Physica B 654 (2023) 414734

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Physica B: Condensed Matter

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DFT investigations of structural stability and structure dependent physical

behavior of SnO2 polymorphs
Kanimozhi Balakrishnan a, Suresh Alagarsamy b, Vasu Veerapandy a, *
a
Department of Computational Physics, School of Physics, Madurai Kamaraj University, Palkalai Nagar, Madurai, 625 021, Tamil Nadu, India
b
Department of Physics, National Institute of Technology, Tiruchirappalli, 620 015, Tamil Nadu, India

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, we investigated the electronic, mechanical and thermodynamic properties of various phases of SnO2
Density functional theory from first principles method. Here the five phases of choice are rutile, α-PbO2, CaCl2, pyrite, and ZrO2. To begin
Tin dioxide with, from the key parameters such as total energy, bond length and cohesive energy of the phases, we theo­
Symmetry
retically estimated their phase stability. Interestingly, the estimated elastic moduli are dependent on the cor­
Phase stability
Elasticity
responding crystal symmetry. These parameters are also comparable with reported values. Further, from the
Phonons phonon dispersion relation, we recognized the dynamically stable phases. In addition, we also calculated the
Debye temperature of the polymorphs from the average wave velocity, νm. Finally, we presented the relationship
between the physical properties of the phases and their structural symmetry sequence. Such a relationship is not
derived earlier in any theoretical and experimental report.

1. Introduction calculation on SnO2 is carried out quite extensively within the frame­
work of density functional theory. For instance, Erdem et al. reported
Density Functional Theory (DFT) is one of the most advanced the structural properties of SnO2 polymorphs, employing the DFT cal­
computational techniques for predicting the physical properties of ma­ culations based on Local Density Approximation (LDA) of ultra-soft
terials with good accuracy. However, the true intent of this theory be­ pseudopotentials (US-PPs). The electronic and thermodynamic stabil­
comes significant in optimizing the most viable candidate from material ity of SnO2 polymorphs and their high pressure behavior were also re­
database. For instance, while designing storage devices like Lithium-ion ported [14,15]. Likewise, K. Parlinski et al. investigated the lattice
Batteries (LIBs), the selection of an appropriate electrode is of prime dynamic property of SnO2 and the pressure-dependence of the lattice
concern for which one requires a stable crystal structure to enhance the constants of SnO2 [16]. Specifically, in SnO2, most of the studies concern
cyclic lifetime and device stability [1]. In this respect, tin dioxide (SnO2) the mechanical and thermal properties of the rutile phase alone. Since,
based nanostructures have been identified to show improved perfor­ the crystal structure of rutile SnO2 is well studied, the focus is now on the
mance in LIBs and supercapacitors [2,3]. The reason is alloying/deal­ rest of the polymorphs [14,17–20]. Yet only a few studies are available,
loying processes to reversibly store/release lithium ions during that too on the mechanical property alone. In this regard, Pratik Kumar
charge/discharge [4]. In general, Alkali, Alkaline and transition metals Das et al. studied the elastic property of four SnO2 polymorphs under
form ionic oxides, which are covalent in nature. Similarly, transparent various pressure and their directional dependence of the young’s
conducting oxides are widely used in devices such as solar cells [5–8], modulus [21]. They also demonstrated that the pressure dependent
smart windows [9,10] and Liquid Crystal Displays (LCDs) [10–13] for shear anisotropy of the tetragonal and the orthogonal phases. In another
their high optical transparency and electrical conductivity. Metal oxides report, Liu et al. employed DFT method to estimate the
are therefore one of the most significant class of materials in engineer­ pressure-dependent elastic constants, shear anisotropy and elastic Debye
ing, science and technology for their unique shape and size dependent temperature of the rutile phase and validate the results [22,23]. In
physical and chemical properties. For this dependency, they are also the general, theoretical predictions of bandgap often fail to match the
rigorously researched materials within theoretical limits. experimentally obtained bandgap. This is usually due to a poor
It is for these reasons; the first-principles electronic structure description of standard local and semi-local functional in the electronic

* Corresponding author.
E-mail address: [Link]@[Link] (V. Veerapandy).

