STEPHEN CHUKWUEMEKA REVIEW PAPER

NAME: STEPHEN UDOCHUKWU CHUKWUEMEKA
I.D NO: 14210334
LECTURER: PAUL AHERN & DR. STEPHEN DANIELS
MODULE: EE541, NANO & MICROELECTRONIC DEVICE MANUFACTURING
PAPER TITLE: Characterisation Techniques for Silicon-based thermoelectric materials.
I hereby declare that the attached submission is all my own work, that it has not previously been
submitted for assessment, and that I have not knowingly allowed it to be used by another student.
I understand that deceiving or attempting to deceive examiners by passing off the work of another
as one's own is not permitted. I also understand that using another's student’s work or knowingly
allowing another student to use my work is against the University regulations and that doing so
will result in loss of marks and possible disciplinary proceedings.
Signed: STEPHEN
Date: 25th
November, 2015


Abstract — In the course of the operations of some
engineering systems – like engines, unwanted heat is
generated. Thoughts to ameliorate this phenomenon
were taken into cognizance, and it led to the
introduction of several means of utilizing this
unwanted heat. A thermoelectric effect is one of the
ways through which this unwanted heat is effectively
used. Hence, thermoelectric (TE) materials play vital
roles in electric generation devices which are
designed to convert unwanted heat energy to
electrical energy. Conversion of heat energy to
electrical energy will help to reduce our dependency
on fossil fuels and emissions of greenhouse gas.
In this paper, new thermal techniques for silicon-
based thermoelectric materials are revealed. Micro-
fabrication and flip-chip processes are used in the
fabrication of silicon-based TE materials. In this
paper, there will be an illustration of the cooling
functionality of the silicon-based TE materials with
thermal images taken by an infrared camera and
how these silicon-based thermoelectric materials can
reduce the thermal resistance of high voltage
electronic chips – like diodes.
Keywords – energy, thermoelectric materials, silicon-based
TE- materials.
I. INTRODUCTION
Universal economic development has brought about
a progressively high request for energy, with the
main energy being fossil fuels, the population and
economic growth are expected to triple the energy
consumption rate by the end of the century, and this
would require an increase in the supply of energy.
Regardless of fossil fuels being the significant
energy supplier, the outflow of greenhouse gasses
from fossil fuels is a significant difficulty for it.
Lately, the demand for alternative energy
technology is at rise due to the greenhouse effects of
the highly-relied-on fossil fuels, the idea is to
develop clean and renewable energy sources.
Innovative work sectors of science and engineering are
the essential drivers in the improvement of alternative
energy sources. What's more, there has being a
developed enthusiasm for the utilization of
Thermoelectric (TE) effect as an alternative source of
energy 3
.
The immediate change of the temperature contrasts in a
material into electric voltages is illustrated through TE
effect 1
. In reality, the TE idea can be just examined as a
reusing procedure of turning a waste product (HEAT)
into helpful assets as electrical energy 1-8
. The materials
that are esteemed pertinent for the uses of the
thermoelectric effect are alluded to as the thermoelectric
materials. For a material to be viewed as a TE material,
it needs to have some unquestionable components that
backing the executions of the TE effect 2
.
The common accessibility of the TE materials is to a
great degree restricted, so this hence brings about the
requirement for the simulated advancement of execution
- enhanced TE materials. TE materials are utilized to
change over heat produced from different sources into
electrical voltage. These sources incorporate car fumes,
bright sun powered radiation and other modern
procedures 4, 5
. Car industry are constantly giving a ton
of assets into the exploration of energy generation
applications with a specific end goal to create electrical
energy from waste engine heats from the radiator
Characterisation Techniques for Silicon-based
thermoelectric materials.
Stephen Chukwuemeka, School of Electronic Engineering, Dublin City University, Glasnevin, Dublin 9, Ireland.
stephen.chukwuemeka2@mail.dcu.ie

