“BASICS OF THERMOELECTRIC

MATERIALS”
INTERNSHIP REPORT
MASTER OF SCIENCE

IN

PHYSICS
BY

U. DIVYA
(20/PPHA/116)

Under the supervision of

DR.K. SETHUPATHI
DEPARTMENT OF PHYSICS

INDIAN INSTITUTE OF TECHNOLOGY

MADRAS
Chennai-600036

August-2021

DEPARTMENT OF PHYSICS

STELLA MARIS COLLEGE (AUTONOMOUS)

CHENNAI-600 086

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 BONAFIDE CERTIFICATE
This is to certify that the INTERNSHIP REPORT entitled “BASICS OF

THERMOELECTRIC MATERIALS” submitted by U. DIVYA (20/PPHA/116) to the

Department of PHYSICS STELLA MARIS COLLEGE, CHENNAI in partial fulfillment of

the requirements for the award of the Degree in MASTER OF SCIENCE in PHYSICS is a

Bonafide record of the work done by the candidate during the academic year 2021-2022.

DR. BELINA XAVIER

Head of the department

Department of Physics

STELLA MARIS COLLEGE

CHENNAI-86.

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 ACKNOWLEDGEMENT
First and foremost, I owe my wholehearted thanks to God, The Almighty, for the success of

this internship program.

I am very thankful to Dr. K. Sethupathi, Professor, Department of Physics, Indian Institute of

Technology Madras for giving me this opportunity, for his encouraging guidance and kind

supervision. It was a very good learning experience for me to have worked on this topic.

I would also like to show my special gratitude to Miss. Akshara, a Research scholar, helped

us in taking up this Internship in a successful way.

I sincerely thank DR. BELINA XAVIER, Head of the Department of Physics, Stella Maris

College, Chennai, for her constant encouragement and support.

Last, but not least, my parents and friends are also important inspirations for me. Henceforth

with due regards, I express my gratefulness to them.

U. DIVYA
20/PPHA/116
2nd M.SC PHYSICS

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 ABSTRACT
Thermoelectric (TE) materials can convert heat into electricity based on the Seebeck effect,

and electric power to cooling based on the Peltier effect. They are very useful for heat energy

harvesting and cooling applications as green and sustainable energy resources. In this report,

we have studied an overview of the physical principles of thermoelectricity, and the

performance parameters of thermoelectric materials as well as examples of the wide range of

applications of thermoelectric modules. Thermoelectricity has a wide range of applications due

to reversible energy conversion. Different thermoelectric materials have also been discussed

based on low, mid, and high temperatures. TE devices come into use in various applications

because of their eco-friendly feature and distinct advantages. Thermoelectric energy has a wide

range of applications in various fields like; electricity generation, refrigeration, air

conditioning, particular heating/cooling, biomedical devices, etc. due to its simple construction

and mechanism, portability.

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 CONTENTS
Introduction ----------------------------------------------------- 6

➢ Discovery of thermoelectricity ------- 6

Thermoelectricity effects-------------------------------------- 7

➢ See beck effect ----------------- 8

Introduction on Thermocouple -------------------------------- 9

➢ Peltier effect ------------------------------- 10

➢ Thomson effect --------------------- 11

The figure of merit -------------------------------------- 12

Temperature based thermoelectric materials ----- 13

➢ Low Temperature ----- 13

➢ Mid-Temperature --------------------------- 15

➢ High temperature ---------------------------- 16

New generation thermoelectric materials -------------- 18

Properties ----------------------------------------- 19

Applications ------------------------- 20

Conclusion ------------------------------------ 22

References ------------------------------------------- 22

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INTRODUCTION:

Thermoelectricity is associated with thermal and electrical phenomena. This process involves

the conversion of thermal (heat) energy into electrical energy or vice versa, by which either

a temperature difference creates an electric potential or an electric potential creates a

temperature difference.

These phenomena are based on more specifically as the See beck effect (creating a voltage

from temperature difference), Peltier effect (driving heat flow with an electric current),

and Thomson effect (reversible heating or cooling within a conductor when there is both an

electric current and a temperature gradient).

