together with the spectroscopic investigations of the fumed silica
it is worth to remind that previous studies proposed a shell-model to
describe the particles structure [19,20]. In this model the overall
nanoparticle is constituted by SiO2 regions with unlike network. For
the interior part, the core, a bulk-like network was proposed in
[19,21], whereas in [4,14] differences between the core and bulk net-
work were suggested. For the external part, the surface-shell, differ-
ences with respect to the bulk materials both for ring statistic and
density were proposed [19,20]. More in details, the calculations
suggested a higher density of this part of the particle [19,20]. Finally,
the same simulations suggested that the structure of the core, the
thickness and the structure of the surface shell are independent
from the particle sizes [19,20].
The present study aims to experimentally explore the structural
properties of nanoparticles of different sizes by Raman and IR spec-
troscopies in order to improve their characterization, the understand-
ing of the structures of the core and of the surface shell and
opportunely consider the shell-model.
2. Experimental
For the present investigation we used commercial Aerosil fumed
silica samples produced by the Evonik Industries [6]. They were syn-
thesized by SiCl4 oxidation in an O2/H2 flame at 1100–1400 °C [6].

0022-3093/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jnoncrysol.2012.11.006
 A. Alessi et al. / Journal of Non-Crystalline Solids 362 (2013) 20–24
The initial powders of nanoparticles were pressed in a uniaxial
mechanical press at about 0.3 GPa to obtain tablets. In Table 1 we re-
port the name of the samples, their nickname, their specific surface
and the primary particle mean diameter (the distributions of the par-
ticle diameters can be found in [6]). The specific surfaces and the par-
ticle diameters were estimated by the physical absorption of N2 (BET
method) and transmission electron microscopy measurements, re-
spectively [6]. The nanoparticles were compared to three representa-
tive commercial silica bulk materials: Suprasil F300 (F300), Suprasil
300 (S300), and Suprasil 1 (S1) [22].
Raman spectra were acquired at room temperature by using a Fourier
Transform Raman spectrometer Bruker RAMII equipped with a 500 mW
Nd:YAG laser at 1064 nm. The applied experimental conditions lead to a
spectral resolution of 5 cm−1. The thickness of the samples was about
2 mm for the nanoparticle tablets and about 1 mm for the bulk
materials.
IR spectra were recorded at room temperature with a Bruker spec-
trophotometer (model VERTEX-70), the experimental conditions
were set to ensure a spectral resolution of 1 cm −1. The samples
used for these measurements were approximately 0.2 mm thick.
For the nanoparticle tablets, amplitude modulation AFM measure-
ments were performed in tapping mode by a Multimode V (Veeco
Metrology) scanning probe microscope. The system is equipped
with a piezoscanner (maximum xy range ~ 14 μm and maximum z
range ~ 3.6 μm) and a four-segment photodetector for cantilever de-
flection monitoring. PointProbe®Plus Silicon-SPM-probes were used
with Al backside reflex coating, resonance frequency ~ 300 KHz and
tip apical diameter ~ 10 nm. All the scans were executed at room tem-
perature and in N2 atmosphere. Further information on the AFM mea-
surements can be found in [23].
In Fig. 1, we report the AFM images recorded for the AEOX50 and
AE380 nanoparticles. These images show that after production of tablets
the particles are still clearly distinguishable and that the inter-particle
voids are present, regardless of the decrease of the particle distance
because of the pressure applied to produce tablets.
Moreover, we underline that the line-shapes of the Raman spectra
recorded for the tablets coincide with those of the spectra recorded
on the same sample in the form of powders. The only modification
is an improvement of the signal amplitude which significantly re-
duces the time required for the acquisition of each spectrum.
3. Results
Fig. 2a illustrates the Raman spectra recorded for the samples
AEOX50, AE200 and AE380. These spectra are reported as examples
of the Raman data acquired for the various types of nanoparticles. In
all the acquired Raman spectra we observed all the characteristic
bands (indicated in the Fig. 2a as SiO2 network, D1 and D2) associated
to the silica materials, in addition to the normal silica bands we ob-
served a band peaked at about 980 cm −1, which is attributed to the
SiOH groups [24]. All the spectra were normalized to the Raman sig-
nal amplitude recorded at 800 cm −1.
According to other investigations [3,12], various spectral features