Stephen Chukwuemeka [14210334] EE541 Nano & Microelectronic Device Manufacturing Review Paper 1
cooling systems, the fumes system and breaking system
and so forth 7, 8 and 9
.
Additionally there are different uses of TE materials,
similar to the TE coolers which are utilized as a part of
the manufacturing refrigerators and some other cooling
systems 4, 5, 11 and 12
. TE cooling uses the PELTIER
thermoelectric effect to produce a heat flux between the
intersections of two material sorts 11, 12
. At the point
when two conduits are in contact through an electric
contact, electrons will normally spill out of the
conductor that has less bound inside of it electrons into
the channel with more bound inside of it electrons 12
,
this is as a consequence of the distinction in the Fermi
level of the two conductors.
Fermi level alludes to the aggregate chemical capability
of electrons 12, 13
. So when two conductors with notable
contrast in their Fermi levels are in contact, there would
be stream of electrons from the conductor with the
higher Fermi level into the conductor with the lower
Fermi level until the Fermi levels turns into the same as
an aftereffect of the change in electrostatic potential
(contact potential) 11, 12 and 13
. The Peltier TE effect is a
developing use of the TE idea.
TE materials gives a great state of dependability with
their applications, and this along these lines results in
their wide applications that ranges from the
improvement of PC chips, infrared sensors and so forth
1, 2, 7, 8, 11, 12
. Regardless of the various uses of TE
materials, a few restrictions upset it improvements, these
constraints incorporate expense and productivity. The
connection with the operations of TE materials are low
effective, thus, an enhanced productivity in TE materials
will bring about more significant headways in the TE
fields 4 - 10
.
The regular TE gadget utilizes two earthenware plates to
conduct heat and protects electrical current 14
. The
thermal conductivity of the most common earthenware
plate, for example, aluminum oxide (Al2 O 3) is around
27.21 Wm-1
K-1
at 300K. At the point when earthenware-
bases TE gadget is touched with a heat source made of
silicon wafer, for instance the silicon submount of a
diode or heating chip of flip-chip bundle, the coefficient
of thermal expansion (CTE) confound may happens.
Utilizing silicon substrate as the substrates of TE
material can be an optional answer for decrease CTE
bungle issue.
In addition, the thermal conductivity of silicon is three
times bigger than aluminum oxide. The cooling
execution of TE gadget can likewise be progressed. In
addition, the manufacture of silicon-based TE gadget is
good for microelectronics what's more, micro-fabrication
procedure. There is significant opportunity to
incorporate silicon-based TE gadget into diode or flip-
chip bundle for thermal administration.
This paper exhibits another thermal administration use
of silicon-based TE gadget with respect to high voltage
diode. Cooling elements of 12-and 16-sets silicon-based
TE gadget are shown by infrared camera. The most
extreme temperature contrasts in the middle of
surrounding and cool side of 12- also, 16-sets TE gadget
are 11.5ºC and 24.9ºC, individually.
The cooling execution of silicon-based TE gadget with
respect to high voltage diode is measured by an
electrical-thermal change strategy. The diode thermal
resistance from connection to surrounding can be
decreased fundamentally.
II. HISTORY AND DEVELOPMENT OF
THERMOELECTRIC MATERIALS
The original advancements of the TE effects is credited
to Thomas Johann Seebeck, between the years 1821-
1823, Seebeck found that circuit made from two unique
metals and with diverse temperatures at the intersections
would avoid a compass magnet 15
.
Seebeck at first expected the magnetism was a
consequence of the temperature distinction between the
two materials and the world's attractive field. Then
again, from further examination of the magnetism
through the researches he carried out, which is called
“The magnetic polarization of ores produced by
temperature differences”, Seebeck identified that when
the ends of two metals joined together under different

