Contoh

Figure of Merit Characterization of Thermoelectric Material :
Determination of Copper Figure of Merit

in the Temperature Range from 50 K to 300 K

A Thesis Submitted to Institut Teknologi Bandung
in Partial Fulfillment of the Requirement
for the Master Degree in Physics

by
Riser Fahdiran
20206004

STUDY PROGRAM OF PHYSICS
FACULTY OF MATHEMATICS AND NATURAL SCIENCES
INSTITUT TEKNOLOGI BANDUNG
2009
Figure of Merit Characterization of Thermoelectric Material :
Determination of Copper Figure of Merit
in the Temperature Range from 50 K to 300 K

A Thesis Submitted to Institut Teknologi Bandung
in Partial Fulfillment of the Requirement
for the Master Degree in Physics

by
Riser Fahdiran
20206004

Certified and approved by

Dr. A. Agung Nugroho
NIP : 132094575
Supervisor

STUDY PROGRAM OF PHYSICS
FACULTY OF MATHEMATICS AND NATURAL SCIENCES
INSTITUT TEKNOLOGI BANDUNG
2009
PEDOMAN PENGGUNAAN TESIS

Tesis S2 yang tidak dipublikasikan terdaftar dan tersedia di Perpustakaan Institut
Teknologi Bandung, dan terbuka untuk umum dengan ketentuan bahwa hak cipta
ada pada pengarang dengan mengikuti aturan HaKI yang berlaku di Institut
Teknologi Bandung. Referensi kepustakaan diperkenankan dicatat, tetapi
pengutipan atau peringkasan hanya dapat dilakukan seizin pengarang dan harus
disertai dengan kebiasaan ilmiah untuk menyebutkan sumbernya. Memperbanyak
atau menerbitkan sebagian atau seluruh tesis haruslah seizin Direktur Program
Pascasarjana, Institut Teknologi Bandung.

Abstrak

Pengkarakterisasian figure of merit untuk bahan termoelektrik telah dilakukan.
Pengukuran resistivitas, termopower dan konduktivitas termal sebagai fungsi dari
suhu dilakukan dengan menggunakan pendingin CTI-Cryogenic Model 350 CP
closed-cycle He. Desain dikontrol secara otomatis menggunakan LabVIEW 8.0
melalui antar-muka GPIB dalam daerah temperature 50 K 300 K setelah
cryostat divakum hingga 10
-6
mbar. Secara umum, pengukuran sifat transport
dilakukan dengan memberikan gangguan luar kepada sampel dan mengukur
responnya. Dalam hal ini, gangguan luar berupa sumber tegangan untuk
pengukuran resistivitas dan sumber panas untuk pengukuran termopower dan
konduktivitas termal. Respon yang didapat berupa tegangan listrik dan beda panas
didalam sampel. Digunakan bahan tembaga sebagai kalibrasi dari desain yang
digunakan dimana resistivitas, termopower dan konduktivitas termalnya sudah
ditentukan dengan baik berdasarkan referensi yang ada. Dari hasil pengukuran
didapatkan kesesuaian bilangan Lorentz dengan referensi yang ada pada suhu 288
K, yaitu 2,45 x 10
-8
W/K
2
. Dari hasil perhitungan didapati bahwa nilai ZT
terbesar dari tembaga pada suhu mendekati 300 K, yaitu 0,6.

