Thermoelectric Material and its Applications

Prof. Ramesh Chandra Mallik

Associate Professor
Department of Physics,
Indian Institute of Science,
Bangalore, India

email : [email protected]

http://www.physics.iisc.ernet.in/~rcmallik/index.html
 Outline
• Introduction to Thermoelectrics
• Thermoelectric properties:
Electrical conductivity, Seebeck coefficient, Thermal conductivity, Electronic
thermal conductivity, Lattice thermal conductivity, Figure of merit
• Concepts of Optimization of the thermoelectric parameters
Alloying, Doping, Filling voids, Microstructure control, Concept of Phonon-
glass electron crystal (PGEC) and Phonon-liquid electron crystal (PLEC)
• Types of Thermoelectric material
Low Temperature- BiSb, CsBi4Te6, FeSb2, YbAgCu4, Mid Temperature-
Chalcogenides, Skutterudites, Tetrahedrites, BiCuSeO, High Temperature-
Lanthanum Telluride, SiGe, WS2
• Synthesis of materials and measurement techniques
• Thermoelectric module and devices
Fabrication and Measurement of device efficiency
• Applications
Exhaust of automobiles, refrigerators, industries, space programs (RTG)

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Basic Requirements for this Course

• Solid State Physics/ Condensed Matter

Physics
• Material Science
• Semiconductor Physics
• Crystallography
• Measurement Technique
• Material Characterizations
 Introduction
• DC Mechanical Generator: 4000 GW

Thermoelectric Device: ZT= 4

• Supper conductor : Which will work at 400 K

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 Different types of Energy and Conversion
Mechanical Energy
Nuclear Energy Chemical Energy

Dynamo

Thermal Energy
Electrical Energy Solar Solar Energy
Panel
Seebeck effect
Thermoelectricity

Peltier effect

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Phonon Spectrum
 Four are important in Energy Research:

* Thermal to Electrical : Thermoelectric Device: ZT= 4 at

room temperature

*Light to Electrical : Solar cell Efficiency = 40 % of Carnet

efficiency at room temperature

• Supper conductor : Which will work at 400 K

• DC Mechanical Generator: 4000 GW

 Various energy requirements

Elsheikh, Mohamed Hamid, et al. "A review on thermoelectric renewable energy: Principle parameters that affect their
performance." Renewable and Sustainable Energy Reviews 30 (2014): 337-355.
 Thermoelectricity

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• Imagine having generators that directly convert heat
to electricity, or refrigeration devices that use
electricity to pump heat from cold to hot, both
without any moving parts or bulk fluids [liquids or
gases like chloroflurocarbons (CFCs) or
hydrochloroflurocarbons (HCFCs)].

• Such thermoelectric (TE) devices already exist. They

are lightweight, small, and inexpensive, and they
completely eliminate the need for CFCs or HCFCs and
heavy compressors in small-scale refrigeration.
• Most refrigeration failures are due to gas leaks or to the
failure of moving parts in the compressor. The former, of
course, may also pose environmental problems.
• TE devices are potentially much less prone to failure
because no moving parts are involved.
• Currently, the world market for TE cooling devices is still
small (about $80 million to $160 million per year). Major
uses for these TE devices include cooling laser diodes
and electronic coolers for picnic baskets. These same
devices can also be used as electrical generators when a
source of heat is present. Yet, if these TE devices are so
useful, why are they not more widely used?
• Presently, the use of TE devices is limited by their low efficiencies.
• The efficiency of a refrigerator is expressed by the coefficient of
performance (COP), which is the amount of cooling divided by the
electrical energy input needed to obtain that cooling.
• The laws of thermodynamics tell us that a maximum efficiency, called
the Carnot efficiency, cannot be exceeded. The COP at Carnot efficiency
is just T cold/(T hot –T cold), where T hot andT cold are the
temperatures of the ambient environment and of the coldest part of the
refrigerator, respectively.
• The real efficiency of any device is often given as a percentage of the
Carnot efficiency. Present TE devices operate at about 10% of Carnot
efficiency, whereas the efficiency of a compressor-based refrigerator
increases with size: a kitchen refrigerator operates at about 30% of
Carnot efficiency and the largest air conditioners for big buildings
operate near 90%.
• Today's TE devices are particularly useful when rapid on-off cycling is
required at low temperature differences. Moreover, TE devices are used,
for example, when the efficiency is a less important issue than small size,
low weight, or high reliability. However, there is no known limit to the
potential efficiency of a TE device, except for the Carnot limit.
 Thermoelectric Effects
• In 1822, German physicist Thomas
1.Seebeck Effect Johann Seebeck observed that
when junctions of two dissimilar
materials (metal or semiconductor)
forming a closed circuit are
maintained at different
temperatures, a voltage is
developed. This is known as the
Seebeck.
• Temperature difference causes a
diffusion of majority charge
carriers from hot side to the cold
side of the thermocouple.
• An electric field is developed
Seebeck coefficient or thermoelectric power between the positive holes in the
is the voltage produced per unit hot region and the excess electrons
temperature difference between the two in the cold region which prevent
junctions of materials. further accumulation of electrons
𝜟𝑽 in cold side.
Thermoelectric power is given by: 𝑺 = 𝒍𝒊𝒎 • A voltage is developed between hot
𝜟𝑻→𝟎 𝜟𝑻
Slack G A, CRC Handbook of thermoelectric edited by Rowe D M,
and cold end of the thermocouple.
CRC, Boca Roton, FL. (1995). 13
Discovery of Thermoelectric Power