temperatures and locked, and a needle with magnetic
properties is set close to their contact intersection, the
needle would turn like it was set near a magnet and the
revolution edge relates to the temperature distinction at
the intersection of the two materials 16
.
After this revelation, Seebeck kept on exploring
distinctive material mixes for the TE effect including
Zinc Antimonide, PbS and Cobalt Arsenide 17, 18
. The
TE effect is also indicated as the Seebeck’s effect.
The improvement takes a shot at the Seebeck's TE
innovations kept on happening after his first trial. What's
more, in 1834, another TE effect was found by a French
watchmaker and Physicist Jean Charles Athanase Peltier,
Peltier figured out that at whatever point current is gone
through two unique metals that are joined together, it
would bring about a warming or cooling impact at the
intersection where both metals meet 20
.
Like Seebeck, Peltier doesn't completely comprehend
the understanding of his revelation and in 1838, Russian
researcher Emily Lenz outlined a pragmatic execution of
the Peltier effect by demonstrating that heat could be
expelled from the intersection of two unique materials
for freeze water contingent upon the bearing of stream of
ebb and flow, and by turning around the ebb and flow
stream, heat can be discharged at the contact intersection
20, 21
.
This TE effect is known as the Peltier's effect.
An expansive clarification and comprehension of both
Seebeck's and Peltier's effects was later created by
William Thomson (Lord Kelvin) in 1854, he found
himself able to utilize the interrelationship among the
Seebeck's coefficient (SC) and the Peltier's coefficient
(PC) to create another TE effect known as the Thomson
effect. Thomson found that the SC and the PC are
connected through thermodynamics 21
.
Thomson suggested that heat is consumed or transmitted
when electrical current stream in material with
temperature slope 21
. The heat consumed or discharged
compares to both the present coursing through the
material and the temperature inclination of the material
and the Thomas coefficient (TC) alludes to the
proportionality constant 21
.
The Seebeck's effect is credited with the TE power
generators while the Peltier's effect is ascribed with the
TE cooling systems, and the Thompson effect is a
thermodynamic mix of both the Seebeck's and the
Peltier's effect. There are different analysts connected
with the improvement of the TE effects, a case is the
Russian researcher Abram Ioffe who was credited in the
advancement of exceptionally effective TE materials,
manufacturing of cooling systems and power systems
based on the Peltier's effect 19, 20 and 23
. There is a steady
development in TE applications and it is assumed there
is much space for improvements 19
.
III. PHYSICS OF THERMOELECTRIC
EFFECT
This area of the review paper would concentrate on
exploring the physics of the TE effect. The investigation
of the physics behind the TE effect would be basically
centered on the three important TE effects, the Seebeck's
effect, the Peltier's effect and the Thomson's effect.
A. THE SEEBECK’S EFFECT
Figure 1: schematic presentation of the Seebeck’s
thermoelectric effect.
As examined before, Seebeck found that when two
distinct materials (material A and B) are joined together
and their contact intersections are held at diverse
temperature (T and T+∆T), an electrical voltage (V)

which is corresponding to the temperature contrast (∆T)
is produced 1, 19, 20, 27 and 28
.
So that:
V ∝ ∆T
The coefficient of proportionality is equal to the ratio of
the created voltage (V) and the temperature contrast
(∆T). α is known as the Seebeck's coefficient 27 - 30
.
α= V/∆T
Why the Seebeck's effect happens; the Seebeck's effect
forms when thermal diffusion results in a net flux of
electrons towards a temperature contrast and
consequently bringing about a voltage distinction.
During equilibrium, the net flux of charge carriers as a
result of electrostatic forces balances the net flux of
electrons due to the thermal diffusion 27, 28
.
B. THE PELTIER’S EFFECT
Figure 2: schematic depicting the Peltier’s
thermoelectric effect with an n-class and a p-class
thermoelectric material (image courtesy of
http://www.caister.com/supplementary/pcr-
troubleshooting/c6f1.html / under Creative Commons License)
The Peltier's effect is viewed as the inverse of the
Seebeck's effect. In the utilization of the Peltier's effect,
temperature distinction (∆T) is affected by the electrical
voltage at the contact intersection as a consequence of
the electrical current connected to the materials 24, 31
.
The Peltier's effect is as an aftereffect of the way that
electrical energy of the charge carrier constituting of a
current is material dependent 24
.
Numerical portrayal:
Q = I (α2 - α1) T
Q is the rate of heat assimilation; α1 and α2 are the
Seebeck coefficient of the materials, with current
spilling out of material with α1 into the material with α2.
The current flows toward the positive charge carrier 29
.
C. THE THOMSON’S EFFECT
The Thomson effect relates the electric field and the
reversible thermal angle in homogenous conductor
materials. Fundamentally, the ingestion of heat as
current flow through a conductor material subjected to
temperature angle 19
. The Thomson's effect is a
consequence of the relationship between the temperature
of materials and the electrical energy of charge carriers.
Electrical energy of charge carrier is an element of
temperature 19
.
Scientific depiction:
𝑑𝑄
𝑑𝑥
= 𝐼𝑇
𝑑𝛼
𝑑𝑇
𝑑𝑇
𝑑𝑥
The Thomson's effect is viewed as a bulk effect. At the
point when TE materials work under the Peltier's effect,
the Thomson's effect may be dismissed however when
TE materials are working under the Seebeck's effect, the
Thomson's effect is regularly represented 19
.

