A BRIEF INTRODUCTION TO

THERMOELECTRIC
MATERIALS

ENGINEERING 45
BY: KRISTIAN MADSEN, JAKE
SPRING 2009
YEAGER, KYLE PETERSON, &
NICK BIDAURRETA.
Santa Rosa Junior College
 THERMOELECTRIC EFFECTS
THE
EMF caused by temperature gradient across two dissimilar conducting metals, which form a closed loop.

Images Sited From Left to Right Respectively:

• http://jondetech.com/documents/about%20thermopiles_thermocouples%20and%20IR-sensors.html
• http://www.ferrotec.com/technology/thermoelectric/thermalRef01/
• http://www.chem.cornell.edu/fjd3/thermo/intro.html
1. http://www.thermoelectrics.com/introduction.htm
 FIGURE-OF-MERIT

THE QUALITY OF A
MATERIALS
THERMOELECTRIC
PROPERTIES ARE
REPRESENTED BY A
SO CALLED FIGURE-
OF-MERIT( Z ), AND
 2
OFTEN EXPRESSED z 
AS Z T, AS THIS IS A 
TEMPERATURE
DEPENDENT
CHARACTERISTIC. 1
 METALS
Metals were initially the center point for research into thermoelectric generation, but metals are
limited with respect to this application for the following reason.

Wiedemann-Franz Law :


 LT

A metals electrical conductivity and
thermal conductivity are related at a
given temperature; therefore, metals
best suited for thermoelectric
applications must posses a high
Seebeck coefficients. 2

2. http://hyperphysics.phy-astr.gsu.edu/HBASE/thermo/thercond.html
SEMICONDUCTORS

http://energyseeds.com/wp-content/uploads/2007/08/dscf5190-2re.jpg
 Thermoelectric Effect In Semiconductors
Thermoelectric power generation is explained by a gradient in conduction band energy, across a
material. This gradient in conduction band energy is caused by an applied thermal gradient.

For homogeneous materials the conduction band energy is directly related to temperature.

Electrons on the hot side of a material have greater conduction band energy than those on the cold
side producing an EMF.3
BAND ENERGY
CONDUCTION

- +

HOT COLD
3. http://ecee.colorado.edu/~bart/book/
 Thermoelectric Effect In Semiconductors
As for conduction band energy, valence band energy is also varied across a material with an
applied thermal gradient. In this case, valence band carriers are termed holes, and correspond to
an absent electron.3
CARRIER ENERGY

EC

Ev

HOT COLD
Thermoelectric Effect In Semiconductors
n-type Materials

- +
For n-type materials, electrons are the primary charge carriers for which applied
thermal gradients produce an EMF in the direction shown above. 3

p-type Materials

+ -
For p-type materials, holes are the primary charge carriers for which applied thermal
gradients produce an EMF in the direction shown above.3
 Thermoelectric Effect In Semiconductors
When connected in series, the two materials produce thermoelectric power capable of powering a
load.
p-type Material

LOAD
і→

n-type Material -
 Zintl Phases
Zintl phases are of interest in this arena, because of their, “electron-crystal, phonon-glass”
properties. These materials have high electron mobility like a crystal (electron-crystal) but
impedes phonon travel like an amorphous glass (phonon-glass). 4

One such material is:

Yb14MnSb11
Which has a very low
thermal conductivity
from 300-1275 K and
has applications in
energy recovery for
space travel. 4 Charts depicting materials properties.4

4. Susan M. Kauzlarich, Shawna R. Browna and G. Jeffrey Snyderb, “ Zintl phases for thermoelectric devices.” The Royal
Society of Chemistry, Dalton Transactions. April 2007, 2099-2107.
 Doping
One method for increasing the Figure of
p 2 kB �1 dn ( E ) 1 dm (E) �
Merit (z) is to increase the Seebeck   k BT � + �
coefficient (α). 3 q �n dE m dE �E  EF

Two methods for increasing α: Where:

T = temperature
n(E) = carrier density at energy E
1. An increased energy dependence of μ(E), for instance by a
μ(E) = mobility at energy E
scattering mechanism that strongly depends on the charge carriers.
EF = Fermi Energy
2. An increased energy dependence of n(E), for instance, by a local
increase in the Density of States (DOS).

