Optimization of Nanostructured Thermoelectric Thermoelectric Materials Materials

Optimization of
nanostructured
thermoelectric thermoelectric
materials
Ali Shakouri
B ki S h l f E i i
materials
Baskin School of Engineering
University of California Santa Cruz
Acknowledgement:
ONR, DARPA DSO,
AFOSR, NSF/DOE,
EFRC, SRC-IFC
GDR Thermoelectricit; Orsay, France; 11 July 2011
A. Shakouri 7/11/2011
World Marketed Energy Use by
Fuel Type 1990-2035
13TW
2050: 25 30TW
yp
13TW
2050: 25-30TW
1 Quad =
1.055 x 10
18
J
2
US Department of Energy; Energy Information Administration (2010)
CO
2
e/ Person (tons) CO
2
e/ Person (tons)
P l ti (billi )
3
Population (billions)
CO
2
Emission Goals (2050-2100)
4
David MacKay, Sustainable Energy Without the Hot Air
ffi i 31%
Energy Use = 99 2 Quad = 105 EJ Power ~3.3 TW
US Energy Flow 2008
Rejected
Energy 61%
1.3TW
efficiency ~31%
Rejected
Energy 58%
1.3TW
efficiency ~32%
Nucl 8 45
Energy Use 99.2 Quad 105 EJ Power 3.3 TW
Solar 0.09
Electricity
Generation
efficiency 32%
Hydro 2.45
Nucl. 8.45
Wind 0.51
Geo 0 35
R id ti l
11.48
Generation
39.97
Natural
Gas 23.84
Geo 0.35
Residential
Commercial
8.58
Coal
22.42
Biomass
Industrial
23.94
25%
Petroleum
37.13
Biomass 3.88
27.86
5 http://eed.llnl.gov/flow
20%
Transportation
Quads
Power Generation Efficiencies of
Different Technologies
ZT S
2
T/ ZT= S
2
oT/k
6
Adapted from Cronin Vining, Nature Materials 2009
Latest Advances in Thermoelectric Materials
Nanostructured Thermoelectrics: Big
Efficiency Gains from Small Features, y ,
Vineis et al. Advanced Materials 2010
7
Kanatzidis et al., Angew. Chem. Int. Ed. 48, 8616 (2009);
see also Snyder and Toberer, Nature Materials (2008)
Cost of enewable energy sources
E.A. DeMeo and J.F. Galdo, DOE report TR-109496, December, 1997 p
http://www1.eere.energy.gov/ba/pba/tech_characterizations.html
0.1
W
h
]
Biomass
Projection 2010
M
&
O
SolarPVResidential
e
[
$
/
k
W
Biomass
Geothermal
PhotoVoltaic
s
t
m
e
n
t
a
n
d
M
o
f
i
t
Hotdryrock
Through
ConcentratedSolar
Gasification
Direct fired
g
y
p
r
i
c
e
SolarThermal
Wind
v
e
r
t
h
e
i
n
v
e
s
t
w
i
t
h
o
u
t
p
r
o
g
Solarthermaltower
Solarthermaldish
SolarPVThinfilm
E
n
e
r
g
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e
d
s
t
o
c
o
v
c
o
s
t
Hydrothermal
WindTurbineclass4
TE
0.01
0 1 1 10
P
r
i
c
e
Windturbineclass6
8
0.1 1 10
Capitalcost[$/W]
Investment(orOvernightcosttobuildasystem)including
materials,fixtureandadditionalequipments
EntropyTransportinTEMaterial
9
A. Shakouri, Annual Review of Material Research (July 2011)
EntropyTransportinTEMaterial
10
A. Shakouri, Annual Review of Material Research (July 2011)
M. Zebarjadi, et al., Phys. Rev. B 74, 195331 (2006)
HighS
2
o inmetalsemiconductor
nanocomposites
Assume: k =1W/mK mobility ~10 cm
2
/Vs
Energy
7
8
4
5
N d
Assume: k
lattice
=1W/mK, mobility ~10 cm /Vs
Metal/Semiconductor
Nanostructure
E
barrier
t
a
l
E
f
5
6
3
T
(
E
b
a
r
r
i
e
r
Non-conserved
Nanostructure
e
m
i
c
o
n
d
u
c
t
o
r
/

M
e
t
B
a
r
r
i
e
r
2
3
4
1
2
Z
T
r
-
E
f

)

/

k
B
T
Distance
D
e
g
.