IV. FABRICATION PROCESSES OF SILICON-
BASED THERMOELECTRIC MATERIALS
The silicon-based TE gadget is created by micro-
fabrication and flip-chip gathering process and is
appeared in Figure 3. The procedure begins with an n-
class <100> silicon wafer. The initial step is to develop
the silicon dioxide of 1200A by warm oxidation as an
electrical protection.
Also, Ti what's more, Cu is individually sputtered on the
protection layer and at that point designed by substance
drawing for electrical interconnection. Next, a partner
divider is characterized by a standard SU-8 process with
a specific end goal to restrict the situation of
thermoelectric legs and decrease the moving issue of TE
legs from the accompanying reflow process 45
.
The bind glue is spread on the electrical interconnection
by surface mount innovation (SMT). The n and p-class
TE wafers made of Bi2Te3 are cut into cubic
measurement of 0.125mm3 by dicing machine. The
figure-of-value of TE wafer is about Z=3.0× 10- 3 (1/K).
At that point, the TE legs are put on the silicon wafer by
pick and place procedure of flip-chip bundle, and the
two silicon bases are adjusted by flip-chip bonder. At
long last, the conductive wires are set on the silicon
substrate and the gadget is finished through the reflow
process by hot plate.
Figure 3: Process flow for the silicon-based TE device
(Jen-Hau Cheng et al, 2005).
Figure 4 shows the structure of silicon-based TE device
and the appearances of 12- and 16-pair devices. The
thickness of SU-8 is about 50um. And the TE legs are
surrounded by SU-8 structure. The dimensions L×W×H
of 12 and 16-pair devices are approximately 9× 10×
1.5mm and 9× 11× 1.5mm, respectively.

Figure 4: SEM picture and appearance of 12- and 16-pair
silicon-based TE devices (Jen-Hau Cheng et al, 2005).
V. SILICON-BASED TE MATERIALS AND THEIR
COOLING CHARACTERISTICS
Keeping in mind the end goal to exhibit the cooling
capacity of 12 and 16- pair silicon-based TE gadgets,
thermal pictures are shot by infrared camera. Figure 3a
and 3b demonstrate the cooling capacity of 12-and 16-
sets gadgets at encompassing temperature of 24.4ºC,
individually. The cooling capacity test of 12-sets gadget
starts with no input power, which the cold side
temperature is 24.6ºC.
With the slow increments of input current, the gadget
begins to chill off and brings about a temperature
diminish at the cold side. At the point when the gadget is
stacked with the input current of 0.34A, the cold side
temperature achieves the minimum point of 12.9ºC and
accomplishes the highest temperature contrast in the
middle of surrounding and cold side of 11.5ºC. In the
wake of coming to the most minimal point, the cold side
temperature begins to go up on the grounds that the vast
majority of information current starts exchanging to
joule heating. At last, the cold side temperature very
nearly ascends to its unique temperature of 24.6ºC at
0.67A.
Input 0.67A Input 1.44A
(a) 12-pairs (b) 16-pairs
Figure 5: Thermal images of 12-pair (a) and 16-pair (b)
silicon-based TE gadgets functioning as a cooler
(Jen-Hau Cheng et al, 2005).
The cooling capacity test of 16-sets gadget additionally
takes after the same steps and technique for 12-sets
gadget. The highest temperature distinction of 16-sets
gadget is 24.9ºC at the data current of 0.75A and is
higher than that of 12-sets gadget due to the extra 4 sets
of TE legs. Figure 6 outlines the trial consequences of
the highest temperature contrast in the middle of ambient

