Journal of Alloys and Compounds 831 (2020) 154836

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Observations of phonon anharmonicity and microstructure changes

by the laser power dependent Raman spectra in Co doped SnO2
nanoparticles
Lalit Kumar Gaur a, Mohan Chandra Mathpal b, *, Promod Kumar c, S.P. Gairola a, **,
Vivek Agrahari d, M.A.R. Martinez b, F.F.H. Aragon b, Maria A.G. Soler b, H.C. Swart c,
Arvind Agarwal d
a
Uttaranchal University, Premnagar, Dehradun, 248007, Uttarakhand, India
b
Institute of Physics, Universidade de Brasília, Brasilia, 70910900, Brazil
c
Department of Physics, University of the Free State, Bloemfontein, ZA, 9300, South Africa
d
Department of Physics, MNNIT, Allahabad, UP, 211004, India

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

Article history: SnO2 nanoparticles are of critical importance owing to their necessity for fundamental studies and highly
Received 6 February 2020 attractive applications in optoelectronic devices and photocatalytic activities. In this study Raman
Received in revised form spectroscopy was rigorously employed to investigate the effect of low concentrations of cobalt doping in
3 March 2020
rutile SnO2 nanoparticles. The effect of annealing temperature and laser power dependent molecular
Accepted 17 March 2020
Available online 21 March 2020
vibrations was used to directly realize the localized microstructural changes and phonons interaction
within the lattice. A large broadening and shifting towards the lower wavenumber side in the Raman
spectra for A1g and B2g modes of vibration were observed. This was mainly attributed to microstructural
Keywords:
SnO2
changes, maximum possible quasiharmonic shift and a large proportion from pure anharmonic shifts as a
Co-precipitation function of increasing laser power. Two approaches were adopted to calculate the localized temperature
Cobalt that has increased due to laser heating during the Raman measurements in the samples. In a more
Nanoparticles feasible and reliable approach the full with at half maxima (FWHM) broadening and frequency shifting as
Laser a function of laser power were directly compared with the previously reported experimental results. In
Raman another approach the well-known Klement model based on the kinematics of three-phonon processes
was also used to determine the localized temperature.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction protein and N-terminal pro-brain natriuretic peptide (NT-proBNP)

Tin dioxide (SnO2), is an n-type semiconductor material with a
stable crystal structure that has been widely studied for its various
applications in optoelectronics, spintronics, photonics, photo-
catalysis, gas sensors, photochemistry, solar cell, protective coat-
ings, transparent electrodes and light-emitting devices etc. [1e7].
Recently, SnO2 based composites materials have emerged to be
useful for biosensor and bioelectronics applications such as photo-
electrochemical immunosensor for the detection of amyloid b-
* Corresponding author.
** Corresponding author.
E-mail addresses: mohanatnpl@gmail.com (M. Chandra Mathpal), spgairola10@
gmail.com (S.P. Gairola).
[8e10]. The high electrical conductivity, high transparency in the
visible range, high reflectivity in the infra-red range, good thermal
and chemical stabilities are the unique features of SnO2 for its
numerous optoelectronic applications. In recent years the various
dopants have been used to improve and modify the structural,
magnetic and optical properties of SnO2 nanomaterials as per need
of the desired applications.
Bouaine et al. have studied the structural, optical and magnetic
properties of low concentration (2%
) of Co-doped SnO2 nano-
particles [2]. In their study the significant structural modifications
and disorder of the SnO2 lattice were realized by Raman spectros-
copy. Substitution of Sn4þ ions with Co2þ ions results in contraction
of the SnO2 lattice and reduction in the oxygen content, triggering
ferromagnetic interactions. Jaiswal et al. observed that the irradi-
ation of Swift Heavy Ion (SHI) beam modifies the surface properties

https://doi.org/10.1016/j.jallcom.2020.154836
0925-8388/© 2020 Elsevier B.V. All rights reserved.
2 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836
and electronic excitation in Co doped SnO2 thin films on Si sub-
strates prepared by radio frequency (RF) sputtering method [4]. The
microwave irradiation method and hydrothermal method were
used by Kar et al. to study the shape dependent and their defect
related structural, absorbance and luminescence properties of SnO2
nanostructured materials [5]. In their study the presence of defects
and their effect were clearly revealed by X-ray diffraction (XRD),
photoluminescence (PL) and Raman spectroscopy. Therefore the
structural information in nanomaterials becomes important in or-
der to analyze the subsequent variation in optical, electronic and
magnetic properties [6,7]. The effect of Co-doping in the structural
and optical properties in SnO2 nanomaterials have been investi-
gated by many researchers [3,11e13], however there is rarely any
information related to the influence of incident laser power under
investigation on the Raman spectra which becomes essential to
understand the role of defects, doping and their microstructural
properties. H. Tsai et al. have recently reported that laser power
induced structural dynamics plays an important role to increase the
efficiency of hybrid perovskite solar cells due to the lattice expan-
sion which helped in relaxation of local lattice strain at the
perovskite-contact interfaces [14]. Zhang et al. have shown the
symmetric and asymmetric mode of vibration causes shifting in
Raman peaks position which is ascribed to large local temperature
variation for commercial rutile phase of TiO2 nanoparticles [15].
They observed the shifting from 611.0 to 606.8 cm1 for the A1g
mode of the rutile phase of TiO2 can result in an increase in tem-
perature from 300 to 619 K, when the incident laser power was
increased from 0.44 to 467.1 mW. Similarly the shift in the position
of the rutile Eg mode of TiO2 at the same laser power was from 451
to 429 cm1 for an increase of temperature from 300 to 735 K.
Raman spectroscopy is a powerful tool to understand the mo-
lecular vibrations inside the crystal lattice and their relation with
structural parameters, quantization effect, lattice contraction and
expansion and particle size variation by observing the broadening
and shifts in the peak positions of Raman bands [16]. This work is
aimed to understand the variation in the structural and Raman
scattering properties of SnO2 lattice which were induced by the low
concentrations of the Co doping synthesized by a co-precipitation
method. The SnO2 nanoparticles were synthesized by Co doping
at different concentrations and then annealed at two different
temperatures of 400  C and 600  C respectively. In order to best
represent the data we have chosen the three samples of undoped
SnO2, 3% and 5% of Co doping in SnO2 nanoparticles. The optically
controlled laser power dependent Raman measurements were
carried out in ambient conditions by using a visible laser light of
wavelength 532 nm to observe and compare the microstructural
variation through the changes in molecular vibrational levels. The
effect of laser power irradiation on Raman spectra of SnO2 nano-
particles is the key part of this investigation. The effect of laser
heating and its role in lattice contraction were confirmed after
annealing the samples at 600  C.
2. Experimental
2.1. Synthesis of SnO2 nanoparticles
All undoped and Co-doped SnO2 samples were synthesized in
aqueous solution by using a chemical co-precipitation method at
room temperature. The undoped SnO2 sample as a reference was
prepared by dissolving tin (II) chloride dehydrate in 100 ml distilled
water to prepare the 0.2 M solution. This reaction was performed
under continuous magnetic stirring for 30 min at room tempera-
ture. Then an aqueous ammonia solution (NH4OH) was added drop-
wise to above solution under constant stirring to maintain a pH
between 8 and 9 (~4.8 ml) and further stirred for 1 h. The aging
precipitate was filtered and washed with double distilled water.
The resulting precipitate was dried at 80  C for 24 h to remove
water molecules. This dried product was crushed into a fine powder
with the help of a pastel mortar and is named as SC0. Finally, the
product was thermally treated in a muffle furnace at temperatures
of 400  C and 600  C for 4 h. For the sake of convenience the final
products of these powder samples were labeled as SC0e400C and
SC0e600C, respectively.
2.2. Synthesis of cobalt doped SnO2 nanoparticles
The series of Co doped SnO2 with a different atomic ratio of 3
and 5 at% of Co dopants were synthesized by adding the cobalt
precursor (CoCl2$2H2O) in the main solution of the SnO2 (SC0) as
described above. In the typical preparation 4.5126 g of the tin
precursor (SnCl2$2H2O) and 3 at% cobalt (II) chloride dehydrate
CoCl2$2H2O (0.142758 g) was dissolved in 100 ml distilled water to
prepare the 0.2 M solution. The sample was further processed and
thermally treated under the same condition as described for sam-
ple SC0. These samples were named as SC3e400C and SC3e600C
after thermal annealing at 400  C and 600  C respectively. Similarly,
other Co doped samples of the series with cobalt chloride dehy-
drate CoCl2$2H2O of 5 at% (0.23793 g) were prepared and named as
SC5e400C and SC5e600C, respectively. The color of powders
turned to gray for the Co doped SnO2 nanoparticles while the
undoped SnO2 was of white color.
To investigate the structural, optical and morphological prop-
erties these powder samples were characterized by X-ray diffrac-
tion (XRD Rigaku D-Max) using a fixed Cu Ka line (l ¼ 1.5406 Å),
field emission scanning electron microscopy (FESEM), high reso-
lution transmission electron microscopy (HRTEM), UV-visible (UV-
Vis) spectroscopy (Lambda 35 PerkinElmer), Fourier transform
infrared spectroscopy (FTIR) and Raman spectroscopy (by 532 nm
laser). The laser spot size was kept small (~1 mm diameter) in most
of the Raman measurements.
3. Results and discussions
3.1. X-ray diffraction (XRD)
The XRD patterns for undoped and Co-doped SnO2 samples
annealed at 400  C and 600  C are depicted in Fig. 1(a) and (b),
respectively. The XRD patterns confirmed the rutile phase of SnO2
(Reference code: 041-1445) nanoparticles [1]. The peaks with the
highest intensities in the XRD patterns were considered for the
calculation of lattice parameters, lattice volume and crystallite
sizes. These calculated values are shown in the Table 1. The
parenthesis in the first column of the Table 1 describes the formula
and unit used for calculations. A brief description of the calculation
of the various parameters is discussed in section SI-1 of the sup-
plementary materials (SM). The average crystallite sizes were
estimated by using the well known Scherrer formula for all the Co
doped SnO2 nanoparticles. The average crystallite sizes for the
samples annealed at 400  C are in the range of 10e18 nm, whereas
19e23 nm for the samples annealed at 600  C. The lattice volume of
the SnO2 lattice decreased with the Co doping, though it started
increasing with the increase in Co concentration from 3 to 5 at%.
The reduced unit cell volume after Co doping is clearly signifying
that in spite of having a large ionic radius of Co (Co2þ ~ 0.745 Å to
0.82 Å) in comparison to Sn (Sn4þ ~ 0.70 Å) the doping did not
expand the lattice thus indicates that the most of the Co2þ ions
were substituting the Sn4þ ions [17,18]. The lattice parameters and
average grain size have decreased after doping with the Co ions
(See Table 1). Therefore it is expected that a fraction of Co ions are
favoring to occupy an interstitial position in the SnO2 crystal and
 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836 3