[Link]
Received 5 October 2020; Received in revised form 9 June 2021; Accepted 6 February 2023
Available online 9 February 2023
0921-4526/© 2023 Elsevier B.V. All rights reserved.
K. Balakrishnan et al. Physica B: Condensed Matter 654 (2023) 414734

properties of strongly correlated materials. In order to improve the

bandgap accuracy and physical behavior predictability, a combination
of HF and DFT theories called hybrid functional, is developed [24,25].
Hence, the purpose of the present study is to investigate the struc­
tural, electronic and mechanical properties of five SnO2 polymorphic
structures using DFT and to investigate the structural stability from
cohesive energy and phonon dispersion spectra calculations. We inves­
tigated the bandgap of these five SnO2 phases which is in good agree­
ment with previous results [26]. Firstly, we calculated the cohesive
energy of all five polymorphs. Later, from density functional perturba­
tion theory (DFPT) [27,28], the lattice vibrational properties of five
phases were estimated. Generally, the lattice dynamics can be calculated
via. two approaches in DFT; one through the direct, and the other
through linear response approach. Here, we used the direct method to
derive the force constant dynamical matrix and phonon frequencies. The
Debye temperature is calculated using the quasi-harmonic approxima­
tion for all polymorphs (QHA) [29]. Finally, all results are interpreted in
Fig. 1. Crystal structures of the SnO2 polymorphs (gray and red colors repre­
terms of the associated symmetry sequence of crystal structure per­ sents Sn and O atoms, respectively. (a) Rutile (P42/mnm) (b) CaCl2 - type
spectives. Even though a number of reports are already available in (Pnnm), (c) α-PbO2-type (Pbcn), (d) Pyrite-type (Pa 3), (e) ZrO2-type (Pbca).
analyzing the SnO2 polymorphs, we have particularly focused on testing
the phase stability and its physical properties from symmetry
[14,15,37]. The third-order Birch–Murnaghan EOS is the relation be­
considerations.
tween the volume of a crystal system and the total energy is given in
Listed below are the sections of this paper: Section 2 describes the
Equation (1).
computational method. Section 3 deals with the calculations of struc­
tural, electronic, mechanical properties and lattice dynamic studies as E(V) = E0
well as comparison with other calculations and experimental results. {[( )
2/3
]3 [( )
2/3
]2 [ ( )2/3 ]}
The results are finally summarized in Section 4. +
9V0 B0 V0 ′
− 1 B0 +
V0
− 1 6− 4
V0
(1)
Other software programs used in this work are Vesta [30] and 16 V V V
XCrySDen [31] for obtaining atomic positions, Bravais -lattice vectors,
images & calculations of conventional cell. The GNUplot program was Where E0 is the total energy, V0 is the equilibrium volume, B0 is the bulk
used to plot the electronic structure of the polymorphs [32,33]. modulus, and B0 is the first derivative of the bulk modulus with respect
′

to pressure. Total energy-volume data fitted to EOS for all phases of

2. Computational method SnO2 is given in Fig. 2. The minimum energy in Fig. 2 indicates the
equilibrium lattice parameter and volume of the unit cell at zero pres­
Our calculations are performed using DFT within the ab initio plane- sure. The cohesive energy is also calculated for all phases of SnO2.
wave approach, with the code PWscf in the Quantum-ESPRESSO pack­ The rutile SnO2 crystallizes in a tetragonal structure with the lattice
age [34]. A projector-augmented wave generalized-gradient approxi­ constants of a = b = 4.737 Å, c = 3.816 Å, and α = β = γ = 90◦ [38,39]. It
mation (PAW-GGA) with Perdew-Burke-Ernzerhof (PBE) [29]. While has two formula units with P42/mnm space group and D14 2h point group
oxygen atom has 2s2 2p4 valence state, Sn atom has 5s2 5p2 which are symmetry containing six atoms. The two Sn atoms occupy the center and
referred from the pseudopotential text respectively. The structural cal­ the apex of the tetrahedron, and each oxygen is coordinated to three Sn
culations took into account the converged kinetic energy cut-off of 60 Ry atoms, which leads to an OSn3. The k-points for the rutile structure
for SnO2 polymorphs. in order to perform the standard calculations, we belong to the simple tetragonal Brillouin zone which are taken from the
used a convergence threshold of 10− 6 eV. Brillouin zone sampling is literature of M. Worsdale et al. [40]. The calculated equilibrium lattice
converged at 8 × 8 × 10 for rutile and CaCl2; 8 × 6 × 6 for α-PbO2; 4 × 2 parameters a and c, as well as the bulk modulus B0 and B0 are given in
′