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 Thomas Johann Seebeck, Undated engraving
Deutsches Museum, Munich

Seebeck's instrument (left) and its experimental use (right)

• Seebeck surveyed many different materials: including ZnSb, PbS and CoAs3 and
made a qualitative ordering of their relative Seebeck effect.
• Gustav Magnus discovered the Seebeck voltage does not depend on the
distribution of temperature along the metals between the junctions in 1851.
• This indication that the thermopower is a thermodynamic state function. This is the
physical basis for a thermocouple.
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 Thermoelectric Effects
2. Peltier Effect • In 1834, French physicist Jean Charles
Athanase Peltier discovered a reverse
phenomenon of Seebeck effect.

• Peltier observed that when an electric current is

applied across the junctions of two dissimilar
materials (metal or semiconductor), a heat is
either absorbed or released according to the
direction of current. This is known as the
Peltier effect.

• Electric current causes a flow of charge carriers

from one material to another material of the
thermocouple.

• The Peltier effect arises due to the different

chemical potential of the charge carriers in the
The rate of heat (Q) evolved or absorbed at materials on either side of the junction.
the junctions when an electric current I • In 1838 Lenz showed that depending on the
direction of current flow, heat could be either
passes through the circuit : removed from a junction to freeze water into ice
𝑸 = 𝜫𝑿 − 𝜫𝒀 = 𝜫𝑿𝒀 𝑰 • Reversing the current, heat can be generated to
where 𝜫𝑿 , 𝜫𝒀 is the Peltier coefficient of melt ice. The heat absorbed or created at the
junction is proportional to the electrical
material X and material Y.
current.
• The proportionality constant is known as the
Peltier coefficient.
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/thermalRef01/ 16
 Thermoelectric Effects
3. Thomson Effect • Twenty years later in 1851,
William Thomson predicted third
thermoelectric effect.
• He observed when a current flows
through unequally heated
conductors, the heat energy is
evolved or absorbed not only at the
junctions but throughout the
materials of the thermocouple.
• This effect is reversible.
• The heat is proportional to both
the electric current and the
temperature gradient.
• The rate of heat produced or
𝜟𝑽
absorbed per unit volume:
Thomson relations: 𝜫 = 𝑻 = 𝐓𝐒 𝒅𝑸
𝜟𝑻
𝒅𝑺 = 𝑲𝑱Δ𝑻
𝑲=𝑻 𝒅𝒕
𝒅𝑻
where 𝜟𝑻 is the temperature
gradient, 𝑱 is the current density and
https://www.ferrotec.com/technology/thermoelectric
/thermalRef01/
𝑲 is the Thomson coefficient.
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 Thermoelectricity- 1900 - 1970
• Edmund Altenkirch was the first to use
the constant property model to derive
the maximum efficiency of a
thermoelectric generator (1909) as well
as the performance of a cooler (1911)
when the design and operating
conditions are fully optimized.
• This correct relationship, later
developed into the 'figure of merit' zT,
that good thermoelectric materials
should possess large Seebeck
coefficients, high electrical conductivity
(to minimize Joule heating due to
electrical resistance) and low thermal
conductivity (to minimize heat loss).
• Early thermal conductivity measurements by A. Eucken on solids
quickly revealed that point defects found in alloys
significantly reduces lattice thermal conductivity - a
strategy that becomes important for thermoelectric
materials.
• During both the world wars thermoelectricity was
extensively studied for possible applications in the wars.
• By the 1950's, generator efficiencies had reached 5%
and cooling from ambient to below 0 C was achieved
• It was believed that thermoelectricity could replace
conventional engines and refrigerators.
• However, by the end of the 1960's the pace of progress
had slowed with some discussion that the upper limit of
zT might be near 1 and researchers were disinterested.
Abram F. Ioffe
• In 1949 Abram Fedorovich Ioffe developed the
modern theory of thermoelectricity using the
concept of the 'figure of merit’ zT.
• He authored classic texts on Semiconductor
Thermoelements and Thermoelectric Cooling
(1956).
• Ioffe also promoted the use of the
semiconductors in thermoelectrics and
semiconductor physics to analyze results and
optimize performance.
• Ioffe and his Institute in Saint Petersburg
actively pursued thermoelectric research and
development in USSR leading to some of the
first commercial thermoelectric power
generation and cooling devices.
• Ioffe was one of the first to promote the use of
alloying to reduce lattice thermal conductivity
by point defects.
H. Julian Goldsmid
• One of the first demonstrations of 0 C
cooling was by H. Julian Goldsmid in
1954 using thermoelements based on
Bi2Te3
• Goldsmid was one of the first to utilize
the thermoelectric quality factor,
identifying the importance of high
mobility and effective mass
combination and low lattice thermal
conductivity in semiconductors that
when properly doped make good
thermoelectric materials.
• Goldsmid authored many introductory
books including Introduction to
Thermoelecricity (2010).
 Thermoelectricity 1970-2000