Table 1
Structural parameters of Co doped SnO2 nanoparticles.

Structural/Optical parameters SC0 SC3 SC5

Lattice constant (Å) a ¼ b ¼ 4.823, a ¼ b ¼ 4.801, a ¼ b ¼ 4.821,

400  C c ¼ 3.217; c ¼ 3.215; c ¼ 3.216;
Lattice constant (Å) a ¼ b ¼ 4.823, a ¼ b ¼ 4.815, a ¼ b ¼ 4.815,
600  C c ¼ 3.217 c ¼ 3.219 c ¼ 3.222
Unit cell volume
(a2c ¼ Å3)- 400  C 74.845 74.089 74.749
(a2c ¼ Å3)- 600  C 74.856 74.619 74.705
Average crystallite size (nm)
400  C 15.6 18.1 10.3
600  C 22.7 21.6 19.6
Band gap (UV)- 400  C 3.6 eV 3.4 eV 3.4 eV
Band gap (UV)- 600  C 3.4 eV 3.3 eV 3.6 eV

3.2. Microscopy analysis (SEM and TEM)

Fig. 1. XRD patterns of undoped SnO2 and Co doped SnO2 nanoparticles annealed at
(a) 400  C and (b) 600  C. Here A corresponds to the partial phase formation of SnO.
(Note: In Y scale a.u. means arbitrary units).
some of it prefer to stay on the surface and grain boundaries of the
SnO2 nanoparticles lattice [12]. After careful investigation a broad,
noisy and weak diffraction peak around 2q~29.6 can be seen in the
SC3 and SC5 samples, which is pronounced in case of the sample
annealed at 600  C as shown in the inset of Fig. 1(b). This peak was
identified as the reflection from the (101) plane of an additional
phase of SnO (Reference code: 001-0891 and 001-0902) [19].
Sangaletti et al. have discussed that a dominant phase of the SnO (at
450  C) can transform into the SnO2 (at 650  C) thin film as a
function of annealing temperature through some intermediate
phase of SnOx (1<x>2) [19]. Though such intermediate phase (such
as Sn2O3, Sn3O4) for transformation from SnO to SnO2 are not
observed in the XRD of these samples but realized in the Raman
spectroscopy as discussed further in the analysis of the Raman
spectra. It is well discussed by Eifert et al. that the direct observa-
tion of an intermediate phase such as Sn2O3, Sn3O4 is difficult by
XRD [20].
The reduction in most of the peak intensities and their broad-
ening with increasing Co concentration indicates that the presence
of Co ions in SnO2 is preventing the growth of nanocrystals [6].
There are no other impurities and crystal phases as observed within
the detection limit of the XRD.
The Fig. 2(aec) and their insets show the scanning electron
microscopy (SEM) images of SC0e400C, SC3e400C and SC5e400C
samples at 1 mm and 100 nm scales, respectively. The non-uniform
nano-sized distribution and agglomeration of spherically shaped
nanoparticles are clearly visible in the SEM micrographs. The Fig. 2
(d) represents the EDX of the SC5e400C sample. EDX confirms the
presence of the compositional elements (Sn, O and Co). In addition
to the presence of Sn, O and Co, the two additional peaks corre-
sponding to the carbon (C) and platinum (Pt) in all the samples
(data not shown) have been observed. The presence of Pt is due to
the processing and imaging of the samples after Pt deposition for
stable microscopic measurements, whereas as the carbon peak is
observed due to the carbon contamination which may be either
from the environment or caused by residues of carbon tape on
sample mounting stage.
There is no other impurity peaks in the samples as shown in the
EDX. Raman spectroscopy is a very sensitive tool to confirm the
presence of carbon (either amorphous or crystalline) as the D-band
and G-band for carbon can be easily detected. So in order to further
confirm that there was no carbon contamination, the Raman
spectra of the SC0e400C sample (other samples not shown here)
was recorded and is shown in section SI-2 (Fig. S1) of SM within the
range of 90e1800 cm1 [21]. In all the samples there was no signal
for the presence of carbon which confirms that the appearance of
carbon peak in EDX pattern was mainly because of contamination.
Transmission electron microscopy (TEM) is useful technique in
order to acquire important information about the surface
morphology and particle size distribution in nanoparticles system.
TEM and the high resolution images were also recorded for one of
the sample SC5e400C. TEM images at different magnification scale
for SC5e400C sample are shown in Fig. 3. From TEM images in
Fig. 3(a and b), it can be inferred that the Co doped SnO2 nano-
particles are either nearly spherical in shape, granular or they form
small clusters of nanoparticle, which are similar to those are
observed in SEM images. Several nanoparticles in Fig. 3(c) are
encircled to visualize the different sizes of the nanoparticles,
whereas the Fig. 3(d) depicts the high resolution image of the area
selected (white circle) in Fig. 3(c). The presence of (101) planes
corresponding to SnO2 nanomaterials (d101 ¼ 0.27 nm) can be
confirmed in HRTEM image suggests the good crystallinity of the
nanomaterials. The particle size distribution curve is plotted in
Fig. 3 (e) indicates that most of the particles are lying in the range of
6e20 nm with an average particle size diameter of 14 ± 6 nm,
which are in good agreement to the crystallite size calculated from
XRD.
4 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836
Fig. 2. SEM images (a) SC0e400C (undoped SnO2), (b) SC3e400C (3% Co doped SnO2), (c) SC5e400C (5% Co doped SnO2); and (d) EDX of SC5e400C.
3.3. Fourier transform infrared spectroscopy (FTIR)
The presence of the different IR active bonds was investigated by
the FTIR spectra of undoped and Co doped SnO2 nanoparticles,
which are presented in Fig. 4. The presence of the main vibration
bands are indicated in the Fig. 4 for SC5 sample annealed at 600  C.
A list of peak positions and their possible mode of vibration is
presented in Table S1 of section SI-3 of the SM.
The absorbance band between 3433 and 3686 cm1 is attributed
to the free stretching vibrations of the OeH group adsorbed on the
surface of SnO2 whereas a peak around 1630 cm1 is for the
bending vibrations mode for the adsorbed water molecules [1,14].
This manifest a large amount of hydroxyl group was in intact with
the undoped and Co doped SnO2 surface. The bands around 2854,
2874, 2924, 2963 are assigned to the symmetric stretching modes
of CeH bonds due to the presence of the residual alcoholic group in
the SnO2 nanoparticles [22,23]. Besides these the presence of other
overlapped low intensity peaks correspond to the CeH bending
mode (such as 1385,1400 and 1460 cm-1 etc.) indicate the presence
of saturated hydrocarbons from organic residuals of the precursors
during synthesis and annealing process or the presence of envi-
ronmental contamination [12,22,23]. The tin oxide exhibits a broad
FTIR absorption bands for stretching mode of SneO bonds vibration
and anti-symmetric vibration for SneOeSn bonds in the region
from 561 to 669 cm1 [11,14,19]. A small shifting in these charac-
teristic peaks have been observed with the increase in the Co
concentration, which may be caused by the differences in the bond
length that occurred when Co ions replace Sn ions in the host lattice
[12,24]. This confirms that at least some of the Sn ions were
substituted by the Co ions inside the SnO2 lattice. Additionally all
the high intensity peaks are common in all the samples indicates
the absence of any other phase such as metallic Co, CoO or Co3O4
etc.
3.4. UV-visible (UV) spectra
UV-Vis absorption spectra of the SC0, SC3 and SC5 samples
annealed at 400  C and 600  C are shown in Fig. 5. The samples
were dispersed in distilled water (DI) and DI water was used as a
reference to record the absorption spectra in a dual beam spec-
trometer. Tauc plot for calculation of direct bandgap of all the
samples are shown in Fig. 6. The absorption band gap energy can be
determined by the following equation [1].
(ahn)n ¼ B (hn - Eg)
where hn is the photon energy, a is the absorption coefficient, B is a
constant relative to the material and n is a value that depends on
the nature of transition (n ¼ 2 for direct band gap, 2/3 for direct
forbidden gap and 1/2 for indirect band gap).
By Beer’s law, absorbance (A) is directly proportional to the
absorption coefficient (a), therefore a plot between (Ahn)2 and hn
(photon energy) gives the bandgap after fitting and extrapolating
the tail of the linear region near point of inflection to the Y ¼ 0
((Ahn)2 ¼ 0) scale in the Tauc plot. The calculated direct bandgap
from Tauc plots are mentioned in the Table 1.
 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836 5

