Tight-binding Band Structure of β- and α-phase Ga2O3

and Al2O3
Sagar Nanda

Sr.No:20628

1 Introduction
Recently, advances in thin film growth and the availability of large, inexpensive, single-crystal
substrates have enabled us to integrate Ga2 O3 and Al2 O3 to form high power electronics.
Doping of these wide-bandgap semiconductors has enabled the creation of transistors and
Schottky diodes based on β-Ga2 O3 with breakdown fields as large as 5.45 MV/cm [2] and
higher variations approaching the theoretical estimate of 8 MV/cm[3]. α-Ga2 O3 and α-Al2 O3
further expand the band gap to 5.2 and 8.8 eV respectively. The successful design of these
future electronic and photonics devices requires accurate modelling and understanding of
the electronic structure and bonding of Ga2 O3 and Al2 O3 which we will discuss further.

2 Crystal Structure
Ga2 O3 exists in two different crystal forms, i.e., α-Ga2 O3 which is rhombohedral while β-
Ga2 O3 is monoclinic. Al2 O3 also exists as α-Al2 O3 which has a rhombohedral lattice similar
to α-Ga2 O3 . The structure and the first Brillouin zone is simulated using the web software
Materials Project and Materials cloud.[4],[5],[6]

1
Figure 1: (a) First Brillouin zone (b) Bonding of Ga and O atoms (c) Crystal structure of
α-Ga2 O3

Figure 2: (a) First Brillouin zone (b) Bonding of Ga and O atoms (c) Crystal structure of
β-Ga2 O3

2
Figure 3: (a) First Brillouin zone (b) Bonding of Al and O atoms (c) Crystal structure of
Al2 O3

3 Derivation of Tight-Binding Model

We derive the tight-binding model using a Wannier function basis. Wannier functions are
a convenient basis for tight-binding models because they are derived from the underlying
band structure of the material, are formally orthogonal, can be localized to atomic sites, and
preserve the site symmetry and coordination. This approach of DFT-Derived tight-binding
has been used successfully to describe the electronic structure of many materials such as
silicon [7] and 2-D materials [8] etc.
We construct the tight binding model from the Wannier function basis by the following
procedure:[1]

1. Extract the DFT hamiltonian matrix element in the Wannier basis[9]

2. Truncate the couplings to nearest-neighbor (Ga,Al)-O and the (Ga,Al)-(Ga,Al) cou-

pling, keeping only the Wannier functions of s-symmetry on the (Ga,Al) basis

3. The (Ga,Al) site energies and (Ga,Al)-O nearest neighbor coupling are the nscaled to
fit to the experimental bandgap and conduction band effective mass.

3
The parameterization of our tight binding model takes the following form:
X X
H= εi |i⟩ ⟨i| + tij e−ik·∆dij |j⟩ ⟨i| + c.c. (1)
i i,j

Here the first term represent the contribution of individual Wannier function to the total
energy, commonly called the on site energy. The second term describes the kinetic energy of
the electrons, commonly called the hopping energy. In Eq (1),|i⟩represents the ith Wannier
function with on-site energy ε. tij represents the hopping term between the ith and jth
Wannier functions with ϕij representing the phase of tij and ∆dij is the displacement vector.
The spectrum can be obtained by solving the following Hamiltonian

4 Solving the Hamiltonian

The Hamiltonian in this case will be a 22 x 22 matrix defined on the basis of 4 Ga-s(Al-s)
and 18 O-p Wannier functions. We can write this in the block diagonal form as [1]
 
† †
HGa:S HGa:s,O:p x
0 HGa:s,O:pz
 
HGa:s,O:px HO:px 0 0 
H=
  (2)
 0 0 HO:py 0 

HGa:s,O:px 0 0 HO:pz

where HGa:s , HO:px , HO:py ,and HO:pz blocks define the coupling within the Ga-s , O − px ,
O − py , and O − pz Wannier function sub-spaces respectively. The HGa:s,O:px and HGa:s,O:pz
blocks describe the coupling between the Ga-s, O − px and O − pz Wannier functions re-
spectively. Considering the Hamiltonian at Γ (k=0), the coupling between Ga-s and O − py
is omitted due to symmetry of the structure at this point and the phase factor becomes 1
making the matrix real.
Each of the block elements are given by
 
εGa1:s + 2tGa1:s,Ga1:s 0 0 0
 
 0 ε Ga1:s + 2t Ga1:s,Ga1:s 0 0 
HGa:s =  

 0 0 εGa3:s + 2tGa3:s,Ga3:s tGa3:s,Ga4:s 

0 0 tGa3:s,Ga4:s εGa1:s + 2tGa1:s,Ga1:s
(3)
which is written on the basis (|GA1 : s⟩ , |GA2 : s⟩ , |GA3 : s⟩ , |GA4 : s⟩ of Ga-s Wannier
functions.