S
e
Density of
0
1
2
-1
0
0 2 4 6 8 10 12 14
T
Conserved
Planar Barrier
Symmetry of DOS near Fermi energy is the main
States
0 2 4 6 8 10 12 14
Fermi Energy (eV)
Fermi energy eV ( free electron
concentration)
11
Symmetry of DOS near Fermi energy is the main
factor determining Seebeck coefficient.
D.VashaeeandA.Shakouri,Phys.Rev.Lett. 92,106103/1(2004)
Epitaxial Nitride HfN/ScN Metal Semiconductor
Multilayers
6 HfN/ 6 S N lti
Rough coherent
interfaces
3
3.5
6nm HfN/ 6nm ScN multi
layers on Silicon
2
2.5
3
T
1.5
2
1030meV
1040meV
1050meV
Z
T
0.5
1
300 400 500 600 700
( ) Temperature (K)
First met al-semiconduct or mult ilayers (5-20nm period; up t o 10m t hick)
12
Purdue (Tim Sands), UCSC, Berkeley
Very low measured t hermal conduct ivity 2.5-7W/ mK
ErAsSemimetalNanoparticles
embeddedinInGa(Al)AsSemiconductorMatrix
Erbium is co-deposited at a growth rate which is a fixed fraction
of the InGaAlAs growth rate (MBE growth)
Solubility limit is exceeded islands are formed (2-3nm ErAs) Solubility limit is exceeded islands are formed (2 3nm ErAs)
ErSb in ErSbin
In
0.5
Ga
0.5
Sb
TbAsin
GaAs
13
JoshZide,ArtGossardandChrisPalmstrm(UCSBandDelaware)
ElectricalconductivityandSeebeck
(theory/experiment)
Electrical Conductivity Seebeck
Si-doped InGaAlAs
0.6% ErAs:InGaAlAs
0.6% ErAs:InGaAlAs
Si-doped InGaAlAs
M. Zebarjadi, et al., Appl. Phys. Lett. 2009
14
J.-H. Bahk et al., Phys. Rev. B 2010 (Si-doped)
J. Zide et al., J. Appl. Phys. 2010
Thermalconductivityreduction
Si-doped InGaAlAs
c
y
) (k
Atoms/Alloys
Nanostructures
c
y
) (k
c
y
) (k
Atoms/Alloys Atoms/Alloys
Nanostructures Nanostructures Si-doped InGaAlAs
F
r
e
q
u
e
n
c
Nanostructures
F
r
e
q
u
e
n
c
F
r
e
q
u
e
n
c
Nanostructures Nanostructures
a
t
k
Wavevector
a
t
k
Wavevector
a
t
k
Wavevector
0.6% ErAs:InGaAlAs
15
W. Kim, et al. Physical
Review Letters 2006
Thermoelectricfigureofmerit
Largest measured
ZT~1.33 at 800K
Zide et al Journal of Applied Physics (2010); Bahk et al to be published (2011)
16
Zide et al. Journal of Applied Physics (2010); Bahk et al. to be published (2011)
The majority of ZT enhancement is from thermal conductivity reduction.
5% power factor enhancement at 800K.
Thermalconductivity
(TDTR)vs.Erconcentration
17
Gilles Pernot et al., MRS 2011
Silicide nanoparticles in SiGe
300K
3.2% nanoparticles
Silicon
Si
0.5
Ge
0.5
NiSi
Predictions:
Ge
NiSi
2
ZT (300K) ~0.5
ZT (900K) 1 8
Predictions:
18
ZT (900K) ~1.8
Natalio Mingo et al. Nano Letters 2009
Nanoparticle Radius [nm]
Powerfactorvs.Erconcentration
"Semimetal/Semiconductor nanocomposites for
thermoelectrics," H. Lu, P. G. Burke, A. C.
Gossard, G. Zeng, J.-H. Bahk, and J. E. Gossard, G. Zeng, J. H. Bahk, and J. E.
Bowers, Adv. Mater., 23 (2011)
19
Embedded nanoparticle scattering for
energy filtering
Born Approximation
Partial Wave technique
El t
Electron wave
nano-
particle
Electron wave
nano-
particle
Perturbation theory
Point size potentials
L b i
Exact solution of Schrodinger
Finite size scattering center
Low barriers
Multiple scatterings => Coherent Potential Approximation
Harder to implement
20
Mult ple scatter ngs oherent otent al pprox mat on
Mona Zebarjadi, et al. Appl. Phys. Lett. 2009
ErAs:InGaAlAs Theory vs. Experiment
21
Zebarjadi M., et al. Effect of nano-particle scattering on thermoelectric power
factor, App. Phys. Lett (2009)
Zebarjadi M., et al., Journal of Electronic Materials (2009)
Optimization of nanoparticle barrier
height and concentration
22
Zebarjadi M., et al. Effect of nano-particle scattering on
thermoelectric power factor, App. Phys. Lett (2009)
Nanoparticlescatteringpotential
0.2
0
0.1
(
e
V
)
r=2nm, Q=1.0e
r=1nm, Q=0.2e
-0.1
P
o
t
e
n
t
i
a
l

