Thermoelectric Properties of Half-Heusler Compound

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Kedar Sharma
IMS14073

Dr School of Physics

April 16, 2019

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Overview

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1 Introduction

2 Motivation

3 Methodology

4 Results and Discussion

5 Conclusion Dr
6 Future Plan

7 References

8 Acknowledgement

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Introduction
Thermoelectric materials

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Thermoelectric materials can convert heat energy to electricity and
vice versa.

The figure of merit of a thermoelectric device for electricity

2
generation: zT = σSκ T
where: σ- electrical conductivity, S-Seebeck constant, κ-Thermal
conductivity and T -Temperature.

conductivity.

Finally zT =
Dr
κ will have both electric (κe ) and lattice (κl ) part of thermal

σS 2 T
κe +κl

Materials with high electrical conductivity and Seebeck constant, low

thermal conductivity preferred (semiconductor).

Semiconductors offers betterMajor

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Project effect. April 16, 2019 3 / 29
Introduction
Half-Heusler(HH) Compounds

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Cubic type structure with composition of XYZ, where X and Y are
transition metals and Z is a p-block element
X,Y and Z occupy ZnS site ( 14 , 41 , 14 ), Primitive site (0, 0, 0) and NaCl
site ( 21 , 12 , 21 ) respectively.
CoY1Sb and CoY2Sn, where Y1 is Ti-group (Ti, Zr, Hf) and Y2 is
V-group (V, Nb, Ta).
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Motivation

Motivation

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Thermoelectric power devices have no moving parts, are very durable,
require little maintenance, and can be fueled by waste heat.

Half Heusler compounds have great potential for medium temperature

(400K-900K) power generation.

Environment friendly, chemically non-toxic and thermally stable

compared with PbTe and skutterudites which have good zT values at
Dr
medium temperature.

In the past few years, researchers were able to achieve zT ≈ 1 for

both n-type and p-type Half-Heusler compounds.

All HH compounds have indirect band gap (except CoTiSb).

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Motivation (contd.)

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Figure: Experimental figure of merit (zT ) Ref 10
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Methodology

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Density Functional Theory
Density Functional Theory(DFT) is a quantum mechanical modelling
method to predict the electronic structure and physical properties of
materials.
Hψ
b = Eψ (1)
Where: Dr
H
b is the Hamiltonian operator,
ψ is the wave function describing the state of particle,
E is the energy of the state.
Uses functionals which are function of electron density ρ(r).

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Density Functional Theory

Many particle hamiltonian

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Here N electron and M nuclei system.
N M N M N N M X
M
1 X 2 1 X 2 X X ZA X X 1 X ZA ZB
Ĥ = − ∇i − ∇A − + +
2 2 riA rij RAB
i=1 A=1 i=1 A=1 i=1 j>i A=1 B>A
(2)
Ĥ = Tˆe + T̂N u + ÛeN u + Ûee + ÛN uN u (3)
Dr
Born-Oppenheimer approximation
MN ucleus >> MElectron
Nuclei are fixed in space compared to electrons.
T̂N u ≈ 0
ÛN uN u ≈ constant

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Density Functional Theory (contd.)
Hamiltonian after Born-Oppenheimer approximation

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Ĥ = Tˆe + ÛeN u + Ûee (4)
Direct numerical solutions are impossible for realistic system.

Hohenberg-Kohn theorem
The external potential uniquely determined by ground state electron
density n(r) and vice-versa.

HK theorem reformulate the many-body problem in terms of the

Dr
density but do not actually solve it.

Kohn-Sham Theorem
Kohn-Sham one particle equation
 
1 2
− ∇ + v ext (r) + vH (r) + vxc (r) ψi (r) = i ψi (r) (5)
2
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Density Functional Theory (contd.)

Kohn-Sham Energy Functional

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Z
E[n(r)] = T [n(r)] + drn(r)vext (r) + EH [n(r)] + Exc (r) (6)

POcc
n(r) = i |ψi (r)|2 electron density
P Zn
vext = − n r−RI potential from the nuclei
0
EH [n] = 1
RR
drdr 0 n(r)n(r ) classical Coulomb energy

Exc [n] =
2
R
Dr |r−r 0 |

drn(r)εxc [n(r)]
exchange and correlation

The exact analytical form of the exchange-correlation functional

remains unknown.
Approximations for εxc [n(r)], i.e. LDA, GGA (PBE).
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Boltzmann Transport Theory
The dynamic behavior of charge carriers can be studied using a

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distribution function, f (r, k, t). The basic form of Boltzmann
Transport Equation (BTE) which describes the distribution of charge
carriers with time.