Kata kunci : Termoelektrik, Resistivitas, Termopower, Konduktivitas Termal
Abstract
Figure of merit characterizations for thermoelectric materials were investigated. Re-
sistivity, thermopower and thermal conductivity temperature-dependent measure-
ments by incorporating the CTI-Cryogenic Model 350 CP closed-cycle He refriger-
ator system were performed. The design was carried out by LabVIEW 8.0 for com-
puter controlled automatic measurement through GPIB interface within the temper-
ature range from50 Kto 300 Kafter the chamber is vacuumized down to 10
6
mbar.
Generally, transport measurements are done by providing an external perturbation
to the sample and measuring the response of the sample. In our case, the exter-
nal perturbation is voltage source for resistivity measurements and heat supply for
thermopower and thermal conductivity measurements. The response is either an
electrical voltage and a heat gradient over the sample. We use standard copper for
calibration of the setup which resistivity, thermopower and thermal conductivity
were already determined precisely from the reference. From the measurements re-
sults we have good agreement of Lorentz number L of copper at temperature 288
K, which values 2.4510
8
W/K
2
. From the calculation result of ZT, copper has
the high value near 300 K, which is 0.6.
Keywords : Thermoelectric, Resistivity, Thermopower, Thermal Conductivity.
Contents
1 Introduction 5
1.1 Background and Motivation . . . . . . . . . . . . . . . . . . . . . 5
1.2 Scope of the Thesis . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3 Outline of the Thesis . . . . . . . . . . . . . . . . . . . . . . . . . 6
2 Theoretical Background 7
2.1 Boltzmann Equation . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Figure of Merit of Thermoelectric Materials . . . . . . . . . . . . . 9
2.2.1 Electrical Conductivity . . . . . . . . . . . . . . . . . . . . 10
2.2.2 Thermopower . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.2.3 Thermal Conductivity . . . . . . . . . . . . . . . . . . . . 13
2.2.4 Figure of Merit . . . . . . . . . . . . . . . . . . . . . . . . 15
3 Experiment 17
3.1 Sample Mount Apparatus . . . . . . . . . . . . . . . . . . . . . . . 18
3.2 Resistivity Measurement . . . . . . . . . . . . . . . . . . . . . . . 19
3.3 Thermopower and Thermal Conductivity Measurement . . . . . . . 21
1
CONTENTS 2
3.4 Platform Temperature Control and T Determination . . . . . . . . 23
4 Results and Discussion 26
4.1 Resistivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.2 Thermopower . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.3 Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.4 Figure of Merit . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5 Conclusion 33
Appendix A 34
Bibliography 42
List of Figures
2.1 A group of electrons moves rigidly through phase space under the
inuence of external electric elds (Madelung, 1996) . . . . . . . . 8
2.2 Resistivity of Copper based on electron gas model . . . . . . . . . . 11
2.3 Thermopower of Copper based on electron gas model . . . . . . . . 13
2.4 Thermal Conductivity of Copper based on electron gas model . . . . 14
2.5 ZT of some thermoelectric materials . . . . . . . . . . . . . . . . . 16
3.1 Measurements setup . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2 Sample Mount Apparatus . . . . . . . . . . . . . . . . . . . . . . . 18
3.3 Resistivity setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.4 Resistivity Measurement Graphical User Interface . . . . . . . . . . 20
3.5 Thermopower and Thermal Conductivity Setup . . . . . . . . . . . 21
3.6 Thermopower and Thermal Conductivity Graphical User Interface . 23
3.7 PID controller . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.1 Resistivity of copper . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.2 Relaxation time of copper . . . . . . . . . . . . . . . . . . . . . . . 27
3
LIST OF FIGURES 4
4.3 Thermopower of copper . . . . . . . . . . . . . . . . . . . . . . . . 28
4.4 Thermal Conductivity of copper . . . . . . . . . . . . . . . . . . . 30
4.5 Lorentz Number of copper . . . . . . . . . . . . . . . . . . . . . . 31
4.6 ZT of copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Chapter 1
Introduction
1.1 Background and Motivation
Thermoelectric materials have attracted many attentions because of the efciency
on converting heat waste into electrical energy directly or vice versa. It can be
used as cooling device or power generation. The process itself doesnt produce any
pollution, so it is very important for energy conservation.
Usually thermoelectric materials were made from alloys which mechanism
based on free electron transport in the materials. Some of thermoelectric materi-
als are Bi
2
Te
3
, PbTe, SiGe, Na
x
Co
2
O
4
and other semiconductor materials. These
thermoelectric materials exhibit high efciency that called gure of merit (ZT).
The gure of merit (ZT) depends on electrical resistivity, thermopower and
thermal conductivity of materials. In obtaining high ZT, we need materials which
possessed high thermopower and high electrical conductivity (low electrical resis-
tivity) but have low thermal conductivity. Semiconductors have low electrical re-
sistivity and high thermopower rather than metals. However, the thermopower and
the resistivity are not independent of each other, but depend on carrier density. Al-
though the thermopower increases logarithmically with decreasing carriers, the re-
sistivity is also enhanced. Consequently, the optimum carrier density is estimated to
be 10
18
- 10
19
cm
-3
[1]. The existence of this contrary parameters becomes problem
in obtaining high ZT.
5
CHAPTER 1. INTRODUCTION 6
Many researches is focusing on obtaining high thermopower in materials be-
cause it gives higher contribution in obtaining high ZT without increasing the elec-
trical resistivity and thermal conductivity. In 1997, Terasaki et.al. [2] have shown
large thermopower in oxide layered compound NaCo
2
O
4
. In this material, ther-
mopower is strongly enhanced by the spin and orbital degeneracy, but the resistivity
is not much affected by the degeneracy [1]. These materials also possess low ther-
mal conductivity due to suppresion from electron spin and orbital contribution [3].
Since then, many thermoelectric researches are focusing on enhancing thermopower
by combining the degeneration level of the transition metal in oxide materials.
1.2 Scope of the Thesis
The gure of merit (ZT) of thermoelectric materials are depends on electrical resis-
tivity, thermopower and thermal conductivity. Determining these three parameters
by experiments is not a simple task if we considered the methods of measurements
and the materials itself. Although it is not simple to measure the parameters, we are
quite sure to build the setup based on our experiences and references. The resistiv-
ity measurements were based on four probe measurements. While thermopower and
thermal conductivity measurements were based on steady state method combined
with differential technique [4-7]. Therefore, this thesis develops the measurements
methods of these three parameters for any kind of bulk materials.
1.3 Outline of the Thesis
In this thesis, Chapter 1 is describing the background and motivation, scope and
also outline of the thesis. Chapter 2 discusses the transport mechanism and gure
of merit (ZT) in thermoelectric material. The experimental procedure of the mea-
surements methods were described in Chapter 3. Chapter 4 explains the results and
discussion. Finally, Chapter 5 gives conclusions of this work.
Chapter 2
Theoretical Background
This chapter will introduce the theoretical background applied in this thesis. The
rst section of this chapter will explain the transport mechanism based on Boltz-
mann equation. This leading us to the gure of merit properties of thermoelectric
material in the next section. For a more detailed theoretical background see Refs.
[8-13].
2.1 Boltzmann Equation
Through electron-phonon interaction, energy and momentum are exchanged be-
tween the electron system and the ion lattice. This interaction is of particular im-
portance when one of the two systems is not in equilibrium. If one accelerates the
electrons of a solid by external electric eld, the energy absorbed from the eld will
be passed on to the lattice by excitation of lattice vibrations, that is, by emission of
phonons. Only in this way a steady state with current ow can be set up, in which
acceleration of electrons by the eld and slowing down by phonon emission are
balanced. When the external eld is switched off, the interaction process ensures
that equilibrium of the electron system is reestablished.
In constructing the nonequilibrium distribution function, we must considered
the collisions in the interval range of time. To describe the complete electron sys-
tem, the distribution function f = f
n
(r, k, t), which gives the occupation probability
of a state characterized by band index n, k-vector k, and space vector r. In equilib-
7
CHAPTER 2. THEORETICAL BACKGROUND 8
rium, f
n
(r, k, t) is the Fermi distribution f
o
. To calculate the distribution function
f
n
(r, k, t) in given external elds, we examine its behaviour with time (Fig. 2.1).
Consider a group of electrons in the volume element d
r
d
k
in phase space. In the
course of time this group will move through phase space. For the short time inter-
val considered, let the form of the group remain essentially unchanged. Then the
total differential quotient
f
/t would be zero if electrons were not scattered from
(k, d
k
) to another (k
, d
k
) and vice versa, by electron-phonon interaction.
Figure 2.1: A group of electrons moves rigidly through phase space under the inu-
ence of external electric elds (Madelung, 1996)
The distribution function follows froma differential equation, Boltzmann equa-
tion. If an external eld drives the electron system into a nonequilibrium state and
is then removed, electron-phonon interaction are responsible for the return of the
system to equilibrium. In this case we also considered the collision that produce
scattering in the system. The Boltzmann equation for electrons take the following
form :
d f
dt
=
f
t
+

k
k
f + r
r
f =
f
t
coll
(2.1)
where :
k =
e
h
(E+vB) (2.2)
and
r =
1
h
k
E (k) (2.3)
The Boltzmann equation for the electrons can easily be solved if it is possible
to describe the electron-lattice interaction through a relaxation time approximation:
f
t
coll
=
f
o
f
(2.4)
And after some mathematical works (see Appendix A), we obtain :
f = f
o
v
_
E
T
T
_
f
o
E
(2.5)
where is relaxation time, = +qV is the electrochemical potential that com-
bines chemical potential and electrostatic potential energy and V is the electrostatic
potential (q = -e for electrons, and +e for holes).
Electron-phonon interaction gives contribution on the behavior of a solid un-
der the inuence of external elds, i.e., transport properties of solids. Along with
electric eld, the term external eld embraces an additional magnetic eld and
a temperature gradient. Electrons driven by these forces carry charge and energy
with them. The elds causes electric current density j
q
and energy current density
j
E
. These currents can be readily determined if the number of electrons n with given
momentum at a given location is known as a function of time. Since the number of
electrons per unit volume can be calculated, the electric current density in a band is:
j
q
=
(ev)n(E)dE =
(ev) f (E)g(E)dE (2.6)

