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THERMOELECTRICITY:

AN INTRODUCTION
Jos A. Flores-Livas
Laboratoire de Physique de la Matire Condense et Nanostructures
Universit Claude Bernard Lyon 1
18/01/2011
I. INTRODUCTION
Thermal conduction in solids.
II. THERMOELECTRICMATERIALS.
Seebeck effect.
III. FIGURE OF MERIT.
IV. CURRENT METHODS (BTE).
Phonon-Boltzmann Transport Equation.
V. STATEOF THE ART.
Outline
2
L
S
Z
o
k
=
I. THERMAL CONDUCTION IN SOLIDS
Fluid particles
Photons (classical electromagnetic waves treated as qsp)
Electrons;
Phonons; (lattice vibration treated as qsp)
Insulators Semiconductors
Phonons
Phonons + Electrons
/
1
1
P B
o
p
E k T
f
e
=

( ) /
1
1
e B
o
e
E k T
f
e

=
+
Fermi-Dirac Distribution
Bose-Einstein Distribution
LT
k
o
=
Metals
Wiedemann-Franz law
Thermal carriers.
3
V
T
S =
A temperature difference between two points in a conductor or semiconductor
results in a voltage difference between these 2 points[1].
Seebeck coefficient
The sign of S:
If electrons diffuse from hot to cold end; then the cold side is negative.
4
Seebeck effect. II. THERMOELECTRIC MATERIALS.
HOT
0
COLD
T
T
V= SdT
}
[1] Thermoelectric effects in metals: Thermocouples S.O. Kasap (2001).
II. THERMOELECTRIC MATERIALS.
- ( ) ( )
av av
e V E T T E T o o = +
2 2
0
-
2
F
k T T
e V
E
t o
o ~
2 2
0
2
F
V k T
T eE
o t
o
~
2 2
0
3
F
k T
S x
eE
t
~
V
S
T
o
o
=
Assumptions;
Free electron theory of metals.
Effective mass constant (e-).
Energy independent.
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Seebeck effect.
Mott-Jones expression-dependent E.
Imagine an electron diffuses from hot to cold
It has to do work against the
potential difference.
Substituting E_average and expanding
the expression of T, one obtain:
Since: , the coefficient Seebeck
is:
2
0
0
3 5
1
5 12
av F
F
kT
E E
E
t
(
| |
= +
( |
\ .

[1] Thermoelectric effects in metals: Thermocouples S.O. Kasap (2001).
III. FIGURE OF MERIT
e
o
L e p
k k k = +
2
e
L
S
ZT T
o
k
=
Electrical
conductivity
Thermal
conductivity
ZT=1 are good, 34 essential for
thermoelectric. The best reported ZT values
have been in the 23 range. [2]
[2] R. Venkatasubramanian, et al., Nature 413, 597 2001
Thermo power
State of the art
Theoretically &
experimentally
6
: ELECTRICAL CONDUCTIVITY
DRUDES model
[3] Advanced Semiconductor Lab. University of Korea
Temperature dependence of resistivity. [3]
q
At
J =
e
x
v
( )
1 2 3
1
[ ... ]
x
dx x x x xN i
e
eE
v v v v v t t
N m
= + + + + =
d
e
e
m
t
=
dx d x
v E =

x d x d
J e E en o = =
t o
t
t
1
S
S N
t

=
2
1 1

C
a T T
t t
t
=
2
1 1
e
T
d T
m T
en e nC

o
= = =
= DV
We define a drift mobility:
Mean scattering
time, often called
relaxation time.
DV increase linearly with E;
The conductivity term, then is;
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0 50 100 150 200 250 300
8x10
1
10
2
1.2x10
2
1.4x10
2
1.6x10
2
1.8x10
2
2x10
2
2.2x10
2
2.4x10
2
2.6x10
2
Pressure 4500 bar
BG_FIT- Parameters
O = 565 K

0
= 71.42 Ocm

f
= 0.69300698 Ocm
m = 1.73612619

O

c
m
]

|


L
o
g
1
0
Temperature [K]
Matthienssens and Nordheinms rule
1 1 1
T i
t t t
= +
1 1 1
d T i
en en en


= = +
0
( ) ( ) ( )
ph mag
T T T = + +
/
0
0
( ) ( 1)
( 1)(1 )
m
m
T
f
z z
T z
T m dz
e e