In the search for high zT materials, a general strategy

guided by the quality factor has been to look for small
band gap semiconductors made from heavy elements.
Glen Slack summarized the material requirements in the
"phonon-glass electron-crystal" or PGEC concept that
the phonons should be disrupted like in a glass but the
electrons should have high mobility like they do in
crystalline semiconductors
• The reliability and simplicity of thermoelectricity enables niche
applications for this solid-state technology even while
conventional processes are more efficient. Besides
thermocouples, a small but stable industry to produce Peltier
coolers based on Bi2Te3-Sb2Te3 formed which now produce
coolers for a variety of products ranging from optoelectronics,
small refrigerators and seat cooling/heating systems. The need
for reliable, remote power sources provides some niche
applications for thermoelectric power generation.

• The maturity of the science, technology and commercial use of

thermoelectricity has lead to a number of focused scientific
meetings and organizations like International Thermoelectric
Society (ITS or ICT)
Current status..
• Interest in thermoelectricity renewed in the 1990's with the
influx of new ideas. The hope that engineered structures will
improve zT, particularly at the nanometer scale has reinvigorated
research in thermoelectric materials. While some of these ideas
have shown to be ineffective, others have lead to entirely new
classes of complex thermoelectric materials.

• The global need for alternative sources of energy has revived

interest in commercial applications and stimulated interest in
developing inexpensive and environmentally-friendly
thermoelectric materials.

• High zT s has been obtained in materials like PbTe, Bi2Te3,

CoSb3, till date highest zT of 2.6 has been found for SnSe single
crystals along the b axis.
 Need for Thermoelectrics

Thermoelectric Generator Module

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Thermoelectric Cooler
 Thermoelectric Module and its
application
Electrically in series and thermally in parallel

CampStove
Powering space missions

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lite-pro

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Efficiency of a thermoelectric material and interrelation of its parameter

J.-C. Zheng, Front. Phys. China, 2008, 3(3): 269-279

 Increase electrical conductivity ()
For high  : n large and m * small (=neµ)

Increase carrier concentration(n)- σ may increasing

by doping . Seebeck is adversely affected. Needs to
optimized rather than only increasing.
Increasing mobility(μ) – σ increases by increasing
μ. Does not affect S directly. Example- Modulation
doping and grain alignment – less scattering
experienced by the carriers.
Increasing Seebeck coefficient (S)

• Resonant doping-Increased effective mass –

increased Seebeck example- Tl doped PbTe.
• Decreasing band offset- decreasing energy
difference between bands increases band
degeneracy and band effective mass. Example -
Mn and Mg alloying in PbTe.
• Energy filtering- Energy dependent scattering –
low energy carriers are scattered S is increased
and σ is decreased
Decreasing thermal conductivity()
• Making solid solution
• Phonon Scattering by Point Defects
• Boundary Scattering
• Scattering of Electrons and Phonons
• Fine-Grained Material with Large Unit Cells
• Phonon-Glass Electron-Crystal(PGEC)
• Phonon-Liquid Electron-Crystal(PLEC)
Thermoelectric materials over the
years

Xiao Zhang, Li-Dong Zhao, Thermoelectric materials: Energy conversion between heat and electricity,
Number of papers in
thermoelectric

Materials Today PhysicsVolume 1, June 2017, Pages 2-6