And the volume of the region is xed, changes in the entropy in the region are
related to changes in internal energy and number of electrons. In this case, the
quantity carried by electrons is no longer its charge but its energy, so the energy
current density is :
j
E
=
E vn(E)dE =
E v f (E)g(E)dE (2.7)
2.2 Figure of Merit of Thermoelectric Materials
Before describing the gure of merit of thermoelectric materials, we take a look
again the eq. 2.6 and 2.7. The uxes electrical current density j
q
and energy
current density j
E
are related to the forces (gradients of the electrostatic potential,
the chemical potential and the temperature). The thermodynamics of irreversible
processes postulates that, when local entropy is represented as a sum of products
of uxes and forces, both are always linearly related to one another. So after some
mathematical works (see Appendix A), in general form (q = -e for electrons, and +e
for holes), electrical current density j
q
and energy current density j
E
becomes :
j
q
= L
11
_
1
q
_
+L
12
(T) (2.8)
j
E
= L
21
_
1
q
_
+L
22
(T) (2.9)
where
L
11
=
2q
2
3m

E=0
f
o
E
g(E) E dE (2.10)
L
12
=
2q
3mT

E=0
f
o
E
(E )g(E) E dE (2.11)
L
21
=
2q
3m

E=0
f
o
E
(E )g(E) E dE (2.12)
L
22
=
2
3mT

E=0
f
o
E
(E )
2
g(E) E dE (2.13)
2.2.1 Electrical Conductivity
In homogeneous solid =( +qV) is identical to the electric eld E =V,
since the chemical potential is then independent of position. In the case of zero
temperature gradient and zero carrier concentration gradient, T = 0 and = 0,
eq. 2.8 becomes :
j
q
= L
11
_
1
q
_
= L
11
_
1
q
+E
_
= L
11
E (2.14)
The electrical conductivity is dened as :
=
j
q
E
= L
11
=
2q
2
3m

E=0
f
o
E
g(E) E dE (2.15)
In another denition by doing some mathematical works (see Appendix A) in eq.
2.15, electrical conductivity is dened as :
=
ne
2
m
(2.16)
The denition of electrical resistivity is the inverse of electrical conductivity ,
so :
=
1
=
m
ne
2
(2.17)
where from this denition, resistivity is inversely depends on relaxation time .
In metals, there are two physically distinguishable sources of scattering which
is scattering by impurities atom and scattering of electrons by phonons. If the pres-
ence of one mechanism does not alter the way in which the other mechanism func-
tions, then the relaxation time will be given by the sums of the separate mecha-
nism. In relaxation time approximation this implies that
1
=
1
i
+
1
ph
(2.18)
On the other hand, a generally valid relaxation time can be dene for the tempera-
ture region T
D
,
D
is Debye temperature. Where in this region
1
T
. Which
means that the resistivity is linearly dependent with temperature. The simulation of
Copper resistivity using Maple 9.0 based on eq. 2.17 are shown in Fig. 2.2.
Figure 2.2: Resistivity of Copper based on electron gas model
2.2.2 Thermopower
When we applied a temperature gradient between two ends of a solid, the electrons
will be maintained in both ends. In the case of non-zero temperature gradient, a
thermoelectric voltage can be measures between two ends of the solid, where j
q
=0.
Hence from eq. 2.8 we obtain :
j
q
= L
11
_
1
q
_
+L
12
(T) = 0 (2.19)
Therefore
T
=

T
=
qL
12
L
11
(2.20)
The thermoelectric voltage between the two ends of the solid is dened as
V =

q
. We can also write eq.2.20 as
V
T
=
L
12
L
11
= S (2.21)
where we dened the thermopower S and describes the thermoelectric voltage caused
by a heat gradient, with the additional condition that no electrical current is allowed
to ow. From this (see Appendix A) we also obtain the thermopower, which is also
called Seebeck coefcient, becomes :
S =
k
B
q
_
_

k
B
T

_
r +
5
2
_
F
r+
3
/2
_

k
B
T
_
_
r +
3
2
_
F
r+
1
/2
_

k
B
T
_
_
_
(2.22)
where r is a coefcient from the denitions =
o
E
r
, F
n
_

k
B
T
_
is the fermi integral.
For metal, where

k
B
T
0, the value of thermopower becomes :
S =
2
k
B
3q
_
k
B
T
__
3
2
+r
_
(2.23)
This value can be either positive or negative depending on r value or how scattering
rate depends on electron energy. In metal, we ignore the weak temperature depen-
dence of and assume = E
F
, the Fermi level is the highest energy occupied by
electrons at 0 K. The simulation of Copper thermopower using Maple 9.0 based on
eq. 2.23 are shown in Fig. 2.3.
Figure 2.3: Thermopower of Copper based on electron gas model
2.2.3 Thermal Conductivity
In the case of zero electrical current density j
q
= 0 and non-zero temperature gradi-
ent, eq. 2.9 becomes (see Appendix A) :
j
E
=
_
L
22
L
12
L
21
L
11
_
(T) (2.24)
Consider a small xed region of the solid within which the temperature gradient is
effectively constant. The rate at which heat appears in the region changes. Then eq.
2.24 will dene the thermal conductivity :
_
L
22
L
12
L
21
L
11
_
= L
22
L
21
S = (2.25)
For metals, S usually very small so that from eq. 2.25 we have = L
22
. If we
use kinetic experession of electron energy, we will have (see Appendix A) :
=
1
3

E=0
f
o
(E)
T
(E ) g(E) v
2
dE (2.26)
When E is far away from , f
o
(E) remains to be either 0 or 1 as the tempera-
ture changes, so that
f
o
(E)
T
is non-zero only when E is close to . Therefore, for
electronics contribution, eq. 2.26 can be approximated by taking v = v
F
(Fermi
velocity) and =
F
(Fermi scattering mean free time ) of Fermi electrons, so
e
=
1
3
v
2
F