4
 HO:px , HO:py ,and HO:pz block is daigonal and can be written as

HO:px = HO:py = HO:pz = εO:p × I6×6 (4)

which is written on the basis (|O1 : pl ⟩ , |O2 : pl ⟩ , |O3 : pl ⟩ , |O4 : pl ⟩ , |O5 : pl ⟩ , |O6 : pl ⟩) of
O-P Wannier function where l=x,y,z.
The coupling between Ga-s and O-px and O-pz is given by
 
tGa1:s,O1:px 0 2tGa3:s,O1:px 0
 

 0 −tGa1:s,O1:px 0 2tGa4:s,O2:px 
t
 Ga1:s,O3:px 0 0 −t 
Ga3:s,O4:px 
HGa:s,O:px =  (5)

 0 tGa2:s,O4:px tGa3:s,O4:px 0 


 0 −2t Ga1:s,O6:px tGa3:s,O5:px 0 

2tGa1:s,O6:px 0 0 −tGa3:s,O5:px
 
tGa1:s,O1:pz 0 2tGa3:s,O1:pz 0
 

 0 −tGa1:s,O1:px 0 2tGa4:s,O2:pz 

t
 Ga1:s,O3:pz 0 2tGa3:s,O3:pz −t 
Ga3:s,O4:px 
HGa:s,O:pz =  (6)

 0 −tGa2:s,O4:pz tGa2:s,O4:pz −2tGa4:s,O4:pz 

 0 −2tGa1:s,O6:pz tGa3:s,O5:pz 0 

2tGa1:s,O6:pz 0 0 −tGa3:s,O5:pz
(hopping strengths connected by symmetries are shown with the same symbol).
From the above Hamiltonian we can construct the band diagram by using standard values
for all the terms[main]. Running a simulation of the above Hamiltonian on python I have
obtained the following graphs 4, 5, 6[1]

5
Figure 4: βGa2 O3

Figure 5: αGa2 O3

6
 Figure 6: αAl2 O3

Figure 7: Comparison of DFT and tight binding model for (a)βGa2 O3 (b) αGa2 O3 (c) Al2 O3
from [1]

7
5 Result and Conclusion
Here we discussed about the basic structure and derived a minimal tight binding model for
βGa2 O3 , αGa2O3 and αAl2 O3 . Running a simulation of this tight binding model satisfacto-
rily reproduces the band diagram throughout the Brillouin zone.

6 Reference

References
[1] J. Appl. Phys. 131, 175702 (2022); doi: 10.1063/5.0074598 Submitted: 9 October 2021 ·
Accepted: 22 March 2022 · Published Online: 3 May 2022

[2] S.Roy, A.Bhattacharyya, P.Ranga, H.Splawn, J.Leach, and S.Krishnamoorthy, “High-k

oxide field-plated vertical (001) βGa2 O3 Schottky barrier diode with Baliga’s figure of
merit over 1GW/cm ,” IEEE Electron Device Lett.42, 1140–1143 (2021).

[3] S. J.Pearton, J.Yang, P. H.Cary, F.Ren, J.Kim, M. J.Tadjer, and M. A.Mastro, “A review
of Ga2 O3 materials, processing, and devices,” Appl. Phys. Rev.5, 011301 (2018)

[4] Anubhav Jain, Shyue Ping Ong, Geoffroy Hautier, Wei Chen, William Davidson
Richards, Stephen Dacek, Shreyas Cholia, Dan Gunter, David Skinner, Gerbrand Ceder,
and Kristin A. Persson

[5] @articleprandini2018precision, title=Precision and efficiency in solid-state pseudopo-

tential calculations, author=Prandini, Gianluca and Marrazzo, Antimo and Castelli,
Ivano E and Mounet, Nicolas and Marzari, Nicola, journal=npj Computational
Materials, volume=4, number=1, pages=72, year=2018, issn = 2057-3960, url =
https://www.nature.com/articles/s41524-018-0127-2, doi = 10.1038/s41524-018-0127-2,
note = http://materialscloud.org/sssp, publisher=Nature Publishing Group UK London

[6] Y. Hinuma, G. Pizzi, Y. Kumagai, F. Oba, I. Tanaka, Band structure di-

agram paths based on crystallography, Comp. Mat. Sci. 128, 140 (2017).
DOI: 10.1016/j.commatsci.2016.10.015 (the ”HPKOT” paper; arXiv version:
arXiv:1602.06402).

[7] I.Souza, N.Marzari, and D.Vanderbilt, “Maximally localized Wannier

functions for entangled energy bands,” Phys. Rev. B65, 035109 (2002).
https://doi.org/10.1103/PhysRevB.65.035109

8
[8] I.Souza, N.Marzari, D.Vanderbilt, M.Higashiwaki, K.Sasaki, A.Kuramata, T.Masui,
S.Yamakoshi, J.Jung, A. H.Macdonald, H.Peelaers, C. G.Van de Walle, D.Gresch, Q.Wu,
G. W.Winkler, R.Häuselmann, M.Troyer, A. A.Soluyanov, C.Franchini, R.Kováčik,
M.Marsman, S.Sathyanarayana Murthy, J.He, C.Ederer, G.Kresse, S.Fang, R.Kuate
Defo, S. N.Shirodkar, S.Lieu, G. A.Tritsaris, E.Kaxiras, S.Carr, S.Fang, H. C.Po,
A.Vishwanath, and E.Kaxiras, “Ab initio tight-binding Hamiltonian for transition metal
dichalcogenides,” Phys. Rev. B92, 1–15 (2012)

[9] S.Coh and D.Vanderbilt, “Python tight binding (PythTB)” (2013).