Fig. 3. TEM images of SC5e400C sample: (a) at 100 nm scale, (b) at 50 nm scale, (c) high resolution image at 10 nm scale, (d) high resolution image at 2 nm scale of the area (white
circle) selected in figure C, (e) Histogram plot for spherically shaped nanoparticles size distribution and their normal distribution curve.

With increasing Co concentration the bandgap initially
decreased from 3.6 to 3.4 eV, which again increased to 3.6 eV for
SC5 sample annealed at 600  C. There are two additional broad
absorption peaks around 428 and 656 nm in the Co doped SnO2
nanoparticles manifest that the Co ions have a significant influence
on the electronic structure of the SnO2 lattice. This observation can
be explained on the basis of the sp-d exchange interactions be-
tween the band electrons and the localized d electrons of the Co2þ
ions substituting Sn4þ ions. The s-d and p-d exchange interactions
give rise to a negative and positive corrections to the conduction-
band and valence-band edges, respectively, leading to narrowing
of the band gap [12,25,26]. Any stress, dopant levels or defects in
the lattice, whose energy states exist in between the bottom of
conduction band and top of valence band may result in reducing
the energy band gap of the nanomaterials [7,13]. These additional
absorption peaks were mainly assigned to the charge transfer from
new electronic states introduced by the 3d electrons of Co2þ cations
to the 3d t2g orbitals of the Sn4þ cations in the conduction band
[11,12]. The additional band around 656 nm can be ascribed to the
ded transitions of Co2þ ions in octahedral site symmetry with a
transition from 4T1g(F) to 4A2g(F) [12].
3.5. Raman spectroscopy
In order to understand the role of Co doping in the SnO2 lattice
the power dependent Raman spectra of SC0, SC3 and SC5 samples
were recorded in the range of 100e900 cm1. Silicon (521 cm1)
has been used to calibrate the spectra by using a green laser
(532 nm) at different power of 1, 10, 25, 40 and 100 mW for all the
measurements. At low power of 1 mW the Raman signals were very
weak for any qualitative analysis so data is not presented here. The
Raman spectra were taken by focusing the laser beam at the same
spot in different five region of the powder samples (data not shown
for different positions here as the results were similar at all the
positions) by first increasing the laser power and then decreasing
the laser power at the same spot in these powder samples. The
6 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836
Fig. 4. FTIR spectra of undoped SnO2 and Co doped SnO2 nanoparticles.
plots of Raman spectra are shown in Fig. 7(aef) for SC0, SC3 and SC5
samples annealed at 400  C and 600  C, respectively. The insets in
Fig. 7 (a & d) are the magnified peak position for the A1g mode of
vibration. The variation in the frequency and FWHM of the A1g
mode of vibration of undoped and Co doped SnO2 nanoparticles at
different increasing (IP) and decreasing laser powers (DP) are
shown in Fig. 8(a and b). The Fig. S2 of the supplementary materials
(SI-4) is shown to compare the Raman spectra of Co doped SnO2 at
400  C and 600  C for a laser power of 100 mW. Though the vi-
bration bands in the low frequency region between 100 and
300 cm1 are complex to understand as the overlapping of several
peaks gives a broad peak in many spectra, therefore in broader
bands the contribution from different band need to be separated. In
low frequency regions the main contribution is from SnO phase,
SnOx (Sn3O4 or Sn2O3) and IR activated modes of E(1) u (TO) and Eu
(1)
(LO). A table for different possible mode of vibration in each sample
is mentioned in Table S2 of section SI-4 of the supplementary
materials.
The first Brillouin’s zone of the SnO2 is formed by two tin and
four oxygen atoms (total 6 atoms) in a unit cell, which is responsible
for the 18 different modes of vibrations. These modes at the centre
of Brillouin’s zone can be written as G ¼ Gþ þ
1 (A1g) þ G2 (A2g) þ G3
þ laser power generally induces thermal expansion due to the change
(B1g) þ Gþ 4 (B 2g ) þ G -
5 (Eg ) þ 2 G -
1 (A2u ) þ 2 G -
4 (B 1u) þ 4 G þ
5 (E u)
[3,24,27e29]. Among these B1g, A1g, B2g modes and doubly
degenerate Eg mode are the Raman active modes and two A2g and
B1u are silent modes. Two others, namely the single A2u and the
triply degenerate Eu modes are IR active modes. A2u has one optic
and one acoustic mode while Eu has two acoustic and one optic
mode. The A1g, B1g and B2g modes are nondegenerate and vibrate in
the plane perpendicular to the c axis. A1g and B2g modes are due to
the expanding and contracting vibration of SneO bonds in a plane
perpendicular to c axis, respectively. The Eg mode is doubly
degenerated and vibrates in the direction of the c axis. In the Raman
active modes Sn atoms are at rest whereas an oxygen atom vibrates.
The B1g mode consists of rotation of the oxygen atoms around the c
axis, with all six oxygen atoms of the octahedral participating in the
vibration. In the A2g infrared active mode, Sn and oxygen atoms
vibrate in the c axis direction, and in the Eu mode both Sn and O
atoms vibrate in the plane perpendicular to the c axis. The silent
modes correspond to vibrations of the Sn and O atoms in the di-
rection of the c axis (B1u) or in the plane perpendicular to this
Fig. 5. UV-Vis spectra of undoped SnO2 and Co doped SnO2 nanoparticles.
direction (A2g) [29].
The clear large shifting towards lower wavenumber side has
been observed as a function of incident laser power for A1g and B2g
mode of vibration (see Fig. 7). Similar observation for shifting in
these two modes can be realized as a function of the Co doping
concentration in SnO2 (see Fig. 9). There is considerably small shift
in the peak position of Raman spectra of each sample at same laser
beam irradiation as a function of annealing temperature (Table S2),
though the peakwidth (FWHM) of A1g mode is significantly reduced
after annealing at 600  C as observed at low laser powers.
In all the samples the magnitude of shifting towards lower wave
numbers as a function of increasing power (up to 100 mW) in A1g
mode (Table 2) are 6.3, 19.2, 17, 6.5, 13.7 and 16.4 Cm-1 respectively.
The similar shifting has been observed for B2g mode of vibrations.
The shifting in A1g peak position as a function of incident laser
power in SC0-400  C and SC0-600  C is small as compared to Co
doped SnO2 samples at the same annealing temperature. The effect
of increasing laser powers can be understand from the fact that
more laser light is being absorbed by electronic transitions which
transfers their energy to the lattice and results in the local heating
of the undoped and Co doped SnO2 lattice [26,30,31]. Increasing the
in the interatomic distance induced in the lattice [30,31].
There is no significant trend for the change in the Eg mode of
vibration either towards higher or lower wavenumber side as a
function of increasing Co concentration and laser power as well.
Interestingly a small shifting towards higher wavenumber side for
A1g and B2g modes of vibration are clearly observable at 100 mW
laser power for the samples annealed at 600  C as compared to
samples annealed at 400  C (Fig. 7 and Table S2). This can be
consider the effect of increasing particle size with an increase in
annealing temperature [32].
Dieguez et al. have reported a detailed experimental and theo-
retical study of Raman spectra of SnO2 nanoparticles as a function
of nanoparticle sizes which were obtained at different annealing
temperatures [32]. Their results showed that the A1g and B2g modes
shift towards lower wave numbers whereas Eg shifts towards
higher wave numbers with the decrease in nanoparticles size.
However, the variation in the Eg mode was considerably small.
Decreasing the power in reverse order at the same spot for SC0
sample showed reversible behavior which recovered the almost
 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836
Fig. 6. Tauc plot for undoped and Co doped SnO2 nanoparticles.
same peak position and FWHM in the Raman spectra with an
enhancement in the peak intensity of A1g and B2g modes of
vibrations.
3.5.1. Observations of anharmonicity
One of the main reason for broadening and shifting in the peak
position due to laser heating effect in the Raman spectra for A1g and
B2g modes as a function of laser power can be correlated with the
work reported by T. Lan et al. group for Raman study of rutile SnO2
and rutile TiO2 nanoparticles at different temperatures [29,30]. T.
Lan et al. group have measured the Raman spectra for commercial
rutile SnO2 at different temperatures ranging from 83 to 873 K [29].
They observed the similar broadening and peak shifting towards
lower wave numbers for the three main peaks (Eg, A1g and B2g) as a
function of increasing temperature during the measurements.
To account this broadening and shifting in their results they
theoretically performed the peak fitting by using the first principles
calculations for the kinematics of phonon-phonon interactions.
Their results showed a large anharmonic shifts and broadenings for
7
all the Eg, A1g and B2g modes of vibration. The quartic anharmo-
nicity was dominant in the B2g mode due to the symmetry of the
oxygen atom displacements, whereas the cubic anharmonicity was
dominant for the Eg and A1g modes of vibrations. The pure anhar-
monicity generally arises from phonon-phonon interactions with
the increase in lattice temperature. This contributes to shifts in
phonon frequencies, but also causes phonon damping and lifetime
broadening of phonon peaks. Therefore the large peak shifting and
broadenings in our samples as an effect of laser heating in undoped
and doped SnO2 indicate that there is a large contribution from
pure anharmonicity [29,30].
A direct comparison with Lan et al. work is done to estimate the
local temperature and to calculate the anharmonicity in our sam-
ples. After comparing the results for FWHM and frequency shift of
the A1g mode for SnO2 nanoparticles as reported by Lan et al. the
local temperature that can be created by laser heating in different
samples are mentioned in Table 2 and a graph is also presented in
Fig. S4 of the supplementary materials. The Klemens model as
discussed in Zhang et al. and Lan et al. works have been also
8 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836