E=0
f
o
(E)
T
(E )dE =
1
3
v
2
F

F
C =
1
3
Cv
F
l
F
(2.27)
where C is the specic heat and l
F
is the mean free path of the respective heat
carrying excitations. From the denition of specic heat :
C =

2
nk
2
B
T
mv
2
F
(2.28)
we can also write thermal conductivity as :
e
=

2
nk
2
B
l
F
3mv
F
T =

2
nk
2
B
F
3m
T (2.29)
The simulation of Copper thermal conductivity using Maple 9.0 based on eq. 2.29
are shown in Fig. 2.4.
Figure 2.4: Thermal Conductivity of Copper based on electron gas model
The ratio between the electron thermal conductivity eq. 2.29 and electrical
conductivity eq. 2.16 is :
=
1
3
v
2
F

F
C
e
2
m
n
F
=
mv
2
F
3ne
2
2
nk
B
T
mv
2
F
=

2
k
2
B
T
3e
2
(2.30)
We dene the Lorentz number
L =

2
k
2
B
3e
2
= 2.4510
8
_
W/K
2
_
(2.31)
So that we obtain the Wiedemann-Franz law :
= LT (2.32)
The Wiedemann-Franz law is valid, if only elastic scattering processes occur, which
is usually the case for low temperatures (only boundary scattering) and for high
temperatures. For intermediate temperatures charge carriers are mainly scattered
by phonons which lowers the value of L.
In good metals, only the electronic contribution to is relevant. The reason is
that the absolute values of from electrons are large, and that phonons are strongly
scattered by the electrons. For bad metals electronic and phononic contributions
can be of the same size. For bad insulators often only the phononic contribution
is relevant at low temperatures, but through the thermal activation of electrons the
electronic contribution becomes more and more important for high temperatures. In
most cases two kinds of excitations are responsible for the heat transport: phonons
and electrons. The theoretical description is usually based on the Debye model in
the rst case, and on the electronic gas theory for the latter case [14]. In mathemat-
ical expression, the thermal conductivity of phonons are given by :
ph
=
k
B
2
2
v
_
k
B
h
_
3
T
3
D
T
0
x
4
e
x
(e
x
1)
2
dx (2.33)
So, in general, the total thermal conductivity can be written as :
=
e
+
ph
(2.34)
For more details about phonons contribution to thermal conductivity see Ref [8].
2.2.4 Figure of Merit
The thermoelectric gure of merit ZT gives a measure for the efciency of a material
for thermoelectric cooling or power generation. The gure of merit ZT is dened
by :
ZT =
S
2
T =
S
2