Calculations indicate that doping

with group III elements Ga, In
and Tl can create resonant
energy levels in a classic
Thermoelectric material, PbTe,
that will lead to an increase in α.
This particular research yielded
z=1.5 @ 773K, double that of the
standard bulk material.

Heremans, J., et al., “Enhancement of Thermoelectric Efficiency in PbTe by Distortion of the Electronic
Density of States,” Science, vol. 321, pp. 554-557, 2008.
 Thin Films
• Thin films are artificial superlattice structures grown from such methods as chemical vapor
deposition and molecular beam epitaxy. They are carefully arranged to increase the
thermoelectric Figure of Merit (z).
• Three approaches to Thin Films that lead to an increase in z:
– Using quantum-confinement effects to obtain an enhanced density of states near the
Fermi Energy.
– Phonon blocking / electron transmitting superlattices, which utilize the acoustic
mismatch between superlattice components to reduce the lattice thermal conductivity.
– Thermionic effects in heterostructures

• Thin films of p-type Bi2Te3 / Sb2Te3 superlattices with quantum well periodicity of 6nm have
been produced with z ≈ 2.4 at room temperature. The highest value for bulk alloys of the
same composition is 1.1.

Venkatasubramanian, R., et al., “Thin-film thermoelectric devices with high room temperature
figures of merit,” Nature, vol. 413, pp. 597-602, 2001.
 Thermoelectrics by
Phase Transformations
• Researchers at Caltech have recognized that the increased figure of merit for
Thin-Films is the result of reduced thermal conductivity and have noted that
this reduction occurs regardless of the orientation of the carefully grown
superlattices. This led to the approach of using controlled transformations and
rapid solidification to obtain “self-organized” nanostructured thermoelectrics
in bulk volumes.
• The Sb2Te3-PbTe pseudobinary, with quenching, becomes Pb2Sb6Te11, which is
not stable above 300°C. Upon annealing, it transforms into adjacent lamallae
of Sb2Te3 and PbTe, which are crystallographically oriented indicating high
quality epitaxal interfaces (the goal of the Thin-Film approach). Interllamellar
spacing can be controlled by the time and temperature of annealing. No data
was available at the time of this report on the z value obtained by this
approach.

http://thermoelectrics.caltech.edu/nanomaterials_page.htm
 Phase Transformations of Pb2Sb6Te11

http://thermoelectrics.caltech.edu/nanomaterials_page.htm
 Nanopowder
• In 2008, researchers at MIT and BC reported a method of creating bulk
thermoelectric material that outperformed all previous bulk materials at a
lower cost of production that theoretically can meet z values of Thin-Films.
• How? By ball-milling crystalline ingots of BiSbTe bulk alloy under inert
conditions, they created a nanopowder of thermoelectric material. They
took this nanopowder and hot pressed it into disks (1.25 – 2.5cm in
diameter, 2 – 15mm thick) using a process such as Spark Plasma Sintering.
• The result was reduced thermal conductivity caused by increased phonon
scattering by grain boundaries and defects.
• Reported z values of 1.4 @ 100°C & 1.2 @ R.T.

• This method is so promising toward further improvement of

thermoelectrics that the creators started a company called GMZ Energy in
late 2008 to manufacture their new product.