The discovery of thermoelectricity:

Already in 1794, Italian physicist Alessandro Volta observed, that a metal rod which ends

were at different temperatures caused a spasm in frog muscles. From today's perspective,

the temperature difference in the metal caused an electric current that excited the muscle.

At the time, however, understanding of electricity was very limited and the cause of the

effect was unclear. It was not before 1822, that Thomas Johann See beck rediscovered the

same effect when he observed the deflection of a compass needle close to two metals

junctions that were kept at different temperatures. In his honor, the direct conversion from

heat to electricity at the junction of two conductors was later called the See beck effect.

Together with the Peltier effect, discovered in 1834, and the Thomson effect, discovered in

1851. Although thermoelectric was known for many years, it took almost a century from

the discovery of the effect to active research in the field. At the beginning of the 20th

century, thermoelectric materials were extensively studied for applications in civilian and

military use. By 1950, many scientists were convinced that thermoelectric would soon

replace conventional refrigerators and heat engines.

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Although these two effects were demonstrated to exist, it was very difficult to measure each

effect as a property of the material because the See beck effect is always associated with two

dissimilar wires and the Peltier effect is always followed by the additional Joule heating that is

heat generation due to the electrical resistance to the passage of a current.

The mechanisms of thermoelectricity were not understood well until the discovery of electrons

at the end of the nineteenth century. Now it is known that solar energy, an electric field, or

thermal energy can liberate some electrons from their atomic binding, even at room

temperature, moving them (from the valence band to the conduction band of a conductor)

where the electrons are free to move. This is the reason why we have electrostatics everywhere.

FIGURE 1:Schematic illustrations of thermoelectric modules for power generation (See beck
effect) and active refrigeration (Peltier effect): (a) the German physicist, Thomas Johann See
beck, (b) See beck effect for the power generation, and applied temperature difference causes
charge carriers in the material (electrons or holes) to diffuse from the hot side to the cold side,
resulting in current flow through the circuit, (c) power generation efficiency as a function of
average ZT ave; (d) the French physicist, Jean Charles Athanase Peltier, (e) Peltier effect for
the active refrigeration, heat evolves at the upper junction and is absorbed in the lower junction
when a current is made to flow through the circuit, (f) cooling efficiency as a function of
average ZTave. Higher ZTave projects higher thermoelectric power generation and cooling
efficiency.

THERMOELECTRICITY EFFECTS:

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The term THERMOELECTRIC EFFECT encompasses three separately identified effects:

1) Seebeck effect

2) Peltier effect

3) Thomson effect

SEEBECK EFFECT:

When two dissimilar metal wires are joined together to form a closed circuit and if the two

junctions are maintained at different temperatures, an emf is developed in the circuit. This

causes a current to flow in the circuit as indicated by the deflection in galvanometer G. This

phenomenon is called the See beck effect. This arrangement is called a Thermocouple and the

emf developed is called thermo emf. The Thermo emf so developed depends on the temperature

difference between the two junctions and metals chosen for the couple.

FIGURE 2: See beck effect.

See beck arranged the metals in a series as follows:

Bi, Ni, Pd, Pt, Cu, Mn, Hg, Pb, Sn, Au, Ag, Zn, Cd, Fe, Sb.

The potential difference is proportional to the temperature difference. The potential difference

V is

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 V =α ΔTAB

where ΔT=Th- Tc and α = αA - αB; αAB is called the See beck coefficient (also called the
AB

thermopower), which is usually measured in (𝜇𝑉/κ).

THERMOCOUPLE:

A thermocouple has two connecting ends called Junctions where one is used in sensing the

radiation at the hot junction and another end usually kept at a constant lower temperature is a

reference or cold junction.

FIGURE 3: Thermocouple image.

Thermocouples, extremely versatile and rugged, are primarily simple

devices and can be made to very small dimensions. They are capable

of operating over a wide range of temperatures.

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*For a given temperature of the cold junction, the temperature of the hot junction for which

the thermo emf becomes maximum is called the neutral temperature (𝜃n) for the given

thermocouple.