T (2.35)
The gure of merit is dened with certain temperature T to know where is the
highest efciency occured in thermoelectric materials temperature. To obtain high
ZT, one must increase the thermopower coefcient S and reduce the resistivity
without increasing the thermal conductivity . For applications, we must have ZT
> 2. Fig. 2.5 shows the ZT of some thermoelectric materials.
Figure 2.5: ZT of some thermoelectric materials
Chapter 3
Experiment
In this thesis, the design and its implementations of resistivity, thermopower and
thermal conductivity temperature-dependent measurements by incorporating the
CTI-Cryogenic Model 350 CP closed-cycle He refrigerator system were performed.
The design was carried out by LabVIEW 8.0 [15] for computer controlled automatic
measurement through GPIB interface [16] within the temperature range from 50 K
to 300 K after the chamber is vacuumized down to 10
6
mbar (Fig. 3.1)[17]. Gen-
erally, transport measurements are done by providing an external perturbation to the
sample and measuring the response of the sample. In our case, the external perturba-
tion is voltage source for resistivity measurements and heat supply for thermopower
and thermal conductivity measurements. The response is either an electrical voltage
and a heat gradient over the sample.
Figure 3.1: Measurements setup
17
CHAPTER 3. EXPERIMENT 18
3.1 Sample Mount Apparatus
The chamber for the sample holder is vacuumized down to 10
6
mbar before the
measurements are taken. After the chamber is vacuumized, He gas are ow into
the cold nger and return it again back to the compressor using closed-cycle prin-
ciple. By doing so, the cold head become colder and could reach 25 K. We use
heat link from the sample holder to the cold head so we can controlled it in high
precision and the thermal equilibrium is obtained on the sample holder (Fig. 3.2).
The sample holder was designed in order to easily introduced the sample into the
chamber without replacing any components under it. Two calibrated silicon diode
temperature sensors were place under the center of the sample holder and another
one were embedded in the center of cold head of closed-cycle refrigerator. Strain
gage heater is embedded in the center of cold head and along with the sensors are
controlled by Lakeshore 330 Autotuning Temperature Controller. Radiation shield
made from copper were used to reect the heat back on the sample. Due to the heat
link, in present, we can only cold down the temperature on the sample holder down
to 45 K. After the sample holder temperature become stable the measurements are
taken.
Figure 3.2: Sample Mount Apparatus
In wiring from the sample to the measurement instruments we uses few types
of wires. From the sample to the sample holder, Pt-wires are used because it has
low electrical resistivity contribution to the measurements. From the sample holder
to the wire connector we used phospor-bronze wires because it has low thermal
conductivity. The wire connector connected to the copper wires that are linked
with the cable from the instruments. Hence, before we obtain the real values of
the properties we substract the measurements results with some corrections. To do
this, we use standard copper block for calibration of the setup which resistivity,
thermopower and thermal conductivity were already determined precisely from the
references. So, the corrections will be :
f
corr
= f
meas
f
Cu
(3.1)
where f denotes the properties (resistivity, thermopower or thermal conductivity)
that we measure.
3.2 Resistivity Measurement
The resistivity of the samples were measured using 4-point probes conguration
using Pt-wires pasted to the sample using silver paste with constant voltage source
(Fig 3.3). Pt-wires were used in order to minimized the electrical resistivity con-
tribution from the wires. Two wires are used as voltage source contact, while the
other two wires are used as current sense contact. Typically, we are measured the
sample with approximate dimensions of 3 x 10 x 1.5 mm
3
.
Figure 3.3: Resistivity setup
The data acquisition were done by taking resistance measurement using Ag-
ilent 34401A Digital Multimeter at a stable temperature controlled by Lakeshore
330 Autotuning Temperature Controller. A custom designed data aquisition pro-
gram using LabVIEW is developed that automates the data acquisition process (Fig
3.4). The cross-sectional area of the samples, which have been measured, is en-
tered into this program. The length between the sense wires is measured from the
inside edge of the two wires and entered into the program. This measurement is
repeated at desired increments of temperature from 50 to 300 K. A typical measure-
ment sequence for the entire temperature range will take 56 h to run the sample
on this apparatus. Another measurements that can also carried out is using Keithley
2400 Source Meter. The data acquisition were done by taking V-I measurement and
within the ohmic region obtained from the V-I slope, the resistivity is taken. The
resistivity were determined using :
= R
A
L
(3.2)
where R is the resistance (in ohms), L is the length (in meters) between the two
sense wire and A is the cross section area (in meters
2
) of the sample.
Figure 3.4: Resistivity Measurement Graphical User Interface
3.3 Thermopower and Thermal Conductivity Mea-
surement
Thermopower and thermal conductivity measurements are made almost simultane-
ously using steady state method combined with differential technique. Typically,
we are measured the sample with approximate dimensions of 3 x 10 x 1.5 mm
3
.
The SMD resistor act as a heater supplier that supply heat current to the sample.
After some interval of time, a small temperature gradient T obtained and gives
rise to a thermal electromotive force. In equilibrium, we sweep the power P versus
temperature difference T and measuring the corresponding thermal voltage V
(Fig 3.5). The sweep must be linear, if it is not a straight line, there are losses due
to convection which need to be corrected for or minimized. From this concept, we
determine thermopower S and thermal conductivity :
S =
V
T
(3.3)
and
=
L
A
P
T
(3.4)
where P is the heat power supply (in Watt), L is the length (in meters) between the
two thermocouple wires and A is the cross section area (in meters
2
) of the sample.
Figure 3.5: Thermopower and Thermal Conductivity Setup
In order to minimize conductive loss, a differential thermocouple is utilized to
measure T so that there will only be two wires available as a heat leak, instead
of four wires if standard thermocouples were used. The chromel (+ wire) - AuFe
0.07 % (- wire) are used as differential thermocouple because it provides excellent
thermal sensitivity in the range 1.4 K - 325 K. Pt-wires are used as V contact in
order to reduce electrical resistivity contribution from the wires. Radiative loss is
also reduced by utilization of radiation shield that will reect the heat back to the
sample.
Lakeshore 330 Autotuning Temperature Controller is used to control the plat-
form temperature and maintained it in an equilibrium condition. The SMD resistor
glued on top of the sample using glue furnace act as a heater supplier is controlled
using Agilent 6625A System DC Power Supply. The heat from SMD resistor is in-
put into the sample until the heat ow is uniform and stable, typically 23 min. The
power through the heater is slightly increased, the temperature difference allowed to
equilibrate. The data acquisition were done by reading T using Agilent 34401A
Digital Multimeter, while V was read using Keithley 2182 Nanovoltmeter through
Keithley 7168 scanner card and Keithley 7001 switch system.
This sequence is repeated several times, resulting in a power verses T sweep
and also V verses T sweep at a given temperature. This power and V sweep is
then t to a straight line, the slope being proportional to the thermal conductivity and
the thermopower respectively. This measurement is repeated at desired increments
of temperature from 50 to 300 K. A typical measurement sequence for the entire
temperature range will take 2430 h to run the sample on this apparatus. A custom
designed data aquisition program using LabVIEW is developed that automates the
data acquisition process (Fig 3.6). The cross-sectional area of the samples, which
have been measured, is entered into this program. The length between the two
thermocouple wires is measured from the inside edge of the two wires and entered
into the program.
Figure 3.6: Thermopower and Thermal Conductivity Graphical User Interface
3.4 Platform Temperature Control and T Determi-
nation
Our goal in measuring the properties is to measure in a specic temperature. There-
fore we can determine the gure of merit precisely correspond to the system tem-
perature. We use Lakeshore 330 Autotuning Temperature Controller to control the
platform temperature precisely. This instrument can stabilize the platform temper-
ature within the deviation from setpoint is about (0.1K0.2K).
When we measure the properties, we divide into two temperature ranges mea-
surements, 50 K - 150 K and 150 K - 300 K. The reason is that the handling for this
two ranges is somehow quite different. In the range of 50 K - 150 K we need high
heater power in the platform to achieve the setpoint and then controlled it with devi-
ation from the setpoint for about 0.2K. Within this temperature range, the system
temperature is easily affected by environment but we can managed it by keep the
chamber with vacuum down to 10
6
mbar. While in the range of 150 K - 300 K less
heater power were needed to achieve the temperature setpoint. In this range, we can
control the platform temperature with deviation from setpoint about 0.1K.
Figure 3.7: PID controller
We use Proportional-Integral-Derivative (PID) controller scheme in control-
ling the platform temperature. To determine the appropriate PID values for the
thermal system at hand using the instrument we use Ziegler-Nichols method [16].
The determination is done empirically, often after spending a large amount of time
trying various combinations of values to see which works best. If this must be done
in a production environment where varying loads must be tested at multiple tem-
peratures, the amount of wasted time can grow quickly. However, we make a home
made PID controller using LabVIEW (Fig. 3.7) to obtain the best value by means
of Ziegler-Nichols method and apply it into the measurement program. The results
is quite good, and the temperature setpoint could be reach within 1 to 2 minutes
before it stable.
To determine the real value of the temperature difference using thermocouple
contact is another problem in the measurements. We need to convert the voltage
V
TC
value from the thermocouple leads into temperature difference T. In doing
this we extracted the voltage value of the leads and differentiate it with the plat-
form temperature T
plat f orm
. After the differentiation then we multiply the inverse
slope
dV
TC
dT
plat f orm
from the differentiation with the V
TC
value leading to the desired
temperature difference:
T =V
TC
.
dT
plat f orm
dV
TC
(3.5)
We dene the system temperature by [4, 5] :
T
sys
= T
plat f orm
+
1
2
T (3.6)
Chapter 4
Results and Discussion
The measurements were done by heating the platform temperature from 50 K to
300 K. While equilibrium state were achieved by controlling the platform, the data
are taken. Every single point of data were then corrected or minimized to reduce
noises and heat convection. The measurements results for copper are shown in this
chapter.
4.1 Resistivity
Figure 4.1 shows the electrical resistivity of copper fromthe measurement and ref-
erence [18-22]. The resistivity temperature dependence was taken from 50 K to 300
K. From eq. 2.17 we found that the resistivity will be linearly dependent with tem-
perature in this range. This was true due to scattering of electrons by phonons. Elec-
trons are assumed to achieve thermal equilibrium with their surroundings through
collisions of electron-phonon interaction. The hotter the region in which a collision
occurs, the faster a typical electron will emerge from the collision. Because of this,
the electron spends only a small fraction of its time near the phonons, where the
potential is strong. Most of the time the electron is far away in a region in which
the potential is weak. This leads to linearly dependent on resistivity in this temper-
ature range measurement. Also we saw from Fig. 4.1, if we continue to measure
the resistivity below 50 K it will shows the residual resistivity of copper, which is
commonly found in metals.
26
CHAPTER 4. RESULTS AND DISCUSSION 27
Figure 4.1: Resistivity of copper
From the interpretation of eq. 2.17 we found that the probability of the elec-
trons suffering a scattering per unit time is equal to
1
. From the measurement we