Fig. 7. Raman spectra of undoped and Co doped SnO2 nanoparticles at different increasing (IP) and decreasing laser powers (DP). (a) SC0-400  C, (b) SC3-400  C, (c) SC5-400  C, (d)
SC0-600  C, (e) SC3-600  C and (f) SC5-600  C. Here # represents molecular vibration corresponding to the formation of Sn3O4 phase, * corresponds to the formation of SnO phase,
A corresponds to the IR active band E2u (TO), and D corresponds to the vibration band of E1u (LO).

performed here to estimate the local temperature generated in

undoped and Co doped SnO2 nanoparticles [15,30]. The frequency
0 1
2
shift and FWHM’s of only A1g mode were considered for compari- DGðT Þ ¼ B1 @1 þ   A
sons as Eg and B1g modes have weak intensities. To calculate the ħu 0
2KB T
FWHM and centre of the peak position each A1g mode in all the e 1
0 1
spectra were fitted to a Lorentzian function. The FWHM as a
function of local variation in temperature can be expressed as B 3 3 C
þ B2 @1 þ   þ   A (2)
[15,30]: ħu0 ħu0 !2
2KB T 2KB T
e 1 e 1
G(T) ¼ G þ DG(T) (1)

where G is the FWHM extrapolated to 0 K in the bulk (~2 cm1) 25 where the first and second terms are due to the effect of the three-
and DG(T) can be written phonon and four-phonon coupling terms respectively. B1 and B2 are
the fitting parameters of three-phonon and four-phonon coupling
 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836
Fig. 8. (a) The frequency shift and (b) Change in FWHM in Raman spectra of undoped and Co doped SnO2 nanoparticles at different increasing (IP) and decreasing laser powers (DP).
terms respectively. Generally, the contribution from the four-
phonon coupling term is negligible so that we can ignore it for
the calculation [15,30]. The similar equations (1) and (2) can be fit
to measure the frequency shift, by replacing the fitting parameters
B1, B2 with A1, A2 respectively and replacing the G by quasiharmonic
frequency shift. After simplifying the above equation the local
temperature caused by laser heating can be approximated as:
ħu
T¼  0  b vðln uÞ
(3)
2KB ln DGðT ÞþB1
DGðT ÞeB1
where ħ is Planck constant divided by 2p, uo is the frequency of
vibration (here taken for A1g mode at different laser powers, KB is
the Boltzmann constant, DG(T) is shift in FWHM w.r.t its bulk value
at 300 K, B1 is fitting parameter in cm1 as calculated from Ref. 25
for our samples). The local temperature calculated from Klement
model is presented in Table 3. Lan et al. reported that for bulk
commercial SnO2 the extrapolated FWHM to 0 K is approximately
8 cm1 for B2g mode, whereas less than 2 cm1 for the Eg and A1g
modes respectively. The bulk value of FWHM for A1g mode was
reported to be ~10 cm1 at 300 K and it was subtracted in each
value of FWHM to get DG(T) for estimating temperature from
equation (3) [29,31]. The intensity of B2g mode in most of the
samples is too weak to obtain any quantitative information (FWHM
and exact peak position). Therefore only the frequency variation of
B2g mode as a function of laser powers are plotted, which follows a
similar trend as observed for A1g mode and depicted in Fig. S3 of
supplementary materials. In the Fig. 8(a and b) frequency shifts or
9
the peak shift Du is defined as u(IP or DP) - u(10 mW); where IP
and DP means increasing or decreasing laser powers. To account for
the contribution from anharmonic shifts as a function of increasing
laser power in our samples the following expression has been used:
[29,30].
   
