AN INTRODUCTION
Jos A. FloresLivas
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).
PhononBoltzmann 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
=
+
FermiDirac Distribution
BoseEinstein Distribution
LT
k
o
=
Metals
WiedemannFranz 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.
5
Seebeck effect.
MottJones expressiondependent 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;
7
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)
BlchGrneisen [4]
8
Phonon conductivity
Nonequilibrium (NEMD)
Equilibrium (EMD) or
GreenKubo
Boltzmann transport equation (BTEs)
The socalled 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.
DFTGround 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/mK.
[6] A. Ward et al., Phys. Rev. B 80, 125203 (2009)
Continuum transport
Theory and the exactly
solve the linearized phonon
(BTE).
11
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: Nonlinear dielectric susceptibility, Grneisen parameters,
PHONONPHONON 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 (GianMarco Rignanese) 2010.
( )
ele ion
E E +
12
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 (GianMarco Rignanese) 2010.
13
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 (GianMarco 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 realspace
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
RS 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
thirdorder order anharmonic IFCs. in there sets of
14
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 reciprocalspace 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 RSpace, where they are given by the third
order derivatives of the total energy respect to the Fourier transformed atomic displacements. [1112]
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 Thirdorder 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
Nonequilibrium 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).
15
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
Threephonon scattering rates are computed from Fermis golden rule with the anaharmonic IFCs
as input [6]:
Threephonon 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
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]:
18
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)
19
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 pBTZ calculation of Si and Ge, Solid
lines represent the isotopically enriched values.
Naturally occuring
Isotopically enriched
Experimental
ab initio (solid lines)
20
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]
21
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 keygold.
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, 37503754, (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:condmat/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 (GianMarco Rignanese) 2010.
A brief introduction to phonons http://www.tddft.org/bmg/seminars.php
23
Mi guel.
Si lvana.
Lauri .
Davi d.
Woyten
and
Gui lherme .
I want to Thanks: my group, and friends.