of the silica related Raman bands (R band peak position, D1 and D2
amplitudes) clearly depend on the particle sizes. In addition, we
Table 1
Name, nickname, specific surface and particle diameter.
Name Nickname Specific surface Particle diameter
AerosilOX50 AEOX50 50 ± 15 40
Aerosil90 AE90 90 ± 15 20
Aerosil150 AE150 150 ± 15 14
Aerosil200 AE200 200 ± 25 12
Aerosil300 AE300 300 ± 30 7 In Fig. 3b we report the zoom of the IR absorbance measurements
Aerosil380 AE380 380 ± 30 7
21
note that the relative amplitude of the SiOH band increases with the
increase of the specific surface.
Before to consider these interesting dependences, by the zoom
(range 700–800 cm −1) of the spectra reported in Fig. 2b we note
that at 800 cm −1 (TO and LO vibrations [25]) our resolution and
the signal to noise ratio do not allow us to evidence significant differ-
ences in the line-shape of this network band. Anyway, it is interesting
to note that, if present, they can not be greater than those reported in
[16] studying the dependence of the Raman signal on the fictive tem-
perature or larger than those reported in [17] studying the Raman ac-
tivity of the densified bulk silica.
This consideration allows us to use these previous investigations
as starting points and terms of comparison to understand the
Raman activities of the different types of nanoparticles.
In the range 1000–1300 cm − 1, where the 1060 cm − 1 and
1180 cm − 1 bands are located [15,16,24], as noted for the 800 cm−1
the eventual differences as a function of the nanoparticle type can not
be discussed thoroughly for the presence of the 980 cm−1 band of
SiOH groups and for the low signal to noise ratio. However, even in
this case it appears that, if present, these differences are comparable
to those reported in [16,17].
The normalization for the 800 cm −1 network band allows a more
quantitative analysis of the spectra recorded as a function of the spe-
cific surface. In Fig. 2c, for example, we illustrate the behavior of the
D2 Raman band in the AE380, AE200 and AEOX50.
The data were obtained after the subtraction of a baseline tangent
to the Raman spectra at 570 and 640 cm −1, this procedure is similar
to that used in [26]. These data, in agreement with previous investiga-
tions [3,12], show that the D2 band relative amplitude (with respect
to the one of the 800 cm −1 band) increases with the reduction of
the nanoparticle sizes. For the bulk materials we observed the higher
D2 relative amplitude in the F300, it is important to note that in this
sample the D2 band has a relative amplitude close to that measured
in the AEOX50.
Fig. 2d illustrates the Raman signal recorded in the range
300–500 cm −1 for the different types of fumed silica nanoparticles
in comparison with the signal recorded for the F300 bulk silica. The
reported data were obtained after the normalization of the overall
spectra for the amplitude measured at about 800 cm −1 and then
they were vertically shifted for illustrative reasons.
We note that the R band shifts towards larger energies on decreas-
ing the particle sizes (increasing the specific surface). To evidence this
phenomenology we draw a dashed line to indicate the position ob-
served in the F300, which exhibits the higher value of the peak posi-
tion of the R band among the here investigated bulk samples.
Finally, even if the strong overlap between the R band and the D1
requires a more accurate procedure of analysis, we note that the rel-
ative amplitude of the D1 band increases as the specific surface rises.
In Fig. 3a we report the IR spectra recorded in the range
1000–5500 cm − 1 for the AEOX50, the AE200 and the AE380
nanoparticles. As for the Raman measurements we note the presence
of the ordinary silica IR bands indicated as SiO2 in the figure. Even in
this case the spectroscopic features of these bands show a dependence
on the nanoparticle types. In addition to the silica related bands we
clearly observe the presence of the SiOH IR absorption at about
3500 cm−1 and in the range 4200–4700 cm−1 [27]. We note that the
3740 cm−1 band related to the isolated SiOH groups [27] is clearly
distinguishable.
The IR spectra also evidence the presence of H2O molecules, which
generate IR bands at about 1630, 3200–3500 and 5200 cm −1 [27,28].
Since one of the IR bands of the H2O molecules strongly overlaps with
the silica band located at about 1630 cm −1 we will focus our atten-
tion on other two spectral regions, where the silica bands are
dominant.
recorded for the AEOX50, the AE200 and the AE380 nanoparticles in
22 A. Alessi et al. / Journal of Non-Crystalline Solids 362 (2013) 20–24

Fig. 1. Right, AFM image of AEOX50 tablet; left, AFM image of AE380 tablet.