* For a given temperature of the cold junction, the temperature of the hot junction for which

the thermo emf becomes zero and changes its direction is called the inversion temperature (𝜃i)

for the given thermocouple.

FIGURE 4: Graph showing the variation of thermo emf with temperature.

PELTIER EFFECT:

When an electric current is passed through a closed circuit made up of two different conducting

materials, one junction is heated and the other junction is cooled. This is known as the Peltier

effect.

The energy that is liberated or absorbed at a junction between two dissimilar materials due to

the passage of unit quantity of electricity is called the Peltier coefficient.

It is expressed in joule/coulomb (volt).

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FIGURE 5: A schematic illustrating a thermoelectric couple or module made of an n-type
(electrons, closed circle arrows) material and a p-type (holes, open circle arrows) material.
This diagram illustrates both the power generation (See beck effect) and electronic
refrigeration (Peltier effect) capabilities of the thermoelectric module.

THOMSON EFFECT:

When a current flows through an unequally heated metal, there is absorption or evolution of

heat throughout the body of the metal. This is known as the Thomson effect.

The Thomson coefficient 𝜎 of metal is defined as the amount of heat energy absorbed or

evolved when a charge of 1 coulomb flows in the metal between two points which differ in

temperature by 1 ℃.

The Thomson coefficient of a metal, expressed in (joule per coulomb per ℃), is numerically

equal to the emf in volt, developed between two points differing in temperature by 1 ℃.

In the positive Thomson effect, it is found that the hot end is at high potential and the cold

end is at low potential. Heat is evolved when the current is passed from the hotter end to the

colder end and heat is absorbed when the current is passed from the colder end to the hotter

end.

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 FIGURE 6: Thomson effect.

FIGURE OF MERIT:

The performance of thermoelectric devices is measured by the figure of merit (ZT).

ZT= 𝛼 2 𝑇/𝜌κ

ZT=𝛼 2 𝜎𝑇/κ

α = See beck coefficient, (μV/K)

ρ = electrical resistivity, (Ω cm)

σ = 1/ρ =electrical conductivity (Ωcm)−1

κ = thermal conductivity, (W/m K).

The dimensionless figure of merit is defined by ZT, where T is the absolute temperature. There

is no fundamental limit on ZT, but for decades it was limited to values around ZT=1 in existing

devices. The larger the value of ZT, the greater is the energy conversion efficiency of the

material. The quantity of 𝛼 2 𝜎 is defined as the power factor. Therefore, both the See beck

coefficient α and electrical conductivity σ must be large, while the thermal conductivity (κ)

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must be minimized. This well-known interdependence among the physical properties makes it

challenging to develop strategies for improving a material’s ZT.

LOW-TEMPERATURE THERMOELECTRIC MATERIALS:

GeTe:

Much effort has recently been put into developing high-performance low-temperature

thermoelectric materials for waste-heat recovery and thermoelectric cooling. The figure of

merit (ZT) at low temperature is achieved by p-type GeTe-based alloys. The average ZT within

the low-temperature range (300–473 K) for the as-synthesized quenched GeTe-based alloys

can reach up to 1.1, which is even better than that of the state-of-the-art commercial

Bi0.5Sb1.5Te3 ingots. Moreover, the as-synthesized samples also show superior thermoelectric

performance in the mid-temperature range, demonstrating great promise for thermoelectric

applications in a broad temperature range. The Ge-vacancy arrays can serve as high-speed

channels with low effective mass for carrier transport but obstacles for phonon transport,

resulting in increased carrier mobility and reduced lattice thermal conductivity simultaneously

for high ZT in the as-synthesized quenched GeTe-based alloys. These findings provide an

intriguing way to enhance ZT and to develop low-temperature thermoelectric materials beyond

Bi2Te3-based alloys.

FIGURE 7: Discovery of low temperature.

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BiSbAg and BiSbZn:

BiSbAg and BiSbZn alloys with the general formula of Bi85Sb15- and Bi85Sb15, respectively,

were prepared by mechanical alloying and subsequent pressure-less sintering. It shows that the

figure-of-merit of sample Bi85Sb14Ag1 reaches a maximum value at 219K, which is twice as

large as that of the reference sample Bi85Sb15. The figure-of-merit was obtained for the sample

Bi85Sb14Zn1 at 155K, which is about 78 percent larger than that of the reference sample Bi85Sb15

at the same temperature. The maximum figure-of-merit value is shifted towards the lower

temperature region.