× 4 for ZrO2-type and 6 × 6 × 6 for pyrite structures. Each phase of SnO2 Table 1. The lattice parameters match well with the experimental and
contains different amounts of formula units where rutile and CaCl2
contain 2 formula units, α-PbO2 and pyrite with 4 formula units, and
ZrO2-type with 8 formula units. The structures were optimized, and the
optimized lattice parameters have been used for further calculations.
Optimized structures of SnO2 polymorphs are given in Fig. 1. The
phonon dispersion and dynamical matrices are calculated for 4 × 4 × 4
gird of wave vectors. The phonon vibrational frequencies at Γ point were
calculated for the polymorphs. Also, the vibrational frequencies and
Debye temperature obtained from the Interatomic Force Constant (IFCs)
by using the PWscf phonon code with thermo_pw [35,36].

3. Results and discussion

3.1. Structure of SnO2 polymorphs

The geometrical optimization is performed for all the phases under

study. All calculations are carried out under zero pressure. The ground-
state properties of SnO2 polymorphs are investigated from their total
energy, the lattice parameters, electronic and mechanical property. The
bulk modulus of SnO2 phases are obtained by fitting the calculated total Fig. 2. Variation of total energy versus volume curve of SnO2 polymorphs
energy with the third-order Birch-Murnaghan equation of states (EOS) crystal structure.

2
K. Balakrishnan et al. Physica B: Condensed Matter 654 (2023) 414734

Table 1 EOS. The equilibrium lattice parameters were calculated and there is
Structural properties of SnO2 under zero pressure, the lattice parameters a, b, only 0.6% discrepancy than those given by Gracia L et al. [45]. The
and c, are in Å; zero-pressure bulk modulus values, B0 are B0 in Gpa, it’s pressure cation with the six-fold is centered in a strongly distorted octahedron
′