the range 1855–1875 cm −1, whereas the zoom of the range 2100– measured in the F300, in which we observed the lower values
2320 cm −1 is reported in the panel c of the same figure. For illustra- among the bulk samples. Panel b of Fig. 3 evidences that for all the
tive reasons in each panel the spectra were vertically translated, fur- nanoparticles the peak of the 1870 cm −1 IR band (silica combination
thermore we report a dashed line to indicate the peak position band of the 1100 and of the 800 cm −1 fundamental modes [28]) is

d a

c b

Fig. 2. a) Raman spectra (range 200–1400 cm−1) recorded in the AEOX50 ( ), AE200 ( ) and AE380 ( ) nanoparticles, in the figure we report the attributions of the Raman
bands in agreement with [15–17,24,25]; b) Raman signal recorded in the spectral range 700–880 cm−1 for F300 ( ), AEOX50 ( ), AE90 ( ), AE150 ( ), AE200 ( ), AE300
( ), and AE380 ( ); c) D2 Raman band in the AEOX50 ( ), AE200 ( ) and AE380 ( ) nanoparticles; d) Raman spectra recorded in the range 300–500 cm−1 for the
AEOX50 ( ), the AE90 ( ), the AE200 ( ) and the AE380 ( ) nanoparticles in comparison with the Raman spectrum of the F300 ( ), the dashed line indicates the R band
peak position measured in the F300.
 A. Alessi et al. / Journal of Non-Crystalline Solids 362 (2013) 20–24 23

b c

Fig. 3. a) IR spectra of the AEOX50 ( ), AE200 ( ) and AE380 ( ) nanoparticles in the range 1000–5500 cm−1; b) zoom of the spectral range 1855–1875 cm−1; c) zoom of the
spectral range 2100-2320 cm−1. In panel b and c the spectra were shifted for illustrative reasons, the dashed line represents the position measured in the spectra of the F300.

observed at lower energies with respect to the one detected in F300 zones with different structures, the recorded spectra are the results of
(1873 cm −1 for the Suprasil W2 [28]). Another interesting finding the contributions related to these zones. More in detail, in [19] simu-
is constituted by the fact that the smaller is the particle the lower is lative calculations have shown that the nanoparticle can be divided in
the value of the peak position of this band. According to the above a core zone, in a surface shell with thickness of about 0.5 nm and in a
reported differences between the spectroscopic features of the bulk transition zone of 0.3 nm. In similar way, the experimental investiga-
and the nanoparticles, panel c of Fig. 3 qualitatively suggests the red tion on the irradiation induced E′γ centers [34] suggested the possi-
shift of the 2260 cm −1 band (peaked at 2258 cm −1 in the F300 and bility to use a simpler scheme, which predicts the presence of a core
at 2265 cm −1 in Suprasil W2 [28]). This band is related to the over- region and of a surface one having a thickness of 1 nm (this value ap-
tone of the bond stretching vibration mode observed at about pears compatible with the sum of thicknesses of the transition and
1122 cm −1 in the IR reflection spectra [29] and it is widely used to surface zones proposed by simulation). Furthermore, the simulation
characterize the silica network properties [29–31]. The IR activity at has highlighted that the structure and thickness of the surface shell
about 1990 cm −1 was also attributed to the silica network [28], and
overlaps to the 2260 cm −1.
Among the reported data the peak position of 1870 cm −1 IR band
appears to be easily analyzable as a function of the specific surface, in
fact its peak is easily detectable.
In Fig. 4 we report the peak positions as measured in the spectra of the
various nanoparticles as a function of specific surface. In the same figure
we report the value recorded in the F300 and a linear fit. It is very inter-
esting to note that the intercept of the fit is similar, within the experi-
mental error, to the value measured in the F300; furthermore we also
note that the value measured for the AEOX50 is close to the one of F300.