  
∂f (r, k, t)  ∂f (r, k, t)  ∂f (r, k, t) 
+ + =0
∂t 
fields ∂t 
scattering ∂t 
diffusion
(7)
where r is a position of charge carrier, k is a wave vector, and t is a
time.
Dr
Velocity and energy relation
dr 1 ∂εi (k)
= v i (k) = (8)
dt ~ ∂k
vi (k) is the group velocity if charge carriers with band index i and
momentum k, whose eigenenergies are εi (k).
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Boltzmann Transport Theory (contd.)

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Fermi-Dirac distribution at thermodynamic equilibrium
1
fio (r, k, t) = ε(k)−µ
(9)
e kb T
+1
Where kb is a Boltzmann’s constant, µ is chemical potential,  is the
energy and T is the temperature.
Derived form of BTE
Dr
∂ (fno (r, k, t)) εn (k) − µ f 1 (r, k, t)
 
∇T + ∇µ · ~vn (~k) = n (10)
∂εi (k) T τ

Where f o (r, k, t) is the distribution of charge carriers at thermal

equilibrium, and f 1 (r, k, t) is first order correction to the distribution
function caused by external fields and scattering.

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Boltzmann Transport Theory (contd.)
Using the first law of thermodynamics

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dU = T dS + µdN (11)
Continuity equation
∂U
+ ∇ · Je = 0 (12)
∂t
Using first law of thermodynamics and continuity equation

Dr Je = T Js + µJN (13)
Onsagers reciprocal relations for electrical and heat current
JN = σE − σS∇(T )
(14)
JQ = σST E − κ∇(T )
Where S is the Seebeck coefficient. These relations can be used to
calculated the thermoelectric properties such as Seebeck coefficient
and electrical conductivity using DFT calculated electronic structure.
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Boltzmann Transport Theory (contd.)
Z
1
JN = 3 v(k)fi1 (~r, ~k, t)dk

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(15)
4π
Z
1
JQ = 3 (εi (k) − µ)v i (k)fn1 (r, k, t)dk (16)
4π
Thermoelectric quantities (BoltzTraP) are calculated using Eq. 15
and 16.
σi,βγ (i, k) = e2 τi,k v β (i, k)v γ (i, k) (17)
Z
σβγ (T ; µ) ∂f (ε, µ, T )
= − σβγ (ε) dε (18)
Dr
τ
τ
vβγ (T ; µ)
=
−1
qT
Z
σβγ (ε)(ε − µ)
∂ε
∂f (ε, µ, T )
∂ε
dε (19)

−1
Z
κβγ (T ; µ) ∂f (ε, µ, T )
= σβγ (ε)((ε − µ)2 ) dε (20)
τ qT ∂ε
Skl (T ; µ) = σ −1 δk vδl (T ; µ)


(21)
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Computational Details

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VESTA Quantum Espresso

GGA Functional which is available as Perdew-Burke-Ernzerhof(PBE)

Dr
K-point mesh of 12×12×12
Convergence criteria 10−6 Ry/unit cell
Python and Shellscript code to plot band and DOS
BoltzTraP code for transport properties

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Results and Discussion

15 band structure(W-L-G-X-W-K) DOS

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14

13
Energy (eV)

12

11

10
Dr
9
0.0 0.5 1.0 1.5 2.0 2.5
0 10 20 30 40 50 60 70 80
k-path DOS

Figure: Band structure and DOS of CoTiSb

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Results and Discussion (contd.)

18 band structure(W-L-G-X-W-K) DOS

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17

16
Energy (eV)

15

14

13
Dr
12
0.0 0.5 1.0 1.5 2.0 2.5
0 10 20 30 40 50 60 70 80
k-path DOS

Figure: Band structure and DOS of CoVSn

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Results and Discussion (contd.)
The equilibrium lattice constant (a0 ) and band gap (Eg ) Ti-group and
V-group Half Heusler compounds. These values are compared with

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reference values(∗ marked) from Ref 10
Type Structure a0 (Å) a∗0 (Å)(exp.) Eg (eV ) Eg∗ (P BEsol) Eg∗ (exp.)
CoTiSb 5.82 5.88 1.12 1.11 0.19
Ti-group CoZrSb 6.03 6.07 1.08 1.08 0.14
CoHfSb 5.99 6.04 1.18 1.14 0.07

CoVSn Dr 5.73 5.98 0.70 0.66 0.75

V-group CoNbSn 5.90 5.96 1.05 1.02 1.00
CoTaSn 5.89 5.94 1.08 1.06 1.30

Almost all values of lattice parameter are matching with experimental

value (Except CoVSn) with under-estimation.
Ti-group band gap higher than experimental value, may be due to the
deviation from stoichiometric composition.
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Results and Discussion (contd.)
Transport Properties at 200K < T < 1000K
2
1.8

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1.6

PF/τ ( 1012 W/m.K2.s )