derivative, unit cell volume V0 in (Å3) and cohesive energy Ecoh are in Ry. with three different Sn–O distances, say 2.06, 2.04 to and 2.11 Å. This is
Theorya Theoryb primarily due to the presence of two additional anions at 3.10 Å in SnO2
in this polymorph. The bulk modulus of α-PbO2-type SnO2 was found to
Rutile – type
a 4.805 4.830 4.715 4.737c be 168.1 GPa which is comparatively smaller than the first two phases,
c 3.260 3.236 3.194 3.186c although it shares the common crystal symmetry with CaCl2– type
B0 177.3 173 228 205c [45–48].
B0
′
5.07 5.4 4 —
In the case of the cubic pyrite structure (space group Pa 3, Z = 4), it
V0 73.71 — 71 —
Ecoh 0.440 — — — has the Th6 symmetry, where oxygen atoms are settled at 8c sites and Sn
CaCl2 – type atoms are at 4a sites. In this structure, each Sn ion has an inner shell of
a 3.161 4.827 4.708 4.653c six O ions with a further two O ions slightly away from Sn. The opti­
b 4.670 4.829 4.720 4.631c
mized lattice parameters and the bulk modulus of this phase is in
c 4.747 3.238 3.195 3.155c
B0 173.8 173 228 204c Table 1. The lattice parameter was approximately 4.7% greater than the
B0
′
5.02 5.6 4 — experimental results reported by Li W, Walther CFJ et al. [25]. The
V0 73.85 — 71 — calculated bulk modulus of this phase of SnO2 is smaller than previous
Ecoh 0.404 — — — results from theoretical calculations [45]. In comparison with other
α-PbO2-type phases, the bulk modulus is the largest, which may due to the high
a 4.738 4.785 4.707 4.744c
b 5.764 5.822 5.710 5.707c
symmetric nature of the cubic structure. The bond distance of Sn–O in
c 5.247 5.306 5.246 5.209c pyrite phase are 2.09 and 3.59 Å. Similarly, the structural optimization
B0 168.1 172 228 208c and the mechanical calculations of ZrO2 (space group Pbca, Z = 8) type
B0
′
4.88 4.6 4 — were carried out and the results are given in Table 1. Furthermore, the
V0 144.90 — 141.2 — ZrO2 phase is comparatively a larger structure than the other poly­
Ecoh 0.411 — — —
Pyrite –type
morphs with 8 formula units. The Sn and O distances are 2.14, 2.09 Å
a 5.1337 5.167 5.066 4.888c and Sn – Sn distance is 3.62 Å. The equilibrium structure of this phase
B0 195.8 198 293 228 occurs at b/a = 1.965 and c/a = 1.015. This is the strongly distorted
B0
′
2.59 5.0 4 — structure due to the larger bond distance. The lattice parameters of this
V0 135.79 — 129.6 — phase also compared with experimental results reported by S. R. Shieh
Ecoh 0.406 — — —
ZrO2-type
[49].
a 5.112 5.145 9.970 4.731d The cohesive energy of the crystal is calculated from Equation (2),
b 10.049 10.132 5.113 9.304 where Ecoh represents the bulk cohesive energy per unit cell, whereby
c 5.214 5.233 5.022 4.893 Ebulk is the energy of the SnO2 formula unit and Eatom for Sn and O single
B0 170.9 185 273 259
free atom.
B0
′
6.46 5.0 4 —
V0 269.05 — 255.2 — Ebulk − NEatom
Ecoh 0.402 — — — Ecoh = (2)
N
a
Reference [14]. The value of cohesive energy required to separate the constituent
b
Reference [45]. atom from the structure is important for the evaluation of the chemical
c
Reference [42].
d bond length of the crystals. The computed cohesive energy of the rutile
Reference [49].
phase SnO2 is approximately 0.440 Ry. This result coincides well with
the experimental value of 0.44 Ry [50]. The values of atomization en­
other theoretical results of I. Erdem et al. [14]. We found out that the ergy of all phases were also calculated as 0.404, 0.405, 0.406, and 0.402
most stable structure of rutile SnO2 occurs at c/a = 0.678. The calculated Ry for CaCl2, α-PbO2, pyrite, and ZrO2 – type respectively.
lattice parameters a and c are 0.2–1.5% smaller than the experimental
values. The calculated bond lengths of Sn–Sn are 3.17 and 4.69 Å which 3.2. Electronic properties of SnO2
is greater than Sn–O bond length 2.04 and 2.02 Å. The bond angle of
Sn–O–Sn is 101.8◦ and the O–Sn–O angle is 90◦ , which corresponds to 3.2.1. Electronic band structure
the experimental results of Arun Kumar Sinha et al. [41]. Here we examine the electronic properties of all the SnO2 poly­
The CaCl2 – type structure has orthorhombic symmetry (Pnnm, Z = 2) morphs. The details of the electronic property provide information on
with D122h point group. This phase possesses similar properties as that of the macroscopic properties of the system such as bandgap, conductivity,
rutile one. The crystal is optimized and the optimized lattice parameters and chemical bonding. So the electronic band structure and density of
are listed in Table 1. The stable structure of this phase occurs at b/a = states for the five different phases of SnO2 are computed using GGA
1.477, c/a = 1.501. Our results for the structural parameters and bulk approximation. The band structure of SnO2 along with the high sym­
modulus in equilibrium crystal structure are in good agreement with the metric Bravais lattice of the tetragonal, orthorhombic, and cubic struc­
available theoretical and experimental values [42–44]. The CaCl2 type tures is presented in Fig. 3a–e. The lowest dense bands, which are below
has two Sn–O distances, say 2.05 Å and four of 2.04 Å. The calculated the Fermi level in all phases, are due to “2p” states of oxygen atoms with
distances of Sn–Sn are 3.18 Å and 4.67 Å, which are slightly greater than a valence bandwidth of around 9 eV. Bands above the Fermi level in all
the rutile structure. The estimated bulk modulus of this phase is found to cases composed of “s" and “p" states of Sn hybridize with O ′′ p" states.
be smaller than the experimental value reported by Haines, J et al. [44] This is also consistent with previously reported and discussed results for
and corresponds to the rutile phase, even though its crystal symmetry is rutile phases. It can be seen that the bandgap occurs at Γ i.e., between
different. Since the lattice parameters in this case, vary from 0.6% to the highest occupied valence band and lowest unoccupied conduction
0.8% compared to the experimental value [44,45]. band. The calculated bandgap energy of rutile is 1.361 eV, which is in
In the orthorhombic α-PbO2 type with space group (Pbcn, Z = 4) has exact agreement with the previous theoretical results. The bandgap of
D14
2h point group symmetry, the oxygen atoms are at 8d sites and Sn at 4c CaCl2, α-PbO2 and Pyrite phases is also located at Γ- Γ point of the
sites. Table 1 shows the results obtained from the Birch–Murnaghan Brillouin zone, which agrees to the direct transition, with a valence