O
| |
= + O
|
O
\ .
}
2 2
6
2 (0)
B tr
f
F
k
e N v
t


=
2
BaSi
Figure. Cooper resistivity (NSC)
Blch Grneisen FIT of BaSi2_Trigonal (SC) [4]
Compounds, (more complicated)
Blch-Grneisen [4]
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Phonon conductivity
Non-equilibrium (NEMD)
Equilibrium (EMD) or
Green-Kubo
Boltzmann transport equation (BTEs)
The so-called RTAs
Varational principles approach
Exactly solve of the
liearized phonon BTE.
The continuum transport
theory
The atomistic technique
Montecarlo, Molecular dynamics, etc
Etc
IV. CURRENT METHODS (BTE).
: THERMAL CONDUCTIVITY
9
[5] Baoling Huang, University of Michigan (2008) Thesis
Phonon conductivity in
Diamond.
DFT-Ground state and its
derivatives trough DFPT
: some examples
10
Linear response of crystal to
determine the harmonic and
third order IFCs
Characteristics [6] :
Strong bond stiffness.
Light atoms.
High phonon frequencies and
High acoustical velocities.
The highest thermal
conductivity of any bulk
material RT- values of
3000 W/m-K.
[6] A. Ward et al., Phys. Rev. B 80, 125203 (2009)
Continuum transport
Theory and the exactly
solve the linearized phonon
(BTE).
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TOTAL ENERGY DERIVATIVES
Many physical properties are derivatives of the total energy, with respect to the
external perturbations. [7]
Related derivatives of the total energy on order are..
1
st
Order : Forces, stress, dipole moment
2
nd
Order: Dynamical matrix, elastic constants, dielectric susceptibility, Born
effective charge tensors, piezoelectricity, internal strains, etc
3
rd
Order: Non-linear dielectric susceptibility, Grneisen parameters,
PHONON-PHONON interaction, etc
Further properties con be obtained by integration over the phononic degrees of
freedom; (entropy, thermal expansion). [8]
[7] Tutorials (RF)of ABINIT http://www.abinit.org/
[8] CECAM Tutorial (Gian-Marco Rignanese) 2010.
( )
ele ion
E E +
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There are 4 different method to get the 1
st
order wave functions. [8]
Solving the Sternheimer equation directly.
Using the Greens function, technique.
Exploiting the sum over states expression.
Minimizing the constrained functional for the 2
nd
order correction to the energies.
With the 1
st
Order wavefunctions, corrections to the energies can be obtained.
More generally, the N
th
order WF give access to the 2
nd
and (2n+1) order energy theorem.
THESE DERIVATIVES CAN BE OBTAINED FROM; [8]
Perturbative approaches
Direct approaches:
Finite differences (Frozen phonons)
Molecular dynamics spectral analysis
methods
[7] Tutorials (RF)of ABINIT http://www.abinit.org/
[8] CECAM Tutorial (Gian-Marco Rignanese) 2010.
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PHONONS
Computation of phonon frequencies and eigenvector as solution of the
GENERALIZED EIGENVALUE PROBLEM :
[6] A. Ward et al., Phys. Rev. B 80, 125203 (2009)
[7] CECAM Tutorial (Gian-Marco Rignanese) 2010.
[9] http://www.tddft.org/bmg/seminars.php (2010)
'
'
'
' 2
1
D ( ,q)e (q)= e (q)
M M
o| |k ok
|k
k k
kk e

Where is the reciprocal space dynamical matrix constructed from the real-space
harmonic IFCs given by:
' ( )
) 0 ; ' '
l
'
' iq R
D ( ,q ( l )e
o| o|
|k
kk k k

= u

D
o|
Notation changed respect to the last
presentation of professor Miguel Marques.[9 ]
Vector position
Indicating the atom
with mass Mk
R-S harmonic IFCs
[10] X. Gonze and J. Vigneron, Phys. Rev. B 39,13120 (1989)
[6] A. Ward et al., Phys. Rev. B 80, 125203 (2009)
Further references:
[11] G. Deinzer, Phys. Rev. B 67, 144304 (2003)
[12] S. Baroni, Solid State Commun. 91, 813 (1994)
The theorem provides an analytic expression for the
third-order order anharmonic IFCs. in there sets of
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2
*
'
1
( ) ( ) ( )
el ion
E
q q q
N u u
o|
o| o|
o |
k k
c
u = u +u =
c c
The matrix reciprocal-space harmonic IFCs is a combination
of electronic and ionic parts [6]:
N = # of cells. The ionic terms involves the second derivative of energy.
The third order anharmonic IFCs are evaluated first in R-Space, where they are given by the third
order derivatives of the total energy respect to the Fourier transformed atomic displacements. [11-12]
3
' ''
' ''
( , ', '')
( ) ( ') ( '')
tot
E
q q q
u q u q u q
o|
kk k
o |
k k k
c
u =
c c c
Thanks to 2n+1 theorem [10] within DFPT Third-order response function is accessible.
{ }
, , q k o
THE LINEARIZED BOLTZMANN EQUATION [6]
0
c
n n
T
T t

u
c c
V =
c c
''
' '' j j j
(q) (q) (q ) e e e =
' '' q q q K = +
Consider a small gradient of temperature:
That perturbs a phonon distribution:
The anharmonicity of the interatomic potential causes phonon scatter inelastically from one another.
Umklampp process correspond to
And normal process is
0 1
n n n