1.4
1.2
1
0.8
0.6
0.4
0.2
0
-0.1 -0.05 0 0.05 0.1
3

2.5

2
σ/τ ( 1020 Ω .m.s )

1.5

0.5

0
Dr Seebeck ( µV . K-1 )

-0.5

3000

2000

1000

-1000
-0.1 -0.05 0 0.05

200 K
400 K
600 K
800 K
1000 K
0.1

-2000

-3000

-0.1 -0.05 0 0.05 0.1

ε - εFermi ( Ry )

Figure: Transport properties of CoTiSb with Chemical potential (µ)

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Results and Discussion (contd.)
Transport Properties at 200K < T < 1000K
2
1.8

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1.6

PF/τ ( 1012 W/m.K2.s )

1.4
1.2
1
0.8
0.6
0.4
0.2
0
-4 -2 0 2 4
2.5

2
σ/τ ( 1020 Ω .m.s )

1.5

0.5

Dr 0

-0.5
-4 -2 0 2 4
3000
200 K 800 K
2000 400 K 1000 K
600 K
Seebeck ( µV . K-1 )

1000

-1000

-2000

-3000

-4 -2 0 2 4
n/uc

Figure: Transport properties of CoTiSb with Carrier Concentration (n/uc)

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Results and Discussion (contd.)
Doping concentration at 900K of all half heusler compounds with their

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Seebeck coefficient, electrical conductivity and power factor. These values
are compared with reference values (∗ marked) from Ref 10
Type Structure Doping PF(S2 σ/τ ) S σ/τ
12 2 20
(e/uc) (×10 W / K ms) (µ ∨ /K) (×10 S / m s )
CoTiSb 0.78 1.75 182 0.54
Ti-group CoZrSb 0.82 1.59 180 0.59
CoHfSb 0.37 1.88 200 0.5
CoVSn 0.77 1.74 181 0.48
V-group CoNbSn
CoTaSn
Dr 0.65
0.67
2.10
1.96
170
180
0.65
0.76

At 900K CoNbSn has the highest power factor.

If we neglect the lattice part of thermal conductivity, the figure of
2
merit (zT = σSκe T ) of CoNbSn at 900K is 0.97.
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Results and Discussion (contd.)

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Figure: Experimental figure of merit (zT ) Ref 10
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Conclusion

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Material structure construction and visualization using VESTA.

We calculated equilibrium lattice constant, Band structure, and DOS

using quantum espresso and analyzed the data.

We calculated thermoelectric transport properties of Ti and V-groups

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and calculated the power factor.

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Future Plan

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We have to calculate lattice part of thermal conductivity to calculate
the accurate figure of merit (zT )

Phonon calculation to understand thermal properties.

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Effect of doping in the figure of merit.

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References

1. P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C.

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Cavazzoni, D. Ceresoli, G. L. Chiarotti, M. Cococcioni, I. Dabo, A.
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Paulatto, C. Sbraccia, S. Scandolo, G. Sclauzero, A. P. Seitsonen, A.
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21, 395502 (2009)
http://dx.doi.org/10.1088/0953-8984/21/39/395502
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2. P Giannozzi, O Andreussi, T Brumme, O Bunau, M Buongiorno
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Kokalj, E Kkbenli, M Lazzeri, M Marsili, N Marzari, F Mauri, N L
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References (contd.)
Nguyen, H-V Nguyen, A Otero-de-la-Roza, L Paulatto, S Ponc, D

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Rocca, R Sabatini, B Santra, M Schlipf, A P Seitsonen, A Smogunov,
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3. Hohenberg, P. Kohn, W. Inhomogeneous electron gas. Phys. Rev.
B 136, B864 (1964).
4. Kohn, W. Sham, L. J. Self-Consistent Equations Including
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5. Born, M. Oppenheimer, R. Zur quantentheorie der molekeln. Ann.
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6. Perdew, J. P. J., Burke, K. Ernzerhof, M. Generalized Gradient
Approximation Made Simple. Phys. Rev. Lett. 77, 38653868 (1996).
7. G. Kresse and J. Hafner, Phys. Rev. B 47 , 558 (1993)

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References (contd.)

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8. G. Kresse and J. FurthmAller, Comput. Mat. Sci. 6 , 15 (1996).
9. Madsen, G. K. H.*; Singh, D. J. Comput. Phys. Commun. 2006
175, 67
10. Mohd Zeeshan, Harish K. Singh, Jeroen van den Brink, and Hem
C. Kandpal Phys. Rev. Materials 1, 075407
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11. Twombly, C.,A study of thermoelectric properties of graphene
materials,Colorado School of
Mines,2015,http://adsabs.harvard.edu/abs/2015PhDT.......142T

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Acknowledgement

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Dr. Amal Medhi (My Project Guide)

My Lab-mates and Friends

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 aft
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