3
K. Balakrishnan et al. Physica B: Condensed Matter 654 (2023) 414734

Fig. 3a. –e. Electronic band structure of different phases of SnO2 for equilibrium crystal structure at high symmetric k – points.

bandwidth of around 9 eV [27]. However, bandgap energy (Eg) of computed for the five phases of bulk SnO2. Zero-energy level indicates
equilibrium structures of other phases are as follows: CaCl2-phase: the Fermi level (EF), which is the chosen origin of energy. The left side of
1.337 eV; α-PbO2 – phase: 1.241 eV; pyrite – phase: 0.866 eV, and ZrO2 – EF illustrates the valence band feature, and the right side the conduction
phase: 0.739 eV [14]. From the results of Eg it is observed that rutile and band in Fig. 4a – e. Fig. 4a shows the partial density of states for the
CaCl2 phases possess almost similar bandgap, which is greater than the rutile structure. It is obvious that the upper valence bands are composed
other phases. Though GGA yields an underestimated value, it is in of O-p bands, which hybridize with 5s and 2p bands of Sn. These are the
agreement with other theoretical calculations. Discrepancies in the upper states of valence band with the bandwidth of 0.6eV–9eV. Whereas
theoretical and experimental bandgap are attributed to the discontinuity the lower conduction bands emanating due to hybridization between Sn-
of the exchange-correlation potentials [46,51–53]. 5s and 2p states with O -2p states. This hybridization leads to a forma­
tion of bandwidth of 0.5 eV–5 eV, approximately in the lower states of
3.2.2. Projected density of states the conduction band. While analyzing the band structure and density of
The total density of states (TDOS) is associated with partial/pro­ states of all the phases, the strongest peak in the valence band mainly
jected density of states (PDOS) at equilibrium lattice constants comprises of O- 2p states and Sn s/Sn p states. Hence, our results

4
K. Balakrishnan et al. Physica B: Condensed Matter 654 (2023) 414734

Fig. 4a. e. Total and partial density of states for SnO2 polymorphs at equilibrium crystal structure.

revealed that the 2p orbital of O atom and 5s, 2p orbital of Sn atom play the undistorted cell and Cij are the elements of the elastic constant
a major role for formation of bands and hybridization process. This is matrix. The elastic tensor has 36 elements, but the elastic constants hold
due to the interaction between the Sn–O and O–O antibonding states. maximum of 21 independent elements. By means of the symmetry of the
O–O bonding is the strongest compared to Sn–O bonding. The lower part unit cell, the number of independent elastic constants for the various
of the valence band is a consequence of bond formation between the symmetry systems can be reduced. From the value Cij of a crystal, we can
atoms. Likewise, the PDOS for all five polymorphs is given in Fig. 4a – e. also calculate the bulk modulus (B) shear modulus (G), Youngs modulus
(E) and Poisson’s ratio (σ) of the polycrystalline materials by the
Voigt–Reuss–Hill (VRH) approximation [54,55]. The bulk modulus B
3.3. Elastic properties
and the shear modulus G based on the average of Voigt and Reuss elastic
moduli are expressed as follows.
The stress tensor σij (r) of an elastic material is related to its strain εkl
( )
(r) by Hooke’s law 1 1
B= BV − BR G = (GV − GR ) (6)
2 2
σij (r) = Cijkl (r) εkl (r), (3)