have = (3.4 4.4) 10
14
s and from the reference the value is around 2.7
10
14
s. It means that the electron undergoes around 10
14
collisions in one second.
In the case where T increases, scattering by phonons becomes more effective and
the resistivity increases linearly. Fig. 4.2 shows the relaxation time in copper.
Figure 4.2: Relaxation time of copper
From the measurement result, we see that the order of magnitude of the copper
resistivity is quite excellent in agreement with the reference, although the value is
quite different somehow. G.K. White in 1953 [19], were doing some experiments
to characterize the thermal and electrical conductivity of copper. He found that dif-
ferent treatment to the samples could give different value of the material properties.
One of them is if we annealed the sample. Our copper sample may be not as pure
as the reference because it already oxidized when we anneal the sample during the
probe contact installation and the specimen was also not the same. In our case, the
sample becomes more insulating than the pure copper from the reference. An-
other reason is emerge from the wire contribution. As we already mention in Sec.
3.1 we used few types of wires to connect the material with instruments. And af-
ter some correction using eq. 3.1, the electrical resitivity of copper was already
corrected by the wire reference value to obtain the measurement result. Vacuum
state in the cryostat could also gives another contribution during the measurement.
Although the cryostat were vacuumized to 10
-6
mbar, there are also possibilities of
environment contribution to the cryostat through heat convection.
4.2 Thermopower
Figure 4.3: Thermopower of copper
Measurement result of thermopower temperature dependence of copper is shown in
Fig. 4.3 along with the reference [24-28]. The thermopower temperature depen-
dence was taken from 50 K to 300 K.
In the measurement result we see above 70 K the thermopower becomes al-
most linear in positive value and from 50 K - 70 K the thermopower was affected
by phonons contributions. In the rst case, above 70 K, the contribution comes from
the electrons in the material. While in the range of 50 K - 70 K, phonons give larger
contributions to the thermopower by means of phonon-drag mechanism. Because
of the temperature gradient generate by the heater, the phonons system were per-
turbed. Through the scattering processes the electrons will then be made aware of
the preferred direction of the phonons. In the other hand, around 100 K, the carriers
in the material were changed from holes to electrons.
From the interpretation of eq. 2.23 correspond to the measurement result we
see that there is a change of the sign of thermopower value in temperature around
100 K due to carriers changes. As already mentioned in sec. 4.1, our sample were
already not as pure as the reference, because its already oxidized when we annealed
the sample during the probe contact installation and the specimen was also not the
same. In the other hand, the phonons contribution occurred in the range of 50 K -
70 K , while a pure copper shows phonons contribution in the range of 50 K - 145
K. This means that our copper sample was impurized by oxygen due to annealing
but need more investigation to certain this. Another reason is emerge from the wire
contribution. As already mention in Sec. 3.1 we used few types of wires to connect
the material with instruments.
And after some correction using eq. 3.1, the thermopower of copper was al-
ready corrected by the wire reference value to obtain the measurement result. Vac-
uum state in the cryostat could also gives another contribution during the measure-
ment. Although the cryostat were vacuumized to 10
-6
mbar, there are also possi-
bilities of environment contribution to the cryostat through heat convection. The
radiation shield was used to minimize it.
4.3 Thermal Conductivity
Measurement result of thermal conductivity temperature dependence of copper is
shown in Fig. 4.4 along with the reference [19, 21]. The thermal conductivity
temperature dependence was taken from 50 K to 300 K.
Figure 4.4: Thermal Conductivity of copper
Although according to eq. 2.29 the thermal conductivity should be linear with
temperature, from measurement result we see that in the temperature range above
80 K the thermal conductivity becomes almost constant. While in the range of 50
K - 80 K the thermal conductivity was affected by phonons contributions. In the
case of above 80 K, the contribution comes from the electrons in the material. The
reason is that the absolute values of from electrons are large, and that phonons
are strongly scattered by the electrons. While in the range of 50 K - 80 K, phonons
give larger contributions to the thermal conductivity. Due to phonons contributions,
eq. 2.29 cannot explain the thermal conductivity correctly but we need to consider
phonons contribution eq. 2.33 to the result.
In the other hand we can also dened the Lorentz number according to Wiedemann-
Franz law on eq. 2.32. Fig 4.5 shows the Lorentz number as a function of temper-
ature. Theoretically the Lorentz number will be constant in all pure metal. This
was true if the scattering process occured only if T >
D
. But we see in the Fig. 4.5
that Lorentz number change as a function of temperature which value has the range
of L = 5.6 10
9
W/K
2
5.6 10
7
W/K
2
where we have a good agreement
with eq. 2.31 at temperature 288 K. The Wiedemann-Franz law is valid, if only
elastic scattering processes occur, which is usually the case for low temperatures
(only boundary scattering) and for high temperatures. For intermediate tempera-
tures charge carriers are mainly scattered by phonons which lowers the value of L
[29].
Figure 4.5: Lorentz Number of copper
4.4 Figure of Merit
Calculation result of gure of merit ZT temperature dependence of copper is shown
in Fig. 4.6. The thermal conductivity temperature dependence was calculated from
50 K to 300 K based on the measurements results.
Figure 4.6: ZT of copper
From the calculation result based on eq. 2.35 we see that ZT of copper are
quite small compare to commercial thermoelectric materials (Bi
2
Te
3
, ZT > 1). The
ZT of copper has the high value near 300 K, which is 0.6. For applications as
a thermoelectric device, we need ZT > 2. So, in general, copper is not a good
thermoelectric material.
Chapter 5
Conclusion
This thesis report the design and its implementation of gure of merit characteriza-
tion for thermoelectric materials. The temperature-dependent measurements setup
incorporating the CTI-Cryogenic Model 350 CP closed-cycle He refrigerator sys-
tem was was carried out by LabVIEW 8.0 for computer controlled automatic mea-
surement through GPIB interface within the temperature range from 50 K to 300 K.
We use standard copper for calibration of the setup which resistivity, thermopower
and thermal conductivity were already determined precisely from the references.
Based on the measurements results we obtained :
Resistivity of copper are linearly dependent with temperature in this range
which values is = 1.2310
8
.m8.610
7
.m.
Thermopower S of copper with temperature in this range has values of S =
0.7V/K2.95V/K.
Thermal conductivity of copper with temperature in this range has values
of = 6.02W/cm.K26.4W/cm.K.
Mean free time of copper with temperature in this range has values of =
(3.44.4) 10
14
s.
Lorentz number L of copper with temperature in this range has values of
L = 5.610
9
W/K
2
5.610
7
W/K
2
.
The ZT of copper has the high value near 300 K, which is 0.6.
33
Appendix A
The Boltzmann equation for electrons take the following form (from eq. 2.1 and
2.4) :
d f
dt
=
f
t
+

