An ab-initio Study of Structural and Electronic Properties of SnO2 Under Pressure

Nabil Beloufa1*,Fasla Souad1, Chercheb Youcef 2and Bekheira Samir3.

1
National Polytechnic School Oran, Laboratory of Micro and Nanophysics (LaMiN), ENPO-
MA, BP 1523, El M’Naouer, 31000, Oran, Algeria.
2
University Relizane , Laboratory of Exact Sciences, BP 48000, Bormadia, 048000
Relizane, Algeria
3
National Polytechnic School Oran, Laboratory of Materials (LabMat), ENPO-MA, BP
1523, El M’Naouer, 31000, Oran, Algeria.
*
Corresponding author: beloufa.nabil@gmail.com

ABSTRACT: In this paper, we studied the structural and electronic properties of SnO 2 using density

functional theory (DFT) based on the full-potential linear augmented plane wave (FP-LAPW) method and

implemented in the calculation code Wien2k. To treat the exchange-correlation potential for the total energy

calculations, using local-density approximation (LDA) and generalized gradient approximation (GGA).

Additionally, The Tran and Blaha modified Becke-Johnson potential TB-mBJ approximation, which

successfully corrects the band-gap problem, was used for the band structure calculations. The calculation of

lattice constant and band-gap values are in good agreement with the available theoretical and experimental

data.

We find in our calculations for the phase transition from the rutile structure (P4 2/mnm) to the phases: CaCl2-

type, α -PbO2-type, pyrite-type , ZrO2-type, fluorite-type and cotunnite-type phase are possible under low

pressures and in good agreement with other theoretical calculations and experimental results. and The

calculation of the density of state gives a detailed explanation of the contribution of the different orbitals.

Keywords: DFT, FP-LAPW, SnO2,GGA, mBJ.

1. INTRODUCTION
Tin dioxide technology is of great importance in the field of microelectronics. The search for electronic

components with transport properties superior to those of SnO 2, leads the research towards IV-VI

semiconducting materials. Components made from these semiconductors have remarkable physical

properties in microwave applications, power electronics and optoelectronics1.

Tin oxide SnO2 can be used as an anode in electrochemical processes for the oxidation of organic

compounds such as phenol2. The electrical properties of tin oxide layers are influenced by the gaseous

chemical environment in contact with the layer. Thus, the absorption by physi sorption or chemisorption of

chemical species on the surface of the layer modifies its conductivity by changing the electronic states of

the semiconductor by moving electrons from the valence band to the conduction band 3. Lithium has long

been used in the manufacture of storage batteries because of its high energy density and energy storage

capacity. In the case of such batteries, the lithium compound forms the cathode and the anode is composed

of carbon graphite. In order to limit the use of the latter, and this to reduce the carbon footprint while

increasing the energy capacities of the batteries, research has turned to the association of lithium with many

oxidants including tin oxide4,5. These associations can be made in the form of a Li 2SnO3/LiMn2O4 mixed

compound6 or in the form of Sn/LiO2 multilayers7 .

The structural parameters of SnO2 were determined experimentally by Bolzan et al. and Huang et al.8,9 .

Calculations of the first principles of electronic structure of tin oxide have been reported in the literature 10,11

. The structural, electronic and optical properties of SnO2 have been studied by Donglin Guo and Guo and

Hu using the functional density theory (FDT) in the local density approximation (LDA) 11. The origin of

spectral peaks has been explained by Qi-Jun Liu et al based on the molecular-orbital bonding theory 12 . at

ambient temperature and pressure SnO2 crystallizes in the rutile tetragonal structure with a space group

P42/mnm, since Jiang et al.13 Under pressure of 18 GPa, the rutile-type tetragonal structure could transform

into the cubic pyrite phase pa3 In addition, Shieh et al 14. X-ray diffraction analysis has shown the existence

of four transition phases. The phase sequence observed for SnO 2 is rutile type (P42/mnm) →CaCl2 type

(Pnnm) →pyrite type (pa-3) →orthorhombic phase I (Pbca) →cotunnite type (Pnam) ZrO 2. While Haines
and Léger15 Bulk SnO2 behaviors, such as phase transition, the properties, electronics and optics 12,15,16. have

attracted sustained investigations both in theories. and Experimental observations 14-16. some calculations on

electronic and optical properties have been performed by many groups, such as ; Meyer et al 17 , Rahman et

al19 , Liu et al12 Barbarat and Matar10, Errico18 and Li et al 20 .