vðln uÞ vðln uÞ
P ¼ gj b þ V ; where gj bðmaximumÞ
vT vT
 
¼ ¼ 1:9 x 105 K1
k vP T
(4)
The left-hand side of this equation is temperature dependent
frequency shift at a constant pressure (isobaric shift) which can be
directly measured by controlling the sample temperature during
the measurements as described by Lan et al. [29]. Here Gruneisen
parameters (gj) are very weakly dependent on temperature
gj ¼ 1.6, thermal expansion coefficient b ¼ 11.7  106/K.
k ¼ 4.5  104/kbar is the isothermal compressibility at room
temperature. Gruneisen parameter is defined as the ratio of the
relative change of the mode frequency to the relative change of
volume. The pure anharmonic shift (second term in right hand side)
can be separated by subtracting the maximum possible quasi-
harmonic shift (gj b ðmaximumÞ ¼ 1.9  105 K1). The contri-
bution from anharmonic shifts are listed in Table 2.
It can be inferred from the Table 2 that the local temperature is
rapidly increasing in Co doped SnO2 nanoparticles as compared to
undoped SnO2 with increasing laser power. The increase in local-
ized temperature leads to the phonon-phonon interactions
10 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836

Fig. 9. (a) The frequency shift and (b) Change in FWHM in Raman spectra of undoped and Co doped SnO2 nanoparticles as a function of Co doping concentration at different fixed
increasing laser powers (IP) and decreasing laser powers (DP).

Table 2
Estimation of local temperature by directly comparing the frequency and FWHM shift from Lan et al. (see Fig. S4 of supplementary materials).
 
Sample Name Frequency Frequency Temperature FWHM Temperature vðln uÞ
¼
vT P
 gj b þ
 
vðln uÞ
vT V

(A1g mode) Mode (u) (cm1) Shift (Du) (K) Shift (K) (x 105 K1) (-1.9  105 K1)23,25 (x 105 K1)

SC0-400 C 10 mW 633.1 0 300 12.2 683
25 mW 632.1 1.1 353 12.8 705 3.0 1.9 1.1
40 mW 631.2 2.0 386 15.2 795 3.5 ,, 1.6
100 mW 626.8 6.3 567 26.1 1310 3.7 ,, 1.8
SC3-400  C 10 mW 628.6 0 300 28.2 1410
25 mW 625.6 3.0 435 28.6 1430 3.5 1.9 1.6
40 mW 622.8 5.8 550 28.9 1445 3.7 ,, 1.8
100 mW 609.4 19.2 1024 34.1 1695 4.3 ,, 2.4
SC5-400  C 10 mW 627.5 0 300 33.4 1661
25 mW 623.4 4.1 479 35.3 1752 3.7 1.9 1.8
40 mW 619.5 8.0 628 48.2 2371 3.9 ,, 2.0
100 mW 610.5 17.0 954 39.8 1968 4.2 ,, 2.3
SC0-600  C 10 mW 635.1 0 300 6.6 519
25 mW 634.6 0.5 332 7 530 2.5 1.9 0.6
40 mW 634.1 1.0 358 8.0 556 2.7 ,, 0.8
100 mW 628.6 6.5 578 16.1 830 3.7 ,, 1.8
SC3-600  C 10 mW 630.9 0 300 16.5 849
25 mW 628.4 2.5 417 20.8 1055 3.4 1.9 1.5
40 mW 626.4 4.5 497 24.4 1228 3.6 ,, 1.7
100 mW 617.2 13.7 848 52.4 2572 4.0 ,, 2.1
SC5-600  C 10 mW 629.3 0 300 29.7 1483
25 mW 626.6 2.7 424 31.9 1588 3.5 1.9 1.6
40 mW 623.7 5.6 543 31.1 1550 3.7 ,, 1.8
100 mW 612.9 16.4 935 43.6 2151 4.2 ,, 2.3
 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836 11

Table 3
Estimation of local temperature by using Klement model from the frequency and FWHM shift presented by Lan et al.

Sample Name (A1g Total change in temperature ¼ DT þ 300 K (room temperature)

mode)
Temperature DT (in K) Based on frequency shift Temperature DT (in K)Based on FWHM shift

Frequency Shift (Du) 3 Phonon coupling (3 þ 4) phonon coupling FWHM shift 3 Phonon coupling (3 þ 4) phonon coupling

SC0-400  C 10 mW 0 0 0 12.2 398 352

25 mW 1.1 89 176 12.8 423 372
40 mW 2.0 178 254 15.2 500 445
100 mW 6.3 570 609 26.1 861 784
SC3-400  C 10 mW 0 0 0 28.2 930 849
25 mW 3.0 268 339 28.6 946 863
40 mW 5.8 517 565 28.9 964 871
100 mW 19.2 1716 1547 34.1 1140 1035
SC5-400  C 10 mW 0 0 0 33.4 1106 1012
25 mW 4.1 353 429 35.3 1171 1071
40 mW 8.0 708 736 48.2 1600 1475
100 mW 17.0 1520 1390 39.8 1319 1212
SC0-600  C 10 mW 0 0 0 6.6 209 181
25 mW 0.5 51 122 7 230 193
40 mW 1.0 95 170 8.0 270 225
100 mW 6.5 592 622 16.1 532 475
SC3-600  C 10 mW 0 0 0 16.5 540 486
25 mW 2.5 217 297 20.8 687 621
40 mW 4.5 398 459 24.4 798 730
100 mW 13.7 1229 1160 52.4 1746 1608
SC5-600  C 10 mW 0 0 0 29.7 975 895
25 mW 2.7 241 318 31.9 1052 964
40 mW 5.6 502 552 31.1 1030 941
100 mW 16.4 1471 1354 43.6 1440 1330

resulting into the increased anharmonic behaviour in the samples
with increasing laser power. Pure anharmonicity not only causes
the shifts in phonon vibrational frequencies, but also contributes
for phonon damping and lifetime broadening (increase in FWHM)
of phonon peaks [29,30]. For A1g modes the pure anharmonicity is
mainly from the cubic terms [29]. Similarly, the large shifting and
broadening for the B2g mode may be attributed to the large
contribution from quartic anharmonicity and the quasiharmonic
behaviors. The large differences observed between the tempera-
tures calculated after laser heating for frequency shifting and
FWHM variation of A1g mode of vibration is shown in Fig. 10. This is
mainly considered due to microstructure changes occurred during

Fig. 10. The comparison between the local temperatures created after laser heating (as a function of increasing laser powers) calculated by Klement Model based on 3 phonon
coupling for frequency shifting and FWHM variation of A1g mode of vibration. These differences are mainly accounted for the microstructure transformation.
12 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836
the measurements which can contribute to the additional FWHM
variation.
This is evidenced by the fact that after thermal annealing at
higher temperature (at 600  C) of all the samples the peak positions
of characteristics vibration bands (Eg, A1g, B2g) of SnO2 is not
significantly changed whereas the FWHM has been drastically
changed. Besides these the symmetric and asymmetric mode of
vibration of oxygen atom can also lead to create such large differ-
ences of temperature gradient due to the changes of the bond
strength and relaxation time in SnO2 nanoparticles as discussed in
detail by Zhang et al. for rutile TiO2 nanoparticles [15].
The clear differences in the local temperature calculated by two
different approach (Klement model versus direct comparison of
experimental data obtained by Lan et al.) as a function of laser
heating is not very clear at this stage, but these differences are likely
to be arise from the deviation of experimental results from theo-
retical models due to large degree of microstructural trans-
formations, particle shape and size effects, symmetry restrictions,
different ratio of cubic to quartic anharmonicity, modeling limita-
tion, and oversimplifying or overestimating the fitting parameters
and variables [15,29,30]. For examples, In Table 3, when Klement
model was used to approximate only the effect of 3 phonon
coupling or the effect of both 3 and 4 phonon coupling, an unrea-
sonable difference in the value of local temperature at certain laser
powers was observed, though in both cases a good fitting of
experimental data was performed. A details discussion about such
ambiguities in experimental and theoretically calculated data is out
of scope of this work, though in future the experiments for in-situ
thermal annealing during Raman measurements may be carried
out for an in-depth study to understand the nature of anharmo-
nicity in these samples.
3.5.2. Observations of microstructural transformations
In all the samples few additional peaks of vibration bands
(except characteristics Raman bands of SnO2) are appeared, some of
which have been formed during annealing or only with increasing
laser power during the measurements. In all the samples the
Raman spectra at low laser powers (for measurements in the order
of increasing powers) show the broad peaks (specially A1g and B2g
mode) indicates the amorphous and nanocrystalline nature of the
prepared samples [5]. Eg mode was not observed in undoped SnO2
sample whereas there is no appreciable change with Co doping in
Eg mode (around 459 cm1) which is accounted for the vibration of
two oxygen atoms opposite to each other but parallel to c-axis. This
mode is highly sensitive to oxygen vacancies than the other modes
indicates the presence of more oxygen vacancies in Co doped SnO2
samples [33]. The weak and broad vibration bands centered around
553 and 588 cm1 (Example: 588-594 cm1 for SC0-600  C sample)
can be assigned to surface-related defect bands originated from
disordering at the particle surface due to oxygen or tin vacancies
(called as M1 and M2 bands) of the SnO2 nanoparticles which
usually appears due to large surface area of the nano-sized SnO2
particles [34]. Hays et al. has reported that the A1g mode (at 630
Cm-1) appear below 1 mol % of Co-doping in SnO2, which was
disappeared for 3 and 5 mol % (3mol %) of Co doping and attrib-
uted to interstitial incorporation of Co2þ ions, phase lose and
related structural modifications of SnO2 nanoparticles [3]. In most
of the samples additional dominating peaks around 147, 171, 260,
305, 340, 503, 534 and 692 Cm-1 were observed for a laser power of