= + ( , ) j q =
T V
Bose distribution function
Non-equilibrium part, proportional to
the small
We solve the linearized
BTE;
Conserving momentum and energy, satisfied:
The c is the collition term that
describes the scattering into
and out of the state. [13]
0 K =
0 K =
[13] Iterative solution; M. Omini and A. Sparavigna, Phys Rev. B 53, 9064 (1996).
[6] A. Ward et al., Phys. Rev. B 80, 125203 (2009).
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T V
0 0 0
' ''
2
, ', '' , ', '' ' ''
' ''
1 1
( 1)( )
2 2
( )
4
n n n
W
N



t
o e e e
e e e

+ +
= u
Three-phonon scattering rates are computed from Fermis golden rule with the anaharmonic IFCs
as input [6]:
Three-phonon matrix elements is given by:
' '
''
' '' ' '
, ', ''
' ' '' ''
' ''
(0 , ' ', '' '')
l l
iq R iq R
l l
e e e
l l e e
M M M

ok |k k
o|
k k k o|
k k k
k k k


u = u

[6] A. Ward et al., Phys. Rev. B 80, 125203 (2009)


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THE HARMONIC AND THIRD-ORDER ANHARMONIC IFCS
Phonon frequencies
R-space anharmonic IFCs
Phonon eigenvectors.
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1 0 0
( 1) n n n F T

| = + V
0
F F F
o o o
= +A
SCATTERING RATES
The scattering events are used in iterative solution to the L-phonon BTE, using
the substitution [13];
The phonon BTE can be recast as:
, , x y z o =
0 0
0
( 1) n n
F
TQ
o
o

e u +
=
, ', '' , ', '' , '
', '' '
1
2
imp
Q W W W


+
| |
= + +
|
\ .

[13] Iterative solution; M. Omini and A. Sparavigna, Phys Rev. B 53, 9064 (1996).
Total scattering rate defined as [6]:
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2
1
zz z z
C
V

k u t =

/
z
z z
TF


t e u =
LATTICE THERMAL CONDUCTIVITY [6]
Considering a temperature gradient along [001] (z) direction.
Starting from:
The phonon scattering time is related to as :
Then, the lattice thermal conductivity:
Where : is the specific heat per mode, and:
0 0 2
( 1)( )
B
C k n n

e | = + 1/( )
B
k T | =
' ''
0
z z
F F

= =
Correspond to 0th a single mode RTA.
[6] A. Ward et al., Phys. Rev. B 80, 125203 (2009)
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THERMAL CONDUCTIVITY RESULTS [6]
[6] A. Ward et al., Phys. Rev. B 80, 125203 (2009)
RTA solution and full converged solution.
(Dashed line represent percent error.)
Results of Full p-BTZ calculation of Si and Ge, Solid
lines represent the isotopically enriched values.
Naturally occuring
Isotopically enriched
Experimental
ab initio (solid lines)
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V. STATEOF THE ART. Mat er ial Challenges
Desirable electronic characteristics.
[14] ACS National meeting , talk of Mercouri Kanatzidis, April 2010.
[15] Tutorial of summer school Michigan State University, Kanatzidiss group 2006.
[15]
[15]
[14]
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Promi si ng systems
Alloys (Zr NiSn)
Zn4Sb3.
Skut t er udit es (CoSb3).
Yb14MnSb11
Bulk nano composit es based PbTe.
Bulk nano composit es based Si,Ge.
Clathrates . (Slacks proposal of PGEC.)
IN THERMOELECTRICITY
All compounds are strongly anisotropic.
There are many promising materials.
Nanostructures reduce the lattice thermal conductivity.
Doping seems to be the key-gold.
Nano saves thermoelectricity?
Predict thermoelectric properties by calculations?
Yes!
SUMMARY+CONCLUSIONS. (literature)
BIBLIOGRAPHY
22
Articles.
Nature 413, 597 2001
Phys. Rev. B 80 125203 (2009)
PRL. 104, 208501 (2010)
Nanoletters, Vol. 8 N. 11, 3750-3754, (2008)
X. Gonze and J. Vigneron, Phys. Rev. B 39,13120 (1989)
G. Deinzer, Phys. Rev. B 67, 144304 (2003)
S. Baroni, Solid State Commun. 91, 813 (1994)
Phys. Rev. B 77 12509 (2008)
arXiv:cond-mat/0602203v1. (2006)
Dalton Trans., 2010, 39, 978992
Thesis.
Al Thaddeus Avestruz. Massachusetts Institute of technology MIT. (1994).
Baoling Huang, University of Michigan (2008).
Books, tutorial and presentations.
Book: Thermoelectric effects in metals: Thermocouples S.O. Kasap (2001).
Tutorials (RF)of ABINIT http://www.abinit.org/
ACS National meeting , talk of Mercouri Kanatzidis, April 2010.
Tutorial of summer school Michigan State University, Kanatzidiss group 2006.
CECAMTutorial (Gian-Marco Rignanese) 2010.
A brief introduction to phonons http://www.tddft.org/bmg/seminars.php
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Mi guel.
Si lvana.
Lauri .
Davi d.
Woyten
and
Gui lherme .
I want to Thanks: my group, and friends.