In our work, we present and discuss the results of our calculations on the structural and electronic

properties of SnO2, and this by considering several phases: type - rutile (P4 2/mnm) , CaCl2 (Pnnm), α-PbO2

(Pbcn), type (Pa-3), orthorhombic phase 1 ZrO 2 type (Pbca), pyrite (Fm-3m) and cotunnite type (Pnam). in

the context of FTD. Calculations were performed using the wien2k code using the FP-LAPW method with

the approximations: LDA, GGA and mBJ.

This paper is organized as follows, in the second section we briefly describe the method used and give

details of the calculation. In the third section we discuss in detail the results concerning the structural and

electronic properties of our compound. Finally, we summarize the results in the fourth Section.

2. METHODOLOGY

In our work, we have studied the structural and electronic properties of SnO 2 compound using the method of

linearized augmented plane waves (FP_LAPW)21, they are based on the formalism of the density functional

theory (DFT)22 and these approximations of the exchange and correlation energy are: the local density

approximation (LDA)23, the generalized gradient approximation (GGA)24 and the Becke and Johnson

modified Becke-Johnson approximation The Tran and Blaha modified Becke-Johnson potential (TB-mBJ)25,

all these approximations are implemented in the Wien2k code26.

The first calculation step is to calculate the energy as a function of volume to determine the equilibrium

parameters corresponding to the volume. This allows us to give the value of the mesh parameter.

In the FP-LAPW method, space is divided into two regions: the non-overlapping spheres centered on each

atom (called muffin-tin spheres) of RMT rays and the interstitial region between the spheres. The basic

functions, electron densities and potentials are developed on the one hand in combination of spherical
harmonics inside the muffin-tin spheres for a maximum value of l max =10 and on the other hand in Fourier

series in the interstitial region with a cut-off radius R MT.Kmax = 8 (RMT is the smallest radius of the muffin-tin

spheres and Kmax represents the largest wave vector in the extension of the plane waves writing the

interstitial region). The core energy cutoff is taken as - 10.0 Ryd Convergence of self-consistent cycles is

only achieved when the total energy difference between successive iterations is less than 10 -5 Ry per

formula unit.

By using the Pack special k-points method27, The integral sover the Brillouin zone are done up to 300 k-

points .The electronic valence configurations for Sn and O are respectively 5s25p2 and 2s22p4.

3. RESULTS AND DISCUSSION

3.1 Structural properties

The structure of tin dioxide is rutile. The unit cell is quadratic and contains six atoms: two tin atoms and

four oxygen atoms. Each tin atom is the centre of an almost regular octahedron formed by six oxygen

atoms, while each oxygen atom is surrounded by three tin atoms located at the vertices of an isosceles

triangle.

The oxygen is in position 4f (space group P42/mnm) given by (u; u; 0), (1-u, 1-u; 0), (1/2+u; 1/2-u; 1/2) and

(1/2-u; 1/2+u; 1/2) with u = 0.30728,29 . The tin occupies position 2a, (1/2; 1/2; 1/2) and (0; 0; 0).

In order to calculate the structural parameters for the phases: (P4 2/mnm), (Pnnm), (Pbcn), (Pa-3), (Pbca),

(Fm-3m) and (Pnam), for the tin dioxide material SnO 2, we studied the variation of the total energy of the

system E as a function of the volume of the elementary mesh V for each phase, using the approximation

LDA and GGA.

We start with the optimization step to determine the minimum energy that corresponds to the equilibrium

energy using the Murnaghan state equation defined as follows30:

 B V   '  V 0   V 0 B 
'

E  V   E 0   ' 0'  . B  1     1

 B ( B  1)    V   V  
(1)
where
E, V is respectively the total energy and the volume of the mesh.

E0, V0 are respectively the energy and the volume of the mesh at equilibrium.

B0, B ́ are the modulus of compressibility at equilibrium and its first derivative with respect to pressure.With

2E 
B0
B0  V B0 
V 2 and P (2)

This equation allowed us to obtain the equilibrium parameter (a 0), the compressibility modulus (B0) and the

corresponding pressure derivative in the equilibrium phase.

When comparing the total energy of several structures, the structure with the lowest energy in this group is

considered the appropriate energy for the system.

In the case of the phases : (P42/mnm) , (Pa-3) and (Fm-3m) , we varied the ratio (c/a), the internal parameter

(u) and the lattice parameter (a) to find the minimization curves.