100 mW. The IR active mode around at 305, 340, 503, 534 and 692
Cm-1 corresponding to E(2) (2)
u (TO), Eu (LO), A2u(TO), B1u and A2u (LO)
modes (TO -transverse optical phonons, LO elongitudinal optical
phonons) respectively are also observed, which indicates the acti-
vation of disordered modes and Raman forbidden modes of SnO2
nanoparticles [15,29]. As reported by Lan et al. the band extending
in the region from 240 to 265 Cm-1 in most of the samples can be
either assigned to the Eu(1)- (TO), and Eu(1)- (LO) mode of vibration
or a secondary phase of disordered SnOx [19,29]. A weak hump
centered around 612 cm1 at different powers was mainly observed
in Co doped SnO2 samples, which is associated to the Eu(3)- TO
mode of vibration in the samples [29]. A weak hump around
718 cm1 in SC3 and SC5 samples at low laser powers is associated
to the Mco mode of vibration due to the Co doping in the samples.
Recently Mehraj et al. reported the similar IR active modes in the
Raman spectra of iron-cobalt (FeeCo) co-doped SnO2 nanoparticles
[33]. The broad band which may consist multiple peaks in the re-
gion 400-600 cm1 (except Eg and B1u mode) may be due to the
contribution from nonstoichiometric, disordered SnOx at the sur-
face and probably due to the high Raman activity from the inter-
action of surface material with adsorbed oxygen [21,32].
In a disordered crystal the presence of imperfections play an
important role which prevents the atoms displacements and their
vibration in phase resulting in the change or breakage of the
crystal’s local symmetry (where wavevector of the lattice vibration
q0 ¼ 0 fails) and therefore change in polarizability tensor. This
change in symmetry is even possible for forbidden Raman vibration
modes due to the loss in long-range order and therefore changes in
phonon density of states and thus making it optically possible to
contribute for the Raman spectra [21,32]. This broad peak is more
pronounced in undoped SnO2 as compared to the Co doped SnO2.
This is the clear indication of nonstoichiometric SnOx at the surface
as the distinct peaks activated by surface disorder (E(2)
u (TO), M1 and
M2 modes) can be directly visualized in Co doped samples at high
laser power of 100 mW [28,32].
The low intensity Raman active modes of B1g and A1g for SnO
phase were observed around 108 and 215 cm 1 respectively in
most of the Co doped SnO2 samples [19]. For SnO, two peaks as
detected by Sangletti et al. also, were observed at 113 and 211 cm1
corresponding to the B1g and A1g modes respectively [19,35]. The
peak positions centered around 147, and 171 were assigned to a
phase related to SnOx (x varying from 1.33 to 1.5), possibly Sn2O3 or
Sn3O4 as discussed by Sangaletti et al. and the group of Wang et al.
in their confocal Raman spectra study of SnO2 nanoribbons [19,21].
It is interesting to note down in case of SC3-400  C and SC3-600  C
samples that the peaks intensity at 147 and 305 cm1 was initially
increased with increasing laser power and these peaks diminished
at high laser power of 100 mW. Further recording the spectra in
reverse order at low powers of 25 and 10 mW (clearly visible in
SC3-400  C) these new peaks were completely vanished. As a result
of the measurements in reverse order the Raman spectra is less
noisy, the broadening of A1g and B2g mode is reduced with the
significant increase in the intensity. Similar observation can be
noted from the Raman spectra of other samples. These results prove
that microstructure changes due to presence of defects, hydroxyl,
methane group’s etc. for partial formation of SnO and non-
stoichiometric SnOx (1<x>2) has been occurred as a function of
laser heating in the SnO2 nanoparticles. Though the continuous
exposure of laser light during measurement drastically reduced the
intensity of these additional phases and results into pronounced
characteristics Raman band of SnO2 nanoparticles. Recently hier-
archical 3D flower like nanostructures of Sn3O4 were prepared by Y.
He at al. and their structure were confirmed after comparing the
XRD and Raman spectra with the reference samples of SnO and
SnO2 [35,36]. Y. He et al. reported that the main characteristic peaks
of Sn3O4 phase are centered at 72, 90, 143, 170 and 238 cm1 [36].
The presence of monoclinic Sn3O4 phase (instead of saying it
nonstoichiometric SnOx (1<x>2) as reported previously) with
increasing laser power can be confirmed in the undoped and Co
doped SnO2 samples after the careful investigations of the Raman
spectra among the results reported by Wang et al. group, Y. He et al.
 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836
group and B. Eifert et al. group [20,21,36]. Though there is no other
direct way to realize the presence of Sn2O3 phase formation
(assigned at 170 cm1 by Wang et al.) as a function of laser heating
but the theoretical and experimental evidenced presented by B.
Eifert et al. strongly suggest the formation of only Sn3O4 phase
[20,21].
The presence of SnO phase as detected in XRD and Raman and
then emergence of monoclinic Sn3O4 phase (not detected in XRD)
during Raman measurements as a function of laser heating in-
dicates the partial transformation of SnO phase into Sn3O4 phase
has occurred as this has no significant influence in the undoped
samples. This strengthens the hypothesis of Wang et al. and Dai
et al. that the SnO2 formation in an oxygen atmosphere takes place
in two steps by first forming and intermediate Sn3O4 phase from
SnO and then stabilizing it to SnO2 phase [20,21,37]. In our samples
this transition to form different phase of tin oxide is caused by laser
heating in ambient conditions. There is no signature for other mode
of vibration related to the carbon impurity, metallic Co, cobalt oxide
and orthorhombic SnO2 etc. in all the samples. Therefore it can be
inferred that the appearance of new vibration bands corresponding
to SnO and Sn3O4 phase and broadening and shifting in the peak
position of Raman spectra for A1g and B2g modes after Co doping at
the same laser power (for ex: either at 10 mW or at 22 mW etc.)
indicates the micro-structural changes and an increase in oxygen
vacancy defects inside the lattice [25,33]. These microstructure
changes (such as lattice expansion, improved crystallinity, phase
transformation etc.) are dominant in Co doped samples.
In case of the SC3 and SC5 samples, while recording the Raman
spectra in reverse order at low powers of 25 and 10 mW, it is
interesting to note that the FWHM of A1g and B2g mode has been
significantly decreased whereas the peak positions have been
slightly shifted towards higher wavenumber side (beside annealing
at 600  C), which is in contrary to as observed for anharmonic