εkl (r) = Sijkl (r) σij (r). (4) Further the Young’s modulus E is given by

Whereas Cijkl is the elastic moduli tensor and Sijkl = (C− 1)ijkl is the
9BG
E= (7)
3B + G
compliance tensor thus the stress and strain are the position dependent.
The linear elastic constants form a 6 × 6 symmetric matrix. The defor­ Poisson’s ratio σ can be calculated from the following
mation leads to a change in the total energy.
3B − 2G
σ= (8)
Etot − E0 1 ∑ 6 ∑ 6 2(3B + G)
U= = Cij (5)
V0 2 i− 1 j=1 The calculated elastic stiffness constant Cij , shear modulus (G),
Young’s modulus (E) and Poisson’s ratio (σ) at equilibrium volume are
Where E0 is the total energy of the unstrained lattice, V0 is the volume of

5
K. Balakrishnan et al. Physica B: Condensed Matter 654 (2023) 414734

given in Table 2. The Young’s modulus, which is a measure of the vibrating in the plane perpendicular to the C- axis [59]. The doubly
stiffness of a material, is the highest for the cubic phase, which means degenerated Eg mode vibrates in the direction parallel to the C-axis in
that it is the stiffest among the phases. From Table 2 we also noted that the Raman modes. The B1g mode possesses rotation of oxygen atoms
the values of E & G decreases in the order of high to low symmetric around the C-axis, with all the oxygen atoms participating in vibration.
crystal structure. The highest bulk modulus of the pyrite phase corre­ In the infrared active A2g mode, the oxygen and Sn atoms vibrate along
sponds to 195.8 Gpa, which means a higher resistance to fracture than the C-axis. Table 3 compares the calculated phonon frequencies at Γ
others. The orthorhombic phases on the other hand possess a low bulk point with the experimental infrared, Raman and other calculated re­
modulus implying that they are easily compressible. Therefore, the sults complementing each other [58,60,61]. The computed phonon
decrease in the values of B0, G, and E from high to low symmetric crystal dispersion curve for high symmetric points in the Brillouin zone, namely
systems suggests that the resistance to deformation becomes weaker as Γ, X, M, Γ, Z, R, A are shown in Fig. 5a. In addition, positive phonon
the stiffness weakens. To our knowledge, such a relation between the frequencies at zero pressure are also obtained and is no shift in mode
elastic constants with the structural order is rarely discussed in any other appears, confirming the stability of the rutile structure SnO2. In general,
theoretical and experimental report before. for a stable crystal, the phonon frequencies will be positive, whereas it is
In addition, the Poisson’s ratio σ can be used to measure the ductility unstable if the frequencies are imaginary [58–60]. Additionally, in
or brittleness of the system. The critical value of Poisson’s ratio which Fig. 5a the phonon density of states is calculated from the dynamical
distinguishes between the ductile and brittle nature of material is 0.26. A matrix phonon code. Here exists a gap accrue around 410 cm− 1 in the
material is considered as ductile if σ > 0.26, otherwise the material is phonon density of states indicating the mass difference between Sn and
brittle. Therefore in the present case, all phases belong to the ductile O atoms. Correspondingly, in the total phonon DOS (PDOS), there are
category [56,57]. These calculated elastic stiffness constants vary from 3 two equal regions, above and below the gap. Similarly, all the phases are
to 5% with other reported theoretical and experimental values [47]. dynamically stable over the entire Brillion zone shown in Fig. 5b – e with
PDOS.
3.4. Phonon dispersion relation
3.5. Thermodynamic properties
The waves of collective atomic vibrations in a periodic solid are
known as phonons. The phonon dispersion relations for our six atoms The thermodynamic properties of SnO2 polymorphs are investigated
unit cell of rutile SnO2 will be obtained here. The crystal possesses with thermo_pw [62,63]. Debye temperature, Debye Vibrational free
totally 18 phonon branches of vibrational modes in the first Brillouin energy, Debye entropy and Debye heat capacity from 0 K to the highest
zone. According to group theory, three among these are acoustical and temperature are determined to achieve the equilibrium normal mode of
the remaining fifteen are optical zone center phonons. Generally, in vibration. Debye temperature is estimated from the average wave ve­
polar materials a macroscopic electric field appears because of long- locity (νm), of all phases from the following Eq. (10) [64].
range columbic interactions at q = 0, because of which frequencies ( )1/3
are analyzed at zone centers. At the zone center, the mechanical rep­ θD =
h 3nρNA
νm (10)
resentation of the normal vibrational modes is given by Ref. [58]. k 4πM