ionized impurity
-0.2 Lack of this deep potential
makes the nanoparticle
scattering weaker than the
-0.3
-10 -5 0 5 10
Position (nm)
scattering weaker than the
ionized impurity scattering,
thereby enhancing mobility.
23
Q-factor : number of electrons donated by a single nanoparticle
Relaxationtimevs.nanoparticle
scatteringpotentialprofile
Low-energy scattering
Low-frequency component
24
Je-Hyeong Bahk , Parthi Santhanam, Z. Bian et al., I 5.4 - I 5.5, MRS 2011
Submitted to APL (2011)
PowerfactorofInGaAswithionized
nanoparticles
20% ~ 20%
enhancement
25
Je-Hyeong Bahk , et al., I 5.5, MRS 2011
Measurementsofsubstrateremovedsamples
Bonding, Substrate
R l P i
26
Removal, Processing
J.H.Bahketal.,acceptedJ.Electron.Mater. 2010.
Cross-plane ZT Measurements
SiN
Neck
Device Gold lead
Gold
ErAs/InGaAlAs
AlN
Gehong Zeng
Key issues:
C i j i if i ( i )
Gehong Zeng
UCSB
Current injection uniformity (aspect ratio)
Heat load from probes or leads
Transient response in 0.1-10 sec
27
p
R. Singh, Z. Bian et al. Appl. Phys. Lett. 94: 212508, 2009
Transient Seebeck measurements
2
300K
S (V/K)
In-plane
-224
1.5
300K
350K
400K
450K
500K
550K
600K
(
m
V
)
Cross-plane
-233
1
650K
700K
k

V
o
l
t
a
g
e

(
0.5
S
e
e
b
e
c
k
300 700K
0
0 0.1 0.2 0.3 0.4 0.5
Ti ( )
28
Time (ms)
<100ns resolution
up to 800K
R. Singh, Z. Bian et al. Appl. Phys. Lett. 94: 212508, 2009
R. Singh et al. Review of Scientific Instruments, 2009
Extraction of Thin Extraction of Thin- -film ZT film ZT
S(V/K) o(/Ocm) K (W/mK)
In-plane data
-224 348 N/A
Cross-plane
-233 347 3 (3e), 5
Single element microrefrigerator
used to extract all thermoelectric
properties of 20m films
Cross plane
233 347 3 (3e), 5
Finite Element
-220 330 5
R. Singh, Z. Bian et al. Appl. Phys. Lett.
94: 212508, 2009
6
5
50
100
150
3
4
5
50
100
150
2.5
3
3.5
4
4.5
50 100 150 200 250
200
250
0
1
2
Temperature
Distribution (Joule)
Temperature
Distribution (Peltier)
29
FIG. 2. Measured (solid lines) and calculated (dashed lines) thermal
50 100 150 200 250
150
200
250
0
0.5
1
1.5
2
Technology Transition:
Stand alone thermoreflectance imaging system
( l i b i 100 0 2C i l 1024 1024) (resolution: submicron, 100ns, 0.2C, pixels: 1024x1024)
30
K. Yazawa, A. Shakouri, Electronics Cooling Magazine, Vol. 3, pp.10-15, March 2011.
http://Microsanj.com
Transient thermal imaging of a
microcooler at high current density
80x80 microns
10
Transient Response 50x50 Micron Device
n
g
e