CuAgSe:

High mobility phonon-glass semimetal CuAgSe has shown promise in recent years as a

potential low-temperature thermoelectric material. It exhibits reasonably strong thermoelectric

performance as well as extremely high carrier mobility, both of which are enhanced when the

material is doped with Ni at the Cu sites. The various measurements on CuAgSe samples doped

with Co and Cr according to the following composition. Results reveal a remarkable sensitivity

of CuAgSe thermoelectric properties to chemical doping in general as well as a particular

sensitivity to specific dopants. This demonstrated tunability of CuAgSe various properties

further the case that high mobility phonon glass-semimetals are strong candidates for potential

low-temperature thermoelectric applications.

CsBiTe:

Optimization of modules based on the new low-temperature thermoelectric material CsBi Te

has been investigated. These materials have shown very promising thermoelectric properties

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for cooling applications in the 100-300 K range, however doping and alloying optimization is

essential toward developing high-efficiency coolers.

MID-TEMPERATURE THERMOELECTRIC MATERIALS:

GeTe:
GeTe is a promising thermoelectric material at medium temperature, but its carrier

concentration tends to go beyond the optimal range for thermoelectrics. This work realized a

significant ZT enhancement from 1.0 to 2.0 by suppressing the formation of Ge vacancies and

band convergence. By simply optimizing the amount of excessive Ge, the hole carrier

concentration is greatly reduced. It is demonstrated that the suppression of Ge vacancies can

optimize the carrier concentration. Further Bi doping facilitates band convergence as featured

by the increased band effective mass and high mobility, which in turn yields large power factors

and low electronic thermal conductivity. Bi doping-induced mass and strain fluctuation also

favor the reduction of the lattice thermal conductivity. Consequently, a maximum ZT of ∼ 2.0

at 650 K with an average ZT of over 1.2 is achieved in the nominal composition Bi0.05Ge0.99Te,

which is one of the best thermoelectric materials for medium temperature applications.

FIGURE 8: Mid-temperature thermoelectric material.

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MnTe:
MnTe has been found to exhibit good thermoelectric properties at medium temperature

recently, but the electrical transport properties, especially the interaction between magnetism

and carriers, are still not fully understood and the synthesis process reported is mainly

composed of melting. Herein, we have a facile method combining mechanical alloying and

spark plasma sintering (SPS) to fabricate high purity MnTe. Carrier concentration is well-tuned

by sodium doping, resulting in a high power factor over 900 (μW m−1 K−2) and a

maximum ZT value exceeding 1.0 at 873 K. The electrical transport properties are analyzed by

the single parabolic band model. Additionally, different electrical transport properties induced

by the magnetic transformation were discussed and clarified by first-principles calculation,

including the increase of carrier concentration, a decrease of mobility, and enhancement of the

density-of-state (DOS) effective mass. The high thermoelectric performance reveals the

potential of MnTe as a promising candidate for medium-temperature thermoelectric materials.

HIGH-TEMPERATURE THERMOELECTRIC MATERIALS:

ZnAlO:

A mixed oxide (Zn1−xAlx)O exhibits promising thermoelectric properties attaining a

dimensionless figure of merit ZT of 0.30 at 1000 °C, which value is much superior to other

oxides and quite comparable to conventional state‐of‐the‐art thermoelectric materials. The

addition of a small amount of Al2O3 to ZnO results in a large power factor of 10-15 to

10−4 W/mK2 showing a marked increase in the electrical conductivity while retaining

moderate thermoelectric power. A large product of the carrier mobility and density of

states would be responsible for the favorable electrical properties of the present oxide. A figure

of merit Z=0.24×10−3 K−1 is attained by (Zn0.98Al0.02)O at 1000 °C, even with high thermal

conductivity. A predominant proportion of the phonon thermal conductivity promises a further

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improvement in the thermoelectric performance by selective enhancement

of phonon scattering.