Γ = A (1g) + A (2g) + B (1g) + B (2g) + E (g) + 2A (2u) + 2B (1u) were h is a Planck constant, k is the Boltzmann constant, ρ is the
density of the crystal per unit cell, NA the Avogadro number, The
+ 4E (u)
calculated Debye temperatures of the phases are given in Table 4. From
(9) Fig. 6 it is found that the Debye heat capacity varies with temperature at
According to Eq. (9), there are four Raman active modes (A1g, B1g, a constant volume. It is also observed that from the calculated θD of the
B2g, and doubly degenerated Eg), two IR active (non-degenerated A2u cubic phase is greater than other phases. At temperatures below 100 K,
and doubly degenerated Eu modes) and two silent modes (A2g and B1u). the results obey the Debye T3 law whereas at higher temperatures, it
Here, the A2u and the two Eu modes are acoustic. In all the Raman active follows that the Dulong and Petit law in classical limit [65,66]. The
modes, the oxygen atoms vibrate but the Sn atoms don’t. In particular, average Debye wave velocity follows the order of crystal symmetry. In
all the Raman modes, A1g, B1g, and B2g, are nondegenerate which are all the Debye model, the Debye frequency limits the mode of vibration of
the molecule. The Debye vibrational free energy increases with
Table 2
increasing temperature and becomes linear at 800 K for all the phases as
Comparison of the calculated phonon frequency (in Thz) at the Γ point with shown in Fig. 7. A crystal with a high Debye temperature is due to its
experimental data for the rutile phase. stiffness, which possesses a high optical phonon frequency. These results
are consistent with the results of the phases’ elastic property as well. The
Mode Present calculation Experimentala Computedb Computedc
Debye temperature thus follows the phase order as cubic > tetragonal >
A1g 17.89 19.13 18.11 19.13 orthorhombic. It is larger for crystals with a high melting point. For all
A2g 10.42 11.93 10.19 10.79
B1g 4.08 3.00 2.94 3.14
phases, CV approaches zero when the temperature approaches zero. The
B2g 21.50 23.44 22.27 22.84 lattice vibration increases and reaches a maximum above 10 K, due to
Eg 13.10 14.27 14.24 14.08 equilibrium position of the atom. The specific heat of most of the crystal
B1u 4.08 4.20 4.41 4.40 is proportional to T3.
B1u 15.76 15.14 14.24 17.54
A2u (TO) 12.63 14.30 13.82 13.82
Eu (TO)
(1) 6.71 7.31 6.75 7.24 3.6. Discussion
Eu (TO)
(2) 8.04 8.8 8.42 8.57
Eu (TO)
(3) 16.75 18.53 16.97 18.43 Starting from the rutile to the pyrite, the minimum energy of the
A2u (LO) – 21.13 19.10 19.70 phases is within 0.9 eV. Despite being the highly stable structure, the
8.04 8.27 8.00 8.36
Eu (LO) equilibrium volume of the rutile phase is minimum compared to the rest
(1)

8.66 10.97 10.61 12.18

Eu (LO) of the phases. Furthermore, the rutile-type and CaCl2 – type exhibit a
(1)

16.75 23.08 21.59 21.09

Eu (LO) similar E-V curve due to the slightly distorted structure of the P4_2/mnm
(3)

a
Reference [60]. and Pnnm space groups. Even though these two phases exhibit similar
b
Reference [14]. structural stability, the c/a and b/a ratios are different. The bulk
c
Reference [58]. modulus of the cubic pyrite phase is greater compared to tetragonal

6
K. Balakrishnan et al. Physica B: Condensed Matter 654 (2023) 414734

Table 3
The Elastic constants, Shear modulus (G) and Young’s modulus (E) and Poisson’s ratio (σ) of SnO2 Phases.
[Link] Space group Crystal type C11 C12 C13 C22 C23 C33 C44 C55 C66 E G σ
(GPa) (GPa)