The structural optimization for these phases is carried out by calculating the total energy based on these

three variables. In the first step, we determined the internal parameter u for a specific volume and c/a ratio,

then we used the internal equilibrium parameter ueq to optimize the c/a ratio to obtain (c/a) eq to (V, ueq).

Then using the parameters ueq and (c/a) eq, we were able to optimize the volume (V 0): (Pnnm), (Pbcn),

(Pbca) and (Pnam), we also optimized the b/a ratio to obtain (b/a)eq.

In Figure 1and 2, bellows we show the minimization curves which represent the variation of the total

energy versus the volume V of the elementary mesh, for the phases studied using the two approximations

LDA and GGA for SnO2 (rutile).

Looking at the two figures 1 and 2 , we see that the rutile structure (P4 2/mnm) represents the most stable

phase for SnO2.

The structural parameters obtained are grouped in table 1 together with the results of other theoretical and

experimental works. The results of the calculations obtained by the two approximations LDA and GGA are

very close and in good agreement with those of the other works cited.
Table 1 gives a summary of the structural parameters of the lattice parameter a 0, the bulk modulus B0 and its

derivative B0', to calculate each phase for the SnO2 compound.

Comparing our results with the experimental results we find that the grid parameters calculated by the GGA

approximation are overestimated and those calculated by the LDA approximation are underestimated;

however the LDA approximation is in good agreement with the experimental results and even with the

theoretical results of previous work.

3.1.1 Transition pressure

The physical properties of a material change under the influence of pressure. In fact, pressure directly

affects the chemical bonds, and thus leads to a change in the crystal structure, and consequently changes the

physical properties.

From our study of structural properties, we have seen that the most stable phase of SnO 2 has the rutile

structure (P42/mnm) but under pressure other phases with other crystal structures could exist.

The transition pressure Pt from one phase to another is determined from the enthalpy equation:

G  U  PV  TS (3)

The relation ship between Gibbs' energy is given by:

 B' 1 
B0V 0   B'
 B' 
G  P   E0  ' 1 P   1
B  1  B0 
 
  (4)

H  E tot  PV (5)

Using the graphs of the enthalpy difference variation as a function of pressure, plotted and grouped in

figures 3 and 4, we have calculated the transition pressures from the rutile phase (P4 2/mnm) to the phases:

The results are shown in Table 2.

Our results obtained by the LDA and GGA approximation for the transition pressure from the rutile phase

(P42/mnm) to the (Pnnm), (Pbcn), (Pa-3), (Pbca), (Fm-3m) and (Pnam) phases are in good agreement with

the other theoretical calculations.

We note that the SnO2 material can transit from the P42/mnm structure to the (Pnnm), (Pbcn), (Pa-3), (Pbca),

(Fm-3m) and (Pnam) phases under low pressures, as shown in Table 2.

3.2 Electronic properties

3.2.1 Band structure

The most significant description of the energy surfaces offered to the electrons is as follows in the

reciprocal or k-wave vector space48. This is usually simplified by description considering the variations of

energy E as a function of k in the three directions of the highest symmetry of this space. In these directions,

and limited to the first zone of Brillouin. The description of the properties of direct gap semiconductors does

not generally requires that knowledge of electronic states in the vicinity of the Brillouin area.

The band structures of SnO2 calculated using the two approximations, GGA and GGA+ TB-mBJ, for the

rutile phase are shown in Figure 5.

In the rutile structure, the Fermi level is set at zero energy; the maximum of the valence band and the

minimum of the conduction band are at the symmetry point Γ. So SnO 2 is a direct gap semiconductor. The

gap widths for the LDA and GGA found are given in Table 3.

According to the results in table (3), the calculated gaps are in good agreement with other theoretical values

of D.Frohlich50 and experimental of M.Nagaswa42. However, it is clear that the approximation mBJ-GGA

gives the gap values closest to the experimental data.

3.2.2 Density of state (DOS)

The electronic state density (DOS ) curve represents the number of electronic states as a function of energy.

For the representation of the DOS, the origin of energy is usually set at the Fermi level. The total and partial

state density curve for SnO2 with GGA and GGA+ TB-mBJ are shown in Figure 6.
From figure 6, we can distinguish four regions:

The first region is located between -21.53 eV and -20.02 eV. It can be seen that there is a strong

participation of the d orbital of (Sn) and the s orbital of (O).