EuInSb: (ZINTL PHASES)

The complex bonding environment of many ternary Zintl phases, which often results in low

thermal conductivity, makes them strong contenders as thermoelectric materials. Here, we

extend the investigation of A5In2Sb6 Zintl compounds with the Ca5Ga2As6 crystal structure to

the only known rare-earth analog. Eu5In2Sb6. Zn-doped samples with compositions of

Eu5In2−xZnxSb6 (x = 0, 0.025, 0.05, 0.1, 0.2) were synthesized via ball milling followed by hot

pressing. Eu5In2Sb6 showed significant improvements in air stability relative to its alkaline

earth metal analogs. Eu5In2Sb6 exhibits semiconducting behavior with possible two-band

behavior suggested by increasing band mass as a function of Zn content, and two distinct

transitions observed in optical absorption measurements (at 0.15 and 0.27 eV). The p-type Hall

mobility of Eu5In2Sb6 was found to be much larger than that of the alkaline earth

containing A5In2Sb6 phases (A = Sr, Ca) consistent with the reduced hole effective mass

(1.1 me). Zn doping was successful in optimizing the carrier concentration, leading to a ZT of

up to 0.4 at ∼660 K, which is comparable to that of Zn-doped Sr5In2Sb6.

NbRhGe:

A new thermoelectric material, NbRhGe, has been studied using the density functional theory.

The components of NbRhGe are not toxic neither they suffer poor chemical and physical

stability. The results showed that NbRhGe is a semiconductor with a band-gap value of 1.62

eV. The compound is both elastically and thermodynamically stable, ductile, and strong. It is

a high-temperature thermoelectric material with a predicted figure of merit (ZT) value of 0.75

at 1050 K.

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YbMnSb:

Compounds of the Yb14MnSb11 structure type are the highest efficiency bulk p-type materials

for high-temperature thermoelectric applications, with reported figures of merit (ZT) as high

as ∼1.3 at 1275 K. Further optimization of ZT for this structure type is possible with the

development of a simple synthetic route. However, this has been difficult to achieve because

of the small amount of Mn required compared with Yb and Sb. A simple synthetic route for

Yb14MnSb11 has been developed utilizing a combination of ball milling and annealing to

produce phase-pure material followed by spark plasma sintering for consolidation. Upon

cycling to temperatures greater than 1272 K, Yb14MnSb11 shows the presence of Yb11Sb10.

Additional samples with 5% and 10% excess Mn were also investigated. Adding 5–10% excess

Mn does not change the low-temperature properties and improves the high-temperature ZT,

resulting in a ZT of 1.1–1.2 at 1000 K for Yb14Mn1.05Sb11, 30–40% improvement over that of

the Sn flux reaction. The increase in ZT is attributed to the optimization of the carrier

concentration. These results provide a reliable method of bulk synthesis of this Zintl phase and

open the way for the discovery of new compounds with the potential for even higher ZT.

NEW GENERATION THERMOELECTRICS:

Although See beck observed thermoelectric phenomena in 1821 and Alten rich in 1911, it took

several decades to develop the first functioning devices in the 1950s and 1960s. They are now

called the first generation thermoelectrics with an average of Z≈1.0. Devices made of them can

operate at ≈5% conversion efficiency. After several more decades of stagnancy, new theoretical

ideas relating to size effects on thermoelectric properties in the 1990s stimulated new

experimental research that eventually led to significant advances in the following decade.

Although the theoretical ideas were originally about prediction on raising the power factor, the

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experimental breakthroughs were achieved by significantly decreasing the lattice thermal

conductivity. Among a wide variety of research approaches, one has emerged, which has led

to a near doubling of ZT at high temperatures and defines the second generation of bulk

thermoelectric materials with ZT in the range of 1.3–1.7. This approach uses nanoscale

precipitates and composition inhomogeneities to dramatically suppress the lattice thermal

conductivity. These second-generation materials are expected to eventually produce power-

generation devices with conversion efficiencies of 11–15%. Third-generation bulk

thermoelectrics has been under development recently, which integrate many cutting-edge ZT-

enhancing approaches simultaneously, namely, enhancement of See beck coefficients through

valence band convergence, retention of the carrier mobility through band energy offset

minimization between matrix and precipitates, and reduction of the lattice thermal conductivity

through all length-scale lattice disorder and nanoscale endo axial precipitates to mesoscale

grain boundaries and interfaces. This third generation of bulk thermoelectrics exhibits high ZT,

ranging from 1.8 to 2.2, depending on the temperature difference, and a consequent predicted

device conversion efficiency increase to ∼15–20%.