k
k
f + r
r
f =
f
t
coll
=
f
o
f
(5.1)
where f
o
is the Fermi distribution :
f
o
(E, T) =
_
1+exp
_
E
k
B
T
__
1
(5.2)
For the steady state case with small temperature/concentration gradient and electric
eld in the certain direction only, the variation of the distribution function in time is
much smaller than that in space, or
f
t
vf , so that we can assume
f
t
0. The
temperature gradient and electric eld is small so that the deviation from equilib-
rium distribution f
o
is small, f
o
f f
o
. f f
o
, and
f
p
f
o
p

f
o
E
E
p
=v
f
o
E
.
With these assumption eq. 2.1 becomes
v
_
f
o
+qE
f
o
E
_
=
f
o
f
(5.3)
We considered electrons in the conduction band where we measure E and
from this band edge. In the case where E (k) =E
C
= 0, we have :
f
o
E
=
f
o
E
or
f
o
= k
B
T
f
o
E
(5.4)
where we dene
E
k
B
T
. From this we also have :
f
o
=
d f
o
d
= k
B
T
f
o
E
(5.5)
34
CHAPTER 5. CONCLUSION 35
and
=
1
k
B
T
(E (k) )
E
k
B
T
2
T =
1
k
B
T

E
k
B
T
2
T (5.6)
From eqs. A.5 and A.6,
f
o
=
f
o
E
_
+
E
T
T
_
(5.7)
Combine eq. A.3 and eq. A.6 we have
v
_

E
T
T +qE
_
f
o
E
=
f
o
f
(5.8)
From E =V and combined it with eq. A.8, we obtain
v
_

E
T
T qV
_
f
o
E
=
f
o
f
(5.9)
and we have eq. 2.5
f = f
o
v
_
E
T
T
_
f
o
E
And if we expand eq. 2.5 we have :
f = f
o
vcos
_
E
T
T
_
f
o
E
(5.10)
After we have the nonequlibrium distribution function, now we determine the
current density caused by the external elds. Because of this elds, the electrons
will have the probability to move in all directions. Where in spherical coordinates
an electron will move in the (, ) direction within a solid angle d = sin d d
with probability d/4. Hence, the electrical current density j
q
and energy current
density j
E
carried by all electrons moving toward the entire sphere respectively
j
q
=
4
d
4

E=0
f (E)g(E)qvcos dE
j
q
=
2
=0
1
4
d

=0
sin cos d

E=0
f (E)g(E)qvdE (5.11)
and
j
E
=
4
d
4

E=0
f (E)g(E)Evcos dE
j
E
==
2
=0
1
4
d

=0
sin cos d

E=0
f (E)g(E)E vdE (5.12)
Combine eq. A.10 with A.11 and A.12, we obtain the electrical current density
j
q
and energy current density j
E
carried by all electrons moving toward the entire
sphere respectively
j
q
=
2
=0
1
4
d

=0
sin cos d

E=0
f
o
(E)g(E)qvdE
+
2
=0
1
4
d

=0
sin cos
2
d

E=0
f
o
E
g(E)qv
2
_
+
E
T
T
_
dE
(5.13)
and
j
E
=
2
=0
1
4
d

=0
sin cos d

E=0
f
o
(E)g(E)EvdE
+
2
=0
1
4
d

=0
sin cos
2
d

E=0
f
o
E
g(E)E v
2
_
+
E
T
T
_
dE
(5.14)
The rst term in the eq. A.13 and A.14 is zero and the second term yields
j
q
=
1
3

E=0
f
o
E
g(E)qv
2
_
+
E
T
T
_
dE (5.15)
and
j
E
=
1
3

E=0
f
o
E
g(E)E v
2
_
+
E
T
T
_
dE (5.16)
From the kinetic energy expression E =
1
2
mv
2
and use it to eliminate v in eq.A.15
and A.16, we obtain :
j
q
=
2q
3m

E=0
f
o
E
g(E)E
_
+
E
T
T
_
dE (5.17)
and
j
E
=
2
3m

E=0
f
o
E
g(E)E
2
_
+
E
T
T
_
dE (5.18)
Eq. A.18 can be expanded as :
j
E
=
2
3m

E=0
f
o
E
g(E)E(E )
_
+
E
T
T
_
dE
+
2
3m

E=0
f
o
E
g(E)E
_
+
E
T
T
_
dE
=
2
3m

E=0
f
o
E
g(E)E(E )
_
+
E
T
T
_
dE +
j
q
q
(5.19)
At temperature T = 0K, the rst term in the right hand side of eq. A.10 is zero, so :
j
E
(T = 0K) =
j
q
q
(5.20)
Because electron do not carry any thermal energy at T = 0K, the thermal current
density will be only the rst term in eq. A.19, so :
j
E
=
2
3m

E=0
f
o
E
g(E)E(E )
_
+
E
T
T
_
dE (5.21)
Eq. A.17 and A.21 can be rearranged as in eq.2.8 - 2.13
j
q
= L
11
_
1
q
_
+L
12
(T)
j
E
= L
21
_
1
q
_
+L
22
(T)
where
L
11
=
2q
2
3m