The second region is located between -19.28 eV and -16.45 eV. This region is dominated by the d-orbital of

(Sn) and the s-orbital of (O).

The third region is located between -6.77 eV and 0.00 eV. In this region the contribution of the p orbit of

(O) is dominant with a very small contribution from the s , p and d orbitals of (Sn).

The fourth region is between 3.10 eV and 14.48 eV. It can be seen that one contribution is from the p orbit

of (O) and the second is that of the s , p and d orbits of (Sn) .

4. CONCLUSION

In this work, we studied the structural and electronic properties of tin dioxide SnO 2. Our Calculations were

performed by the linearized augmented plane wave method (FP-LAPW) within the framework of the

density functional (DFT) implemented in the code (Wien2K). To determine the exchange and correlation

potential, we used the generalized gradient approximation (GGA), the local density approximation (LDA)

and the “Becke Johnson Potential” technique (mBJ) modified by Tran-Blaha (TB-mBJ).

Our study provided a detailed description of the structural and electronic properties, such as: structural

optimization, transition pressure, band structure, total and partial density of state. Our results clearly

indicate that:

-The lattice parameters (a, c/a), the internal parameter (u), the bulk modulus 𝐵0 and its derivative 𝐵0′ are in

good agreement with the theoretical results and the experimental data.

-The structural properties were subsequently studied using generalized gradient (GGA) and local density

(LDA) approximations. We find in our calculations, the usual trends, namely that the GGA, contrary to the

LDA, overestimates the lattice parameter and underestimates the bulk modulus.
- Our results for the phase transition from the rutile structure (P4 2/mnm) to the (Pnnm), (Pbcn), (Pa-3),

(Pbca), (Fm-3m) and (Pnam) phases are in good agreement with the other theoretical calculations and the

experimental results.

- Phase transitions for this material from the rutile structure (P4 2/mnm) to (Pnnm), (Pbcn), (Pa-3), (Pbca),

(Fm-3m) and (Pnam) are possible under low pressures.

-The band structures calculated for this compound indicate the presence of a direct gap at the high

symmetry point Γ , using the (mBJ) approach. The calculated results are in agreement with other theoretical

calculations and are underestimated compared to the experimental data.

-For this material , we can see that the fact of having an energy gap of 0.816 to 2.892 eV makes it a material

rich in applications. It is used in photovoltaic cells since its gap belongs to the visible spectrum of solar

energy. Solar energy is considered one of the most important renewable energies today. SnO 2 is also used

in gas detectors and as a catalyst for the production of Hydrogen.

- The calculation of the state density gives a detailed explanation of the contribution of the different orbitals

5. ACKNOWLEDGMENT

We are particularly grateful for the assistance given by Prof. Souad Fasla and Youcef Chercheb

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MESFETs with Au/WSiN T-shaped gate, IEEE Transactions on Electron Devices 40(1), 18-24.
http://doi.org/10.1109/16.249418.
49. M.A. Bezzerrouk , M. Hassan , R. Baghdad , S. Reguieg , M. Bousmaha , B. Kharroubi , B. Bouhafs .
(2015) .Thermodynamic, structural and electronic, properties of SnO 2: By GGA and GGA trans-blaha-
modified Becke–Johnson (TB-mBJ) calculation. http://doi.org/10.1016/j.spmi.2015.02.046.
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photons Phys Rev.Lett.41, 1750. http://doi.org/10.1103/PhysRevLett.41.1750
Tables
Table 1: Structural parameters of SnO 2 at equilibrium in the different phases: the lattice parameter a 0, the
bulk modulus B0 and derivative B', compared to other works
Other
Present Work
SnO2 calculations
Experimental
results
LDA GGA LDA GGA