1. P42/mnm Tetragonal This work 213 129 118 – – 363 94 – 182 233 92 0.267
Other theorya 202 137.1 125.8 370.0 83.2 173.7
2. Pnnm Orthorhombic 365 109 115 196 132 204 179 87 85 218 85 0.27
This work
3. Pbcn Orthorhombic 238 121 120 265 104 304 79 93 111 220 86 0.27
This work 241.6 154.2 121.1 256.9 83.5 257.8 74.9 94.2 111.9
Other theoryb
4. Pa 3 Cubic 311 102 – – – – 95 258 103 0.256
This work 327.2 135.2 108.4
Other theoryb
5. pbca Orthorhombic 316 166 175 318 113 306 66 81 54 210 82 0.28
This work 329.7 164.6 135.4 353.0 127.2 346.6 61.0 82.0 75
Other theoryb
a
Reference [25].
b
Reference [47].

Fig. 5. ae. Computed phonon dispersion curve at high symmetric k points along with phonon density of states for five polymorphs of SnO2. The positive frequency at
Γ point of the phases indicates that the phases were dynamically stable.

(rutile) and other orthorhombic (CaCl2, PbO2, ZrO2) phases. This is bandgap. ZrO2 is the only phase with an indirect bandgap whereas all
interestingly in the order of highly symmetric cubic to asymmetric the others are of direct bandgap type. Hence, the rutile phase is the most
orthorhombic phases. The bandgap of rutile is also higher compared to stable for which it finds versatile applications. The structural stability of
other polymorphs, which means that the rutile has a strong interatomic the phase is also in agreement with the results of cohesive energy and
bond leading to its stable structure. The bond length is of the order of phonon dispersion spectrum. The cohesive energy of rutile is 5.99 eV/
ZrO2 > Pyrite > PbO2 > CaCl2 > Rutile, which again implies that the atom, which is comparatively greater than the other four phases, again
rutile is more stable than other phases, which is consistent with the indicating stability. The real frequency in the phonon spectrum around Γ

7
K. Balakrishnan et al. Physica B: Condensed Matter 654 (2023) 414734

Table 4 4. Summary
Calculation of Debye Temperatur e (θD), Debye Heat capacity (Cv), Debye wave
velocity (νm) of tin dioxide polymorphs. In summary, the structural, electronic, elastic, and thermodynamic
Phases Debye The Debye heat capacity Cv Average Debye properties of the different phases of SnO2 under zero pressure are
Temperature θD at limit 800 K (J/K/N mol) wave velocity νm investigated within density functional theory. The calculated ground
(K) (m/s) state properties are in good agreement with experimental and other
Rutile 517.17 152.13 4007.88 theoretical results. Based on the electronic band structure and the partial
CaCl2 496.20 152.38 3848.09 density of states, the band gap and the type of band gap for the phases of
PbO2 508.99 152.23 3922.17
SnO2 were interpreted. Pyrite has a relatively high bulk modulus cor­
Pyrite 550.61 151.73 4151.08
ZrO2 489.04 152.47 3677.20 responding to its elastic nature obtained from EOS. Moreover, from the
Poisson’s ratio it is inferred that all the phases are ductile, based on the
Pugh’s criteria. The lattice dynamic property of the phases was obtained
from QHA. The calculated heat capacity of the phases is close to the
Dulong-Petit limit 3R at 150.01 J/m/k at temperature 800 K. Further,
from the phonon dispersion relation, equation of states, cohesive energy,
and bond length the stability of the rutile phase has been proved. In the
perspective of symmetry, we finally discussed the physical qualities of
tin dioxide polymorphs. All these calculated parameters are of great
importance in selecting and modelling of materials for various elec­
tronic, energy, and biological applications.

Credit author statement

K.B: Formal analysis, Investigation, Methodology, Software, Writing-

Reviewing and Editing, Visualization, Data Analysis. S.A: Methodology,
Data analysis, Reviewing and Editing. V. V: Supervision, Conceptuali­
zation, Reviewing.

Declaration of competing interest

Fig. 6. Debye heat capacity Cv, at different temperature of SnO2 polymorphs.
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.

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