E=0
f
o
E
g(E) E dE
L
12
=
2q
3mT

E=0
f
o
E
(E )g(E) E dE
L
21
=
2q
3m

E=0
f
o
E
(E )g(E) E dE
L
22
=
2
3mT

E=0
f
o
E
(E )
2
g(E) E dE
For electrical conductivity in eq. 2.15,
f
o
E
is non zero only when E is close to
, and can be approximated to as delta function
f
o
E
(E ) (5.22)
Combine eq. 2.15 and A.22, we have (q = -e, for electrons) :
=
j
q
E
= L
11
=
2e
2
3m

E=0
(E ) g(E) E dE
=
2e
2
3m
(E ) g
E=

E=
=
2e
2
3m
g
F

F
(5.23)
We can use E
F
=
mv
2
2
to reduce eq. A.23 to :
=
e
2
3
g
F
v
2
F
F
(5.24)
Note that electron concentration can be calculated (with g(E) =
(2m)
3
/2
2
2
h
3
E
1
/2
) as :
n =

E=0
f
o
(E)g(E)dE =
E
F
E=0
1
2
2
_
2m
h
2
_2
3
E
1
/2
dE
=
1
3
2
_
2m
h
2
_2
3
E
3
/2
F
=
2
3
g
F
E
F

2
3
g
F
(5.25)
Combine eq. A.23 and A.25, we have eq. 2.16
=
ne
2
m
From eq. 2.21, we have
S =
L
12
L
11
=
1
qT
_
E=0
f
o
E
(E )g(E) E dE
E=0
f
o
E
g(E) E dE
_
=
1
qT
_

E=0
f
o
E
g(E) E
2
dE
E=0
f
o
E
g(E) E dE
_
(5.26)
Combine eq. A.26 with g(E) =
(2m)
3
/2
2
2
h
3
E
1
/2
, we have :
S =
1
qT
_

E=0
f
o
E
g(E) E
2
dE
E=0
f
o
E
g(E) E dE
_
=
1
qT
_

E=0
f
o
E
E
2+r+
1
2
dE
E=0
f
o
E
E
1+r+
1
2
dE
_
(5.27)
The eq. A.27 can be simplied using the product rule :

E=0
f
o
E
E
s
dE = f
o
E
s
|
0
s

E=0
f
o
E
s1
dE =s

E=0
f
o
E
s1
dE (5.28)
Use eq. A.28 to reduce eq. A.27 to :
S =
1
qT
_

_
r +
5
2
_
E=0
f
o
E
r+
3
2
dE
_
r +
3
2
_
E=0
f
o
E
r+
1
2
dE
_
(5.29)
The two integrals in eq. 29 can be simplied with the reduced energy =
E
k
B
T
and
=

k
B
T
to

E=0
f
o
(E )E
n
dE = (k
B
T)
n+1

0
f
o
(, )
n
d = (k
B
T)
n+1
F
n
() (5.30)
where the Fermi-Dirac integral is dened as :
F
n
() =

0
f
o
(, )
n
d (5.31)
Use eq. A.30 to reduce A.29 to :
S =
1
qT
_
k
B
T
_
r +
5
2
_
F
r+
3
/2
()
_
r +
3
2
_
F
r+
1
/2
()
_
(5.32)
So we can dened eq.2.21. :
S =
k
B
q
_
_

k
B
T

_
r +
5
2
_
F
r+
3
/2
_

k
B
T
_
_
r +
3
2
_
F
r+
1
/2
_

k
B
T
_
_
_
For metal, where =

k
B
T
0, the Fermi-Dirac integral can be expressed in
the form of a rapidly converging series :
F
n
() =

0
f
o
(, )
n
d =
1
n+1

0
f
o

n+1
d
=
1
n+1

0
f
o
n+1
+
m=1
d
m
n+1
d
m
=n
( )
m
m!
_
d
=
1
n+1

0
f
o
n+1
+(n+1)
n
( ) +(n+1)n
n1
( )
2
2
+...
_
d
F
n
() =

+1
n+1
+n
n1
2
6
+... (5.33)
If we use only the rst two terms of eq. A.33 to express the two fermi-Dirac integrals
in eq. A.32, we obtain for electrons in metals :
S =
k
B
q
_

_
r +
5
2
_
F
r+
3
/2
()
_
r +
3
2
_
F
r+
1
/2
()
_
=
k
B
e
_
_
r +
3
2
_
F
r+
1
2
()
_
r +
5
2
_
F
r+
3
2
()
_
r +
3
2
_
F
r+
1
2
()
_
=
k
B
e
_
_
_
_
_
r +
3
2
_
_
r+
3
2
r+
3
2
+
_
r +
1
2
_
r
1
2

2
6
_
_
r +
5
2
_
_
r+
5
2
r+
5
2
+
_
r +
3
2
_
r+
1
2

2
6
_
_
r +
3
2
_
r+
3
2
r+
3
2
_
_
_
_
So we have eq. 2.23 :
S =
2
k
B
3q
_
k
B
T
__
3
2
+r
_
In determining the thermal conductivity, rst we change eq. 2.8 to :
1
q
=
L
12
L
11
(T) +
j
q
L
11
(5.34)
Use eq. A.34 to eliminate from eq. 2.9 to obtain :
j
E
= L
21
_
L
12
L
11
(T) +
j
q
L
11
_
+L
22
(T)
=
L
21
L
12
L
11
(T) +
j
q
L
21
L
11
+L
22
(T)
=
_
L
22
L
21
L
12
L
11
_
(T) +
j
q
L
21
L
11
In the case of j
q
= 0 and T = 0, we have eq.2.9 :
j
E
=
_
L
22
L
21
L
12
L
11
_
(T)
where we dene eq. 2.10, which is the thermal conductivity :
=
_
L
22
L
21
L
12
L
11
_
= L
22
L
21
S
For metals, S usually very small so that from eq. 2.25 we have
L
22
=
2
3mT

E=0
f
o
E
(E )
2
g(E) E dE
Note that
f
o
T
=
f
o
T
=
d f
o
d
E
k
B
T
2
(5.35)
Compare eq. A.35 with eq. A.4, we can obtain :
f
o
E
=
T
E
f
o
T
(5.36)
And combine eq. A.34, eq. A.35 and eq. A.36, we have :
=
2
3m

E=0
f
o
T
(E )g(E) E dE (5.37)
By using kinetic energy expression for electron, E =
1
2
mv
2
, we have eq.2.26 :
=
1
3

E=0
f
o
(E)
T
(E ) g(E) v
2
dE
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Figure of Merit Characterization of Thermoelectric Material :

Determination of Copper Figure of Merit

(ev) f (E)g(E)dE (2.6)

. From the measurement we

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