Bed Proudel, et al., “High-Thermoelectric Performance of Nanstructured Bismuth Antimony Telluride Bulk Alloys,” Science,
vol. 320, pp. 634-638, 2008.
 Nanopowder

Bed Proudel, et al., “High-Thermoelectric Performance of Nanstructured Bismuth Antimony Telluride Bulk Alloys,” Science, vol. 320, pp. 634-638, 2008.
 Practical Devices
Many common thermoelectric devices suffer from high manufacturing costs or toxicity of the
materials (Lead-Tellurium, Cobalt-Antimony, etc), this makes them unsuitable for real world use.
New techniques in growing a thermoelectric device using Magnesium and Silicon (both non-
toxic materials) are expected to reduce costs from $900 per 100grams (semi-commericially) to
mass production of $450 for 100grams with even more expected price drops.5
Advantages and Abilities of Mg2Si
 Mg2Si Electrodes Operate with temperature
difference of 500⁰ C
 With a 10-Ω Load, Electrodes can generate up
to 2mA @ 48mV.
 Tests on small samples have been able to
generate at 0.2 (W/cm2)
 Prototype device consisting of 12 wafers (7x7
cm) is expected to generate 118 W of power with
a ∆T=250 ⁰ C
 Applications in using waste heat in the fluegas of
Representation of Thermoelectric Effect in Mg2Si.5
power plants, incinerators, and exhaust of cars

5. Ondrey, Gerald. "A new Mg2Si-production process promises to advance thermoelectric devices.” Chemical Engineering 115.3 (March
2008): 14(1)
 Practical Devices

Theoretical description of a Thermoelectric device. 7

7. http://www.nature.com/nature/journal/v413/n6856/images/413577aa.2.jpg
 Silicon Nanowires
Another safe and practical material is Silicon. Same Seebeck coefficient and electrical resistivity
of doped bulk Si but when designed with diameters of 20-300nm they exhibit 100-fold reduction
in thermal conductivity with a figure of merit of zT=0.6 at room temperature. Si nanowire arrays
show high-performance, scalable thermoelectric materials.6

Synthesis
 Aqueous electroless etching (EE) method: Solution of
Silver Nitrate (AgNO3) and Hydrofluoric (HF) Acid reacts
on the surface of Si wafers and is then washed off with
concentrated Nitric Acid to remove the Silver.
 Vapour-Liquid-Solid (VLS) growing method: The old-
common method of using a liquid substrate and then
introducing the Si as a vapour deposit (via adsorption)
onto the liquid and diffuses into the droplet.
Advantages
 Si nanowires have a large difference in mean free path
lengths b/w electroncs and phonons @ R.T. (110nm for
electrons and ~300nm for phonons).
 Easy and inexpensive for large-scale wafer
manufacturing

SEM image of a Pt-bonded EE Si nanowire (Scale = 2 micrometers).6

6. Hochbaums, Allon I., Renkun Chen, Raul Diaz Delgado, Wenjie Liang, Erik C. Garnett, Mark Najarian, Arun Majumdar, and Peidong
Yang. "Enhanced thermoelectric performance of rough silicon nanowires." Nature 451.7175 (Jan 10, 2008): 163(6)
 Silicon Nanowires

a) Cross-sectional SEM of an EE)Si nanowire array, B) Bright-field TEM of a segment of an EE Si wire. C)

High-Res TEM of EE Si nanowires, d) High-Res TEM of VLS Si nanowires.
6. Hochbaums, Allon I., Renkun Chen, Raul Diaz Delgado, Wenjie Liang, Erik C. Garnett, Mark Najarian, Arun Majumdar, and Peidong
Yang. "Enhanced thermoelectric performance of rough silicon nanowires." Nature 451.7175 (Jan 10, 2008): 163(6)
Thermoelectric Metallic Alloys

 All members of the alloys are from

elements adjacent to the semiconductors
on the Periodic Table of Elements.
 They Produce very low Seeback
Coefficients (50+/-10 mu V).
 Without the presence of some
semiconductor these alloys are
practically useless.
Thermoelectric Metals

 Some alloys do not require the aide of

semiconductors. Aluminum doped Zinc
oxide and NaCo2O4 were made; and
when tested, produced a Thermoelectric
Voltage of 86 mu V.
Sources

 American Ceramic Society. Journal of

the American Ceramic Society
. Columbus: Oct 2004. Vol. 87, Iss. 10;
pg. 1890
 Copyright 2009, Technology Business
Journal