and cold side versus electric current power of 12-sets
and 16-sets silicon-based TE gadget.
Figure 6: The cooling characteristic of 12-pair and 16-
pair silicon-based TE gadget (Jen-Hau Cheng et al, 2005).
VI. THERMOELECTRIC MODULE
The usefulness rule of refrigeration frameworks is based
the usage of the Peltier's TE effect. The Peltier's effect is
executed in the improvement of TE modules that
delivers a temperature distinction when electrical current
moves through TE material.
TE modules are viewed as strong state energy
converters, ordinarily TE modules comprise of a cluster
game plan of many p-class and n-class thermocouples
joined together in arrangement electrically and they are
likewise associated thermally in parallel course of action
30, 32 - 34
. The components of a TE module are typically
inserted in electrical protecting material keeping in mind
the end goal to keep up the separating in the module
furthermore shield it from unsatisfactory working
environment 32, 33
.
Figure 7: A cross-sectional view of a TE module
revealing the module elements arrangement of the p/n
class materials. (Image courtesy of
http://edge.rit.edu/content/P09451/public/Home under
Creative Commons License)
TE modules can be utilized for heating, cooling and
energy generation purposes, in this way the coefficient
of thermal extension of the module material ought to be
considered amid the configuration of the module due to
conceivable disappointments that may happen because
of created burdens amid gathering and heat impacts amid
use 34 - 36
.
Amid the operation of a TE module, there are 5
important physical procedures occurring.
1. Thermal Convection: Refers to the exchange of
warmth through the P-class module components and the
n-class module components 34, 35
.
2. Joule Heating: Describes the warmth scattering
procedure on the resistive components 36
.
3. Peltier Heating/cooling impact: Describes the
ingestion/scattering of warmth at the intersection of two
unique material sorts (p/n) when current moves through
the intersection 24
.

4. Seebeck Power Generation: Describes how the
procedure of warming/cooling of the intersection of two
disparate material sorts (p/n) creates an electrical
potential at the intersection 19, 20
.
5. Thomson Effect: Describes the thermodynamic
relationship between the Peltier effects and the Seebeck
effect amid operation of the module 32, 34
.
TE modules can likewise be interconnected in a blend of
parallel or series formation or a mix of both parallel and
series formation to make bigger module gatherings with
a specific end goal to accomplish bigger TE results. TE
modules are normally interfaced with hot side and cold
side heat exchangers 30
, the interface game plan of a TE
module is pivotal in the configuration, as the interface is
required to effectively move heat energy all through the
module, an ill-advised interface outline will restrain the
interface warm exchange and subsequently bringing
about performance limitations of TE systems 30
.
VII. TRENDS AND IMPROVEMENTS IN
THERMOELECTRIC MATERIALS
This area of the review paper would concentrate on the
examination of significant patterns and advancements in
the applications of the TE effects, recent improvements
in TE applications include:
A. THERMOELECTRIC OXIDES
One of the developing trends in TE applications is
implementation of oxides in the improvement of
thermoelectric materials, there are a few points of
interest included in the utilization of metal oxides in the
advancement of TE material for vitality era, the metal
oxide TE materials would be more rough and more less
demanding to be prepared than traditional TE materials
and conceivably have a high scope of working
environment. An illustration of TE oxides is the class of
NaxCo2O4; these compounds have viable TE properties
that make them very suitable for TE applications 37
.
These materials are a member from an extensive class of
layered metal bronze that structures edge shared
octahedral oxide layers in the transition metals 37, 38
.
Furthermore they contain combined valence CO ions
with vagrant electrons inside the layers and a
nonstoichiometric measure of Na ions between the
layers 38
. There are numerous focal points of these
material structures in TE applications.
B. SKUTTERUDITES
Another prominent developing trend in the utilization of
TE effect is the utilization of Skutterudites in TE
applications, Skutterudites are hydrothermal mineral
gem materials that contain nickel, they have a high p-
class portability values and a substantial n-class TE
values. These are great TE material attributes that
endorses low thermal conductivity in TE materials 39
.
Skutterudites additionally has a substantial number of
ISO-structural materials 39
.
The thermal conductivity of Skutterudites can be shifted
by filling the voids inside of the structure with vast
materials of little breadth, for example, trivalent rare
earth ions 39
. The warm conductivity decrease compares
to the measure of particles consolidated inside of the
Skutterudites 39
.
Figure 8: Crystal structure of a filled skutterudite
SmRu4P12. (image courtesy of
http://www.spring8.or.jp/en/news_publications/press_release/
2008/080310-1/ under Creative Commons License)

