ME 381R Lecture 20:

Nanostructured Thermoelectric Materials

Dr. Li Shi

Department of Mechanical Engineering

The University of Texas at Austin
Austin, TX 78712
www.me.utexas.edu/~lishi
lishi@mail.utexas.edu
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 Thermoelectrics
• Thermoelectric (Peltier) cooler:
250C
• Thermocouple:

250C

• Seebeck effect: T1 T2
Bi, Cr, Si… Metal Q
∆V Pt Pt Cold
S=
∆T
V
I p n I
• Thermoelectric refrigeration:
no toxic CFC, no moving parts
Hot
• • •
Electronics Optoelectronic Automobile
s

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 Thermoelectric Cooling Performance
Metal Q
Venkatasubramanian et al. Nature 413, 597
Cold
Nanostructured 2.5-25nm
p n I thermoelectric materials Bi2Te3/Sb2Te3 Superlattices
I
Harman et al., Science 297, 2229
Hot Quantum dot superlattices

• Coefficient of Performance (COP≡

Q/IV)
2
CFC unit
COP

1
Bi2Te3
0
0 1 2 3 4 5
ZT
• ZT: Figure of Merit
Seebeck coefficient
Electrical
S 2σ conductivity
ZT ≡ T 3
κ Thermal conductivity
 Thin Film Superlattice Thermoelectric Materials
 Thin film • Phonon (lattice vibration wave)
superlattice transmission at an interface
Incident
phonons Reflection

Interface

Transmission

 Approaches to improve Z ≡ S2σ/κ :

--Frequent phonon-boundary scattering: low κ
--High density of states near EF: high S2σ in QWs
Quantum well
Barrier (smaller Eg)
(larger Eg)

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 Electronic Density of States in 3D
2D projection of 3D k space • Each state can hold 2 electrons
ky of opposite spin(Pauli’s principle)

( 4πk 3 3) k 3
dk • Number of states with wavevectore<k:

k N = 2⋅ = V
( 2π L ) 3 3π 2
kx

2 2
E = k / 2m
2π/L

•Number of states with energy<E:

V 2mE
N= ( )3 / 2
Density of States 3π 2 2

dN
m 2mE Number of k-states available between
De ( E ) = dE = 2 2 2
energy E and E+dE 5
V π
 Electronic Density of States in 2D
2D k space (kz = 0) • Each state can hold 2 electrons
ky of opposite spin(Pauli’s principle)
dk • Number of states with wavevectore<k:

πk 2 k2
k N = 2⋅ = A
( 2π L ) 2 2π
kx

2 2
E = k / 2m
2π/L

•Number of states with energy<E:

mE
Density of States
N= 2
A
π
dN
m
De ( E ) = dE = 2
Number of k-states available between
energy E and E+dE 6
A π
 Electronic Density of States in 1 D

ψ k ( x ) ∝ eikx
k = 2nπ/L; n = ±1, ± 2, ± 3, ± 4, …..
ψ(x+L) = ψ(x)
1D k space (ky = kz =0)
-6π/L -4π/L -2π/L 0 2π/L 4π/L
k
• Each state can hold 2 electrons k
of opposite spin(Pauli’s principle)
N = 2⋅
• Number of states with wavevectore<k:
( 2π L )
2 2
E = k / 2m
•Number of states with energy < E:
2mE
Density of States N= L
π
dN
m
De ( E ) = dE Number of k-states available between
= energy E and E+dE 7
L 2 Eπ
 Electronic Density of States

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Ref: Chen and Shakouri, J. Heat Transfer 124, p. 242 (2002)
 Low-Dimensional Thermoelectric Materials
Thin Film Superlattices of Nanowires of
Bi2Te3,Si/Ge, GaAs/AlAs Bi, BiSb,Bi2Te3,SiGe

Al2O3 template Top View

Nanowire

Barrier Quantum well

Ec
E
Ev
x 9
 Potential Z Enhancement in Low-Dimensional Materials

•Increased Density of States near the Fermi Level:

high S2σ (power factor)

•Increased phonon-boundary scattering: low κ

 high Z = S2σ/κ:

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Thin Film Superlattices for TE Cooling
Venkatasubramanian et al, Nature 413, P. 597 (2001)

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 Z Enhancement in Nanowires
Theory Experiment

Nanowire
Prof. Dresselhaus, MIT
Phys. Rev. B. 62, 4610
Heremans et at,
Phys. Rev. Lett. 88, 216801
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Challenge: Epitaxial growth of TE nanowires with a precise doping and size control
 Imbedded Nanostructures in Bulk Materials
•Nanodot Superlattice Data from A. Majumdar et al.

InGaAs 0.8ML
5x1018 Si-doped InGaAs

0.6ML
ErAs
Si-Doped ErAs/InGaAs SL
0.4ML (0.4ML)
Undoped ErAs/InGaAs SL
0.2ML (0.4ML)

Plan View

Hsu et al., Science 303, 818 (2004)

[11
0] •Bulk materials
100 nm with embedded
Cross-section
nanodots

AgPb18SbTe20 AgSb rich

10 nm
ZT = 2 @ 800K
Images from Elisabeth Müller Paul Scherrer 13
Institut Wueren-lingen und Villigen, Switzerland
 Phonon Scattering with Imbedded Nanostructures
LO

Frequency, ω
TO

TA
LA

Spectral
distribution of 0 π/a
Wave vector, K
phonon
energy (eb) & v
group velocity
(v) @ 300 K

Phonon Scattering
eb
Nanostructures
Atoms/Alloys

ωmax
Frequency, ω
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Long-wavelength or low-frequency phonons are scattered by imbedded nanostructures!
 Challenges and Opportunities

• Designing interfaces for low thermal conductance at high temperatures

• Fabrication of thermoelectric coolers using low-thermal conductivity, high-ZT

nanowire materials

• Large-scale manufacturing of bulk materials with imbedded nanostructures

to suppress the thermal conductivity

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