Rutile(P42/mnm)
a(Å) 4.725 4.858 4.8235 4.73735 4.73832
4.7131
u 0.3044 0.3065 0.30632,37 0.30640 0.30741
0.30318
c/a 0.672 0.673 0.65838 0.67340 0.67241
0.6634
V0 485.96 513.573
22131
B(GPa) 216.046 179.2593 19239 20843 20518
4.7636
B' 5.227 5.0899 4.842 5.1344
CaCl2 (Pnnm)
a(Å) 4.696 4.855
4.70732
c/a 0.670 0.671 0.67232 0.67831
0.67132
b/a 0.970 0.975 0.97532 0.99531
0.9732
V0 481.966 508.477
22132
B(GPa) 193.288 213.145 19545
4.632
B' 5.121
α-PbO2(Pbcn)
a(Å) 4.778 4.847 4.82831
c/a 1.136 1.117 1.11431
1.11432
b/a 1.2131 1.221 1.21331
1.21332
V0 477.9302 504.3851
20139
B(GPa) 219.413 185.991 20439
B' 5.937 5.314 4.739
Pyrite (Pa-3)
a(Å) 5.872 5.079
5.06230-45
u 0.342 0.346 5.06631 32835 30746
0.33535
V0 442.5509 470.4063 23031 27133
2133528130-45
B(GPa) 239.358 180.7466
4.732
B' 4.68 4.84
ZrO2 (Pbca)
a(Å) 9.86 10.076 9.9731
c/a 0.507 0.503 0.50431 0.50814
b/a 0.517 0.512 0.51331 0.52614
V0 435.915 469.279
B(GPa) 259.808 212.37 27331 28531 25914
B' 4.68 4.932 431 5.132 414
Fluorite (Fm3m)
a (Å) 4.993 5.116 4.97240
u 0.25 0.25 0.2540
V0 434.917 460.813
B(GPa) 211.97 204 28840
B' 3.818 4.855 4.532
PbCl2 (Pnam)
a(Å) 5.22 5.088 5.32355.247 1.17735
c/a 1.325 1.289 4.9931 4.9737
b/a 0.647 0.64 1.25131
0.60435
V0 419.776 453.764 0.6537
B(GPa) 244.1 208 22947
4.537
B' 5.43 4.72 437

Table 2: The values transition pressure of SnO2.

Our Work Other work Experimental results
Transition pressure
(GPa) LDA GGA LDA GGA

(P42/mnm) - (Pnnm) 8.19 13.37 10.0118 2.418 11.818,33

(P42/mnm) - (Pbcn) 17.65 6.80 - 1732,33 1218,33
(P42/mnm) - (Pa-3) 19.13 17.78 18.318 22.118 2118,33
(P42/mnm) - (Pbca) 26.76 22.91 - 1832,33 50 –7418,33
(P42/mnm) - (Fm-3m) 30.63 26.48 - 2432,33 52.118,33
(P42/mnm) - (Pnam) 35.31 34.16 - 3332,33 54- 11718,33

Table 3: The gap of SnO2 (rutile phase)

SnO2 Other Experimental
Present Work
calculations results

GGA+ TB- GGGA+ TB-

GGA GGA
mBJ mBJ

0.816 0.7737 2.8649

Eg (Γ- Γ) 2.8920 3.637
8 0.83239 2.7639
Figures
E n e r g y (R y )

3
Volum e(u,a)

Figure 1: Calculated total energies as a function of primitive cell volume for the different phases using
LDA.
 E n e r g y (R y )

3
Volum e(u,a)

Figure 2: Calculated total energies as a function of primitive cell volume for the different phases using
GGA.
Enthalpy difference (eV)

Transition presure (GPa)

Figure 3: Phase transition using LDA.

 Enthalpy difference (eV)

Transition presure (GPa)

Figure 4: Phase transition using GGA.

8
8
7
7
6 6
5 5
4 4
3
(a) 3 (b)
2 2
1
)
y(ev

1
EF
ergy(ev)

EF
erg

0 0
n

n
E

-1 -1
-2 -2
-3 -3
-4 -4
-5 -5
-6 -6
-7 -7
-8
R
-8
            R  

Figure 5: Band structure in rutile phase using (a) GGA and (b) GGA + TB-mBJ.
 20 20

16 (a) 16
(b)
12 Tot 12
Tot
8 8

4 4

1.00 1.00

0.8 0.8

0.6 0.6
Sn
/atom)

0.4 0.4

/atom)
Sn
(states/eV

0.2 0.2

(states/eV
0.0 0.0
2.0
2.0
S

s
O

S
D

O
1.6 1.6

D
1.2 p 1.2 p O
0.8 d O 0.8 d
0.4 0.4

0.0 0.0

-25 -20 -15 -10 -5 0 5 10 15 -25 -20 -15 -10 -5 0 5 10 15

E n e r g y( e V) Energy(eV)

Figure 6: Total and partial DOS of SnO2 in rutile phase using (a) GGA and (b) GGA + TB-mBJ.