C. CLATHRATES
Another trending material that is producing interests in
TE frameworks is Clathrates. Clathrates are chemical
substances that comprise of grids that trap or contain
atoms 40
. Like Skutterudites, Clathrates additionally
have confine like structures which take into account the
rattling system that permits the change of their thermal
conductivity property.
The specific Clathrates class which is for the most part
successful for TE application is the class-i and class-ii
Clathrate hydrates, there are different material
organizations that contained these two classes, these
materials of interest from both bonding and physical
properties point of view 40
. The bonding class in
Clathrate hydrates is somewhat like the ones found in
diamond-structure group 14 components and their
unmistakable thermal conductivity properties makes
them a decent material choice for TE applications 40, 41
.
D. THIN FILM THERMOELECTRIC
MATERIALS
In the Engineering field of semiconductor, there is an
on-going routine of system scaling down, and with TE
applications like TE coolers being one of the significant
segments in semiconductor systems, size lessening of TE
materials is such a vital issue 42, 44
. By and large
business energy utilizations of the TE effect does not
exploit the huge possibilities offered by low dimensional
structures, it has being tentatively demonstrated that low
dimensional TE materials display an expanded Figure of
Merit (ZT) contrasted with other cumbersome materials
43
, these low-dimensional materials are alluded to as the
thin- film TE materials. There is a generating trend in the
examination of these thin films TE materials, and the
purpose behind this latest improvement is the
hypothetically anticipated increment in their figure of
benefits estimation of their super-grids as a consequence
of a few effects 42, 43
.
There are two main ways to deal with the improvement
of thin film TE gadgets, viz: IN-PLANE LEGS and
CROSS –PLANE LEGS. The IN-PLANE legs
methodology produces a high number of thermocouples
which actually implies high voltages, and a
diminishment in their thermal conductivity properties,
and along these lines the subsequent in a low
temperature angle over the slender layers 44
. The
CROSS PLANE legs methodology has control of low
electrical resistance and limited parasitic heat flow
through the substrate, the thin film TE materials are
gotten through the utilization of MEMS 44
Figure 9: sample of a thin film TE material developed by
FUJIFILM. (Image courtesy of http://phys.org/news/2013-
02-fujifilm-thermoelectric-material.html/ under Creative
Commons License)
V. CONCLUSION
In this paper, new thermal techniques for silicon-based
thermoelectric materials were revealed as well as the
characterization processes involved in the manufacturing
of silicon-based thermoelectric (TE) materials. The
functionality of silicon-based thermoelectric materials
was highlighted in the course of the writing of this
paper. Thermal Images depicting the cooling
functionality of silicon-based thermoelectric materials
were taken and discussed in this paper as seen above.
The initial paragraphs were highlights on the
background/ history, improvement and the physics
behind thermoelectric materials.

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