behaviour. The broadening and shifting as a function of Co doping
concentration can be understood from the relationship between
crystallite size and phonon momentum distribution based on
Heisenberg uncertainty principle. This can be written as DX. DPħ2/
4, where DX is the particle size, DP is the phonon momentum
distribution, and ħ is the reduced Planck’s constant [16,33]. As the
particle size decreased, the phonon is increasingly confined within
the particle and the phonon momentum distribution increased.
This broadening of the scattered phonon momentum is according
to the law of momentum. This phonon dispersion causes asym-
metric broadening and may lead to a shift of the conservation of
Raman bands. This broadening is reduced and the relative peak
intensity (for A1g mode) is enhanced when the measurements were
repeated in reverse order at low laser powers of 10 and 25 mW. This
clearly suggests that the continuous exposure of laser light with
different laser powers might have increased the crystallite size and
therefore the local structural modification were occurred during
measurements which further improved the localized crystallinity
at the same spot. This is an addition to the effect of thermal
annealing where the similar shifting towards higher wavenumber
is already explained.
So overall peak broadening and shifting in the entire range of
spectra can be considered for three main reasons of (i) large
anharmonic behaviour due to phonon-phonon interaction (mainly
A1g and B2g), (ii) microstructure changes (including particle size
effect) occurred with laser heating in most of the samples (Eg, A1g
and B2g) and (iii) partial presence of SnO and mainly the presence of
Sn3O4 phase in Co doped SnO2 nanoparticles.
4. Conclusions
Co-doped SnO2 nanoparticles synthesized by chemical co-
13
precipitation method showed interesting laser power dependent
phonon anharmonicity and microstructural variation during
Raman measurements. All the peaks in the Raman spectra were
well identified and assigned to the respective vibrational modes of
bulk SnO2, SnO phase, forbidden Raman bands and a non-
stoichiometry SnOx phase which is mainly assigned to the Sn3O4
phase in all the samples. The activation of IR active modes and
Raman forbidden modes in the samples were observed due to the
presence of large surface disordering, symmetry breakage and lack
of long range ordered crystal structure in the nanoparticles surface.
The emergence of new phases, and broadening and shifting in the
peak position of Raman spectra for A1g and B2g modes after Co
doping at the same laser power (for ex: either at 10 mW or at
22 mW etc.) strongly indicated that the micro-structural changes
were occurred during measurements. The continuous exposure of
laser light at the same spot of measurements has improved the
crystallinity of Co doped SnO2 nanoparticles. The results indicate
that an intermediate phase of Sn3O4 was formed from SnO, which
was then stabilized to the SnO2 nanocrystals as a function of
increasing laser powers. These results are essentially very impor-
tant in order to avoid any erroneous conclusions about structural
and optical properties of various wide bandgap semiconductors
nanomaterials and to carefully use them for various optoelectronics
application.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Lalit Kumar Gaur: Methodology, Data curation, Writing - orig-
inal draft. Mohan Chandra Mathpal: Conceptualization, Software,
Supervision, Writing - review & editing, Validation. Promod
Kumar: Methodology, Visualization, Investigation, Validation. S.P.
Gairola: Supervision, Resources, Validation. Vivek Agrahari:
Methodology, Data curation. M.A.R. Martinez: Formal analysis,
Resources. F.F.H. Aragon: Software, Validation, Formal analysis.
Maria A.G. Soler: Visualization, Resources, Investigation. H.C.
Swart: Formal analysis, Visualization, Resources, Validation. Arvind
Agarwal: Supervision, Resources.
Acknowledgments
One of the author is thankful to CAPES -PNPD fellowship, Brazil
for providing the funding to conduct this research (Process No-
23106.067256/2018-51).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jallcom.2020.154836.
References
[1] V. Agrahari, M.C. Mathpal, M. Kumar, A. Agarwal, Investigations of optoelec-
tronic properties in DMS SnO2 nanoparticles, J. Alloys Compd. 622 (2015)
48e53, https://doi.org/10.1016/j.jallcom.2014.10.009.
[2] A. Bouaine, N. Brihi, G. Schmerber, C. Ulhaq-Bouillet, S. Colis, A. Dinia, Struc-
tural, optical, and magnetic properties of Co-doped SnO2 powders synthe-
sized by the coprecipitation technique, J. Phys. Chem. C 111 (2007)
2924e2928, https://doi.org/10.1021/jp066897p.
[3] J. Hays, A. Punnoose, R. Baldner, M.H. Engelhard, J. Peloquin, K.M. Reddy,
Relationship between the structural and magnetic properties of Co-doped SnO
2 nanoparticles, Phys. Rev. B 72 (1e7) (2005), 075203, https://doi.org/
14 L.K. Gaur et al. / Journal of Alloys and Compounds 831 (2020) 154836
10.1103/PhysRevB.72.075203.
[4] M.K. Jaiswal, R. Kumar, Studies of dense electronic excitation induced modi fi
cation in cobalt doped SnO 2 thin fi lms prepared by RF sputtering technique,
J. Alloys. Compd. 648 (2015) 550e558, https://doi.org/10.1016/j.jall-
com.2015.07.050, 550e558 Contents. 648.
[5] A. Kar, S. Kundu, A. Patra, Surface defect-related luminescence properties of
SnO 2 nanorods and nanoparticles, J. Phys. Chem. C 115 (2011) 118e124.
[6] V. Agrahari, A.K. Tripathi, M.C. Mathpal, A.C. Pandey, S.K. Mishra, R.K. Shukla,
A. Agarwal, Effect of Mn doping on structural , optical and magnetic properties
of SnO 2 nanoparticles, J. Mater. Sci. Mater. Electron. 26 (2015) 9571e9582,
https://doi.org/10.1007/s10854-015-3620-0.
[7] Y.B. Guillen-Baca, C.A. Vilca Huayhua, K.J. Paz Corrales, A.F. Carlos-Chilo,
F.F.H. Arago
n, M.C. Mathpal, S.W. da Silva, J.A.H. Coaquira, W. Sucasaire,
J.A. Guerra, D.G. Pacheco-Salazar, Lattice strain effects on the structural
properties and band gap tailoring in columnarly grown Fe-doped SnO 2 films
deposited by DC sputtering, J. Phys. D Appl. Phys. 52 (2019) 465306, https://
doi.org/10.1088/1361-6463/ab3968.
[8] Y. Zhang, M. Wang, Y. Wang, J. Feng, Y. Zhang, X. Sun, B. Du, Q. Wei, Label-free
photoelectrochemical immunosensor for amyloidb-protein detection based
on SnO2/CdCO3/CdS synthesized by one-pot method, Biosens. Bioelectron.
126 (2019) 23e29, https://doi.org/10.1016/j.bios.2018.10.045.
[9] Y. Zhang, R. Xu, Q. Kang, Y. Zhang, Q. Wei, Y. Wang, H. Ju, Ultrasensitive
photoelectrochemical biosensing platform for detecting N-terminal pro-brain
natriuretic peptide based on SnO2/SnS2/mpg-C3N4 amplified by PbS/SiO2,
ACS Appl. Mater. Interfaces 10 (2018) 31080e31087, https://doi.org/10.1021/