4. Discussion

Both the Raman and the IR measurements have evidenced a de-

pendence of the network related activities on the nanoparticle specif-
ic surface, such dependence appears to be above the variability
observed in the untreated (not irradiated or densified) bulk systems
[29,32,33]. To interpret our data it is important to underline that in
a shell-like model, which divides the overall nanoparticle in different
Fig. 4. Peak position of the 1870 cm−1 IR band measured in the fumed silica nanoparticles
(●), position measured in the F300 (○) and linear fit (y=1869.6+0.0149×S.) of the data
related to the fumed silica materials ( ).
24 A. Alessi et al. / Journal of Non-Crystalline Solids 362 (2013) 20–24
as well as the structure of the core are independent from the particles
sizes [19]. Within a shell model with two regions: the core and the
surface, our data can be used to extract information regarding their
structures in comparison with the bulk systems. For example, the
AEOX50 (with a radius of about 20 nm) can be reasonably considered
as representative of the core, neglecting the small contribution arising
from the about 1 nm of the surface shell.
The Raman and the IR measurements indicate that the spectro-
scopic features of the bands observed in the AEOX50 appear to be dif-
ferent from the ones of the S300 and S1 but close to the ones of the
F300. The difference observed among the bulk materials were related
to the different thermal histories [16,35].
The similarity between the F300 and the AEOX50 indicates that the
core has a structure close to one of the bulk system traditionally inves-
tigated. This suggestion is also supported by the intercept value calcu-
lated by the liner fit of Fig. 4.
By contrast, increasing the specific surface the experimental data
become more and more affected by the contribution of the surface
shell. This simple consideration implies that our data support the
idea that the surface has a strongly modified network with respect
to the one of the bulk systems. More in detail, our data, in agreement
with previous ones [3,12], indicate that the ring statistic is shifted to
the lower member rings. Furthermore, by using the relation between
the R band and the Si–O–Si angle distribution [16,17] we can guess
that the maximum of the Si–O–Si angle distribution is located at
lower values. This suggestion is qualitatively supported by the appar-
ent red shift of the 2260 cm −1 (the strong overlap with another more
intense IR band limits an accurate analysis in the smaller particles).
To have a more quantitative idea on the structural properties of
the surface shell it is important to note that in [34] the EPR measure-
ments suggested that the recorded E′γ signals were originated essen-
tially by the defects induced in the core and that the defects
concentration follows the law:
 
1 (1999) 169.
C E′Si ∝ −δ
S
ρ [8]
where ρ is the particle density, S is the specific surface and δ~1 nm is the
thickness of the surface shell. The term δ×S essentially is needed to sub-
tract to the total mass of the particles the contribution of the surface shell:
mS
≈ρ
δ
S
mp
ms and mp are the mass of the surface zone and of the overall particle, re-
spectively. Eq. (2) allows to estimate that about the 80% (ρ=2.21 g/cm3
is used) of the AE380 nanoparticle mass is due to the surface shell. As a
consequence we can approximately attribute the Raman and the IR spec-
tra of these nanoparticles to the surface shell.
In the Raman spectra of these nanoparticles the R band is blue
shifted of about 20 cm −1 which implies a significant decrease of the
Si–O–Si angle, such datum is confirmed by the IR data that indicate
a clear red shift of the 1870 cm −1 band of about 7 cm −1 and a possi-
ble red shift of the 2260 cm −1 (this implies a shift of the 1100 cm −1
IR band related to the Si–O–Si angle [13,18]). As a final consideration
we note that assuming the possibility of extending the study on the
densified bulk materials [17] to the surface shell and to the core (fur-
ther investigations could indicate the validity of such assumption),
one obtains a surface shell density of about 10% higher than the one
of the ordinary silica (2.21 g/cm −3), whereas for the core the differ-
ences should be not higher than 2%, both values appear compatible
with the simulative predictions [19].
5. Conclusion
We investigated the structure of commercial silica nanoparticles dif-
fering for sizes by Raman and IR techniques. Our investigation reveals
that the variability of the silica network related bands observed in the
nanoparticles is above the one observed for untreated bulk materials.
Within the shell-model the here reported data suggest that the core
structure is close to some encountered in bulk materials as the commer-
cial silica Suprasil F300. At variance the surface shell, having a thickness
of about 1 nm (as suggested by previous investigations), appears to
have a strong modified structure as indicated by the shifts of the
Raman R band and of the 1870 cm−1 IR one. The properties of these
bands suggest a lower value of the Si–O–Si angle (the data on the
2260 cm−1 band qualitatively agrees with this conclusion). The modifi-
cations observed in the surface shell structure regard also the ring sta-
tistic, which is shifted towards the lower member rings as testified by
the D1 and D2 Raman bands. All these data agree with the tendency in-
dicated by the simulation. In addition, since in bulk systems such varia-
tions were related to the density increase, our data seem to support the
simulative prediction of the shell-model regarding this topic.
Acknowledgments
The authors are grateful to the people of the LAMP group (http://
www.fisica.unipa.it//amorphous) at the Department of Physic of the
University of Palermo for the useful discussions. The authors acknowl-
edge the financial support provided by Assessorato Regionale BB.CC.AA.
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