PROPERTIES OF THERMOELECTRIC MATERIALS:

•Absence of moving parts

•High reliability

•Quietness

•Lack of vibrations

•Low maintenance

•Simple start-up

•No pollution

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•Light weight

•No noise

•Precise temperature control: within +/‐ 0.1C.

APPLICATIONS:
➢ Thermoelectric devices are used in larger machines as part of power generation. A great

example of this is a diesel engine. The Thermoelectric Project in Maine aims to

“recover waste heat from large marine Diesel engines using Thermoelectric

technology.” Their “green machine” works to recover energy.

FIGURE 9: Green machine.

➢ Another application is Seiko’s Thermic watch, which uses body heat to power its

thermoelectric device.

FIGURE 10: Seiko thermic watch.

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 ➢ Thermoelectric Generators:

Thermoelectric Generator (TEG) is also known as See beck generator, converts heat energy

(temperature difference) into electrical power directly without having any rotating

part/mechanism. These TEG’s generates electrical energy from waste heat energy from

automotive, aerospace, industrial. the TE is better for electricity generation than solar

technology but the low efficiency of TEG is a drawback.

➢ Electronic Devices Cooler:

Many high-power electronics devices such as microprocessors, power

amplifiers and computers used in servers continuously run

and provide service to customers; during the run, a large amount of heat is produced within in

system and it must have dissipated from

the system to avoid hardware failure and malfunction. Thus, cooling is required to enhance the

performance and life of electronic

devices. TE coolers have many advantages over a traditional cooling system such as being

compact in size, vibration-free because of no moving part, maintenance less, run using DC

supply.

➢ Other Applications

There are several other applications of thermoelectricity and also, it has the potential for further

development because of its simplicity, compact in size, work on DC voltage, portability, no

rotating element, etc. Various medical applications of TE such as wearable sensors for

electroencephalography (EEG), electrocardiography (ECG),

electromyography (EMG) etc, human implantable devices (like; cardiac pacemaker, cardiac

defibrillator, neurological stimulator, etc).

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CONCLUSION:

Thus the Thermoelectric materials act as a device for converting heat energy into electrical

energy. Thermoelectric materials have developed an introduction for Nanotechnology. The

uniqueness and simplicity of the TE principle for reversible conversion of energy; from one

form to another form make it more and more useful for various applications. Also, it has good

future scope because of environmental issues and technological advancement. The only

drawback it has low efficiency on its own but the integrated use of thermoelectricity can

increase the performance of existed systems.

REFERENCES:
1) TC Harman, JM Honig, “Thermoelectric and thermomagnetic effects

and applications”,377 (1967).

2) Krishna Raj Adhikari., “Thermocouple: Facts and Theories”, The Himalayan Physics,

6 & 7, 10 (2017).

3) Jeon H.W, et al., “Electrical and thermoelectrical properties of undoped Bi2Te3-Sb2Te3

and Bi2Te3-Sb2Te3-Sb2Se3 single crystals”, Journal of Physics and Chemistry of

Solids,52, 579 (1991).

4) Safa Kasap, “Thermoelctric effects in metals-thermocouples”, 2 (1997).

5) D. K. C. MacDonald, “Thermoelectricity”, Dover Publications, 46, 1 (2006).

6) Davide Beretta, et al., “Thermoelectrics: From history-a window to future”, Material

science and Engineering, 138, 210 (2019).

7) Cronic B. Vining, “Fifteen years of progress and Things to Come”, European

Conference on Thermoelectric (ECT), (2007).

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