acsami.8b11312.
[10] N. Zhang, Y. Wang, G. Zhao, C. Wang, Y. Li, Y. Zhang, H. Wang, Q. Wei,
A photoelectrochemical immunosensor based on CdS/CdTe-cosensitized SnO2
as a platform for the ultrasensitive detection of amyloid b-protein, Analyst
145 (2020) 619e625, https://doi.org/10.1039/c9an01848d.
[11] A. Punnoose, J. Hays, Possible metamagnetic origin of ferromagnetism in
transition-metal-doped SnO2, J. Appl. Phys. 97 (2005) 97e100, https://
doi.org/10.1063/1.1853331.
[12] B. Babu, C.V. Reddy, J. Shim, R.V.S.S.N. Ravikumar, J. Park, Effect of cobalt
concentration on morphology of Co-doped SnO 2 nanostructures synthesized
by solution combustion method, J. Mater. Sci. Mater. Electron. 27 (2016)
5197e5203, https://doi.org/10.1007/s10854-016-4413-9.
[13] F.F.H. Arago
n, L. Villegas-Lelovsky, L. Cabral, M.P. Lima, J.C.R. Aquino,
M.C. Mathpal, J.A.H. Coaquira, S.W. da Silva, L.C.C.M. Nagamine, S.O. Parreiras,
P.L. Gastelois, G.E. Marques, W.A.A. Macedo, Tailoring the physical and
chemical properties of Sn1 x Co x O2 nanoparticles: an experimental and
theoretical approach, Phys. Chem. Chem. Phys. 22 (2020) 3702e3714, https://
doi.org/10.1039/c9cp05928h.
[14] H. Tsai, R. Asadpour, J. Blancon, C.C. Stoumpos, O. Durand, J.W. Strzalka,
B. Chen, R. Verduzco, P.M. Ajayan, S. Tretiak, J. Even, M.A. Alam,
M.G. Kanatzidis, W. Nie, A.D. Mohite, Light-induced lattice expansion leads to
high-efficiency perovskite solar cells 70 (2018) 67e70.
[15] Y. Zhang, C.X. Harris, P. Wallenmeyer, J. Murowchick, X. Chen, Asymmetric
lattice vibrational characteristics of rutile TiO2 as revealed by laser power
dependent Raman spectroscopy, J. Phys. Chem. C 117 (2013) 24015e24022,
https://doi.org/10.1021/jp406948e.
[16] M.C. Mathpal, A.K. Tripathi, M.K. Singh, S.P. Gairola, S.N. Pandey, A. Agarwal,
Effect of annealing temperature on Raman spectra of TiO2nanoparticles,
Chem. Phys. Lett. 555 (2013) 182e186, https://doi.org/10.1016/
j.cplett.2012.10.082.
[17] B. Choudhury, A. Choudhury, Luminescence characteristics of cobalt doped
TiO2 nanoparticles, J. Lumin. 132 (2012) 178e184, https://doi.org/10.1016/
j.jlumin.2011.08.020.
[18] N. Wan, X. Lu, Y. Wang, W. Zhang, Y. Bai, Y. Hu, Improved Li storage perfor-
mance in SnO 2 nanocrystals by a synergetic doping, Nat. Publ. Gr. (2016)
1e11, https://doi.org/10.1038/srep18978.
[19] L. Sangaletti, L.E. Depero, B. Allieri, F. Pioselli, E. Comini, G. Sberveglieri,
M. Zocchi, Oxidation of Sn thin films to SnO2. Micro-Raman mapping and x-
ray diffraction studies, J. Mater. Res. 13 (1998) 2457e2460, https://doi.org/
10.1557/JMR.1998.0343.
[20] B. Eifert, M. Becker, C.T. Reindl, M. Giar, L. Zheng, A. Polity, Y. He, C. Heiliger,
P.J. Klar, Raman studies of the intermediate tin-oxide phase, Phys. Rev. Mater.
1 (2017) 1e6, https://doi.org/10.1103/PhysRevMaterials.1.014602.
[21] F. Wang, X. Zhou, J. Zhou, T.K. Sham, Z. Ding, Observation of single tin dioxide
nanoribbons by confocal Raman microspectroscopy, J. Phys. Chem. C 111
(2007) 18839e18843, https://doi.org/10.1021/jp709701s.
[22] A. Stevanovic, M. Bu, Z. Zhang, J.T. Yates, Photoluminescence of TiO 2 : effect of
UV light and adsorbed molecules on surface band structure, J. Am. Chem. Soc.
134 (2012) 324e332, https://doi.org/10.1021/ja2072737.
[23] J. Chen, E.A. Pidko, V. V Ordomsky, T. Verhoeven, E.J.M. Hensen, J.C. Schouten,
T.A. Nijhuis, Catalysis science & technology, Catal. Sci. Technol. 3 (2013)
3042e3055, https://doi.org/10.1039/c3cy00358b.
[24] V. Agrahari, M. Chandra, M. Sachin, K. Mahendra, Cr modified Raman , optical
band gap and magnetic properties of SnO 2 nanoparticles, J. Mater. Sci. Mater.
Electron. 27 (2016) 6020e6029, https://doi.org/10.1007/s10854-016-4525-2.
[25] A. Bouaine, N. Brihi, D. Jijel, Structural , optical , and magnetic properties of
Co-doped SnO[dw]2[/dw] powders synthesized by the coprecipitation tech-
nique, J. Phys. Chem. C 111 (2007) 2924e2928.
[26] L.K. Gaur, P. Kumar, D. Kushavah, K.R. Khiangte, M.C. Mathpal, V. Agrahari,
S.P. Gairola, M.A.G. Soler, H.C. Swart, A. Agarwal, Laser induced phase trans-
formation influenced by Co doping in TiO2 nanoparticles, J. Alloys Compd. 780
(2019) 25e34, https://doi.org/10.1016/j.jallcom.2018.11.344.
[27] J. Mazloom, F.E. Ghodsi, Spectroscopic , microscopic , and electrical charac-
terization of nanostructured SnO 2 : Co thin films prepared by sol e gel spin
coating technique, Mater. Res. Bull. 48 (2013) 1468e1476, https://doi.org/
10.1016/j.materresbull.2012.12.069.
[28] S. Mehraj, M.S. Ansari, Structural , electrical and magnetic properties of ( Fe ,
Co ) co-doped SnO 2 diluted magnetic semiconductor nanostructures, Phys. E
Low Dimens. Syst. Nanostruct. 65 (2015) 84e92, https://doi.org/10.1016/
j.physe.2014.08.016.
[29] T. Lan, C.W. Li, B. Fultz, Phonon anharmonicity of rutile SnO2 studied by
Raman spectrometry and first principles calculations of the kinematics of
phonon-phonon interactions, Phys. Rev. B 86 (1e7) (2012) 134302, https://
doi.org/10.1103/PhysRevB.86.134302.
[30] T. Lan, X. Tang, B. Fultz, Phonon anharmonicity of rutile TiO2 studied by
Raman spectrometry and molecular dynamics simulations, Phys. Rev. B 85
(1e11) (2012), 094305, https://doi.org/10.1103/PhysRevB.85.094305.
[31] T. Sato, T. Asari, Temperature dependence of the linewidth of the first-order
Raman spectrum for SnO2 crystal, J. Phys. Soc. Jpn. 64 (1994) 1193e1199.
[32] A. Die
guez, A. Romano-Rodríguez, A. Vila , J.R. Morante, The complete Raman
spectrum of nanometric SnO2particles, J. Appl. Phys. 90 (2001) 1550e1557,
https://doi.org/10.1063/1.1385573.
[33] S. Mehraj, M.S. Ansari, Alimuddin, Structural , electrical and magnetic prop-
erties of ( Fe , Co ) co-doped SnO 2 diluted magnetic semiconductor nano-
structures, Phys. E Low Dimens. Syst. Nanostruct. 65 (2015) 84e92, https://
doi.org/10.1016/j.physe.2014.08.016.
[34] F.H. Arago
n, J.A.H. Coaquira, P. Hidalgo, S.W. Da Silva, S.L.M. Brito, D. Gouve^a,
P.C. Morais, Evidences of the evolution from solid solution to surface segre-
gation in Ni-doped SnO2 nanoparticles using Raman spectroscopy, J. Raman
Spectrosc. 42 (2011) 1081e1086, https://doi.org/10.1002/jrs.2802.
[35] Y. He, D. Li, J. Chen, Y. Shao, J. Xian, X. Zheng, P. Wang, RSC Advances Hier-
archical 3D Nanostructures under Visible Light y, 2014, pp. 1266e1269,
https://doi.org/10.1039/c3ra45743e.
[36] Y. He, D. Li, J. Chen, Y. Shao, J. Xian, X. Zheng, P. Wang, Sn 3 O 4 : A Novel
Heterovalent-Tin Photocatalyst with Hierarchical 3D Nanostructures under
Visible Light, 2013, pp. 1e10.
[37] Z.R. Dai, Z.W. Pan, Z.L. Wang, Z.L. Dai, Z.R., Z.W. Pan, Wang, Growth and
structure evolution of novel tin oxide diskettes, J. Am. Chem. Soc. 124 (2002)
8673e8680, https://doi.org/10.1021/ja026262d.