(
C
)
I 1A
10s
6
8
t
u
r
e

C
h
a
n
1.7A, 166s
I=1A
2
4
Theory
Experiment
T
e
m
p
e
r
a
t
20s
50s
-2
0
10
-7
10
-6
10
-5
0 0001 0 001
S
u
r
f
a
c
e

31
10
7
10
6
10
5
0.0001 0.001
Time(s)
Y. Ezzahri, J. Christofferson, et al., J. Appl. Phys, 106, 114503, (2009)
ErAs:InGaAs thick layer growth
SEM
63
SEM
63 m
32
Hong Lu, Art Gossard, UCSB
Nonlinear Peltier Coefficient
200

InGaAs
150
200

10
16
P lti ffi i t
V
)
10
16
cm
-3
5x10
16
cm
-3
100
P
e
l
t
i
e
r

m
V
10
5*10
16
10
17
10
18
Peltier coefficient
can increase
significantly with
i
e
r

(
m
V
10
17
cm
-3
50
P
g y
bias, especially at
low temperatures.
P
e
l
t
i
Doping =10
18
cm
-3
0 1 2 3 4
0
current 10
5
A/cm
2

Current (10
5
A/cm
2
)
33
( )
M. Zebarjadi, K. Esfarjani & A. Shakouri , Appl. Phys. Lett., 91, 122104 (2007)
N : The Greens function of the total energy density propagation K(t x) in a solid
EnergydensitypropagationinTEmaterials
N
2
: The Green s function of the total energy density propagation K(t,x) in a solid
material when there is delta-function excitation P(t)
( )
( )
, K q
i q
N q M
o e
e = =
P(t)
( )
( )
( )
2 2
2
2
,
1
Q
C
N q M
P
D q
M i i D q
e
e e
e
e et
= =
(
= +

K(t,x)
( )
( )( )
2
2 2 4
1
q C
q Q q C Q C
M i i D q
i iD q i iD q D D q
e et
e et e et
(
+

A
A = + + +
t
q
total relaxation time of energy carriers (funct. of wavevector q)
D
Q
heat diffusion constant
D h diff i t t
B. S. Shastry,
D
C
charge diffusion constant
coupling factor between
charge and energy density
*
*
1
Z T
Z T
=
+
Rep, Prog, Phys 72,
016501, (2009)
Y. Ezzahri and A.
Shakouri;
34
g gy y
Z
*
high frequency limit of figure of merit
1 Z T + Shakouri;
Phys. Rev. B, 79,
184303, (2009)
Solar Cells
(Efficiency+ Cost $/W) (Efficiency+ Cost $/W)
35
Cronin Vining, Nature Materials 2009
TE module & cold side heat
exchanger g
Heat exchanger in hot gas flow
Thermal network circuit
1D model
(3D heat spreading)
h
T
s
2
1
RI
q
h

+
(3D heat spreading)
n
Substrates
Electrodes
Thermoelectric
Leg
thickness
T
h
sh
k
2
1
RI
h
SIT
w
TE
q
k
TE
module
n
p
n
p
p
p
n
p
n
Module
T
c
sc
q
c
2
2
1
RI
c
SIT
module
current
Cold side
Heat exchanger
Coolant
T
a
c
external thermal resistance
+
36
external thermal resistance
+
K. Yazawa and A. Shakouri, Energy Payback Optimization of Thermoelectric Power
Generator Systems, Proceedings of ASME IMECE2010, IMECE2010-37957
Maximum power output
I mpedance mat ch
( El ect r i cal and Ther mal )
T
s
T Z m + = 1
Max i mum pow er out put
q
h

+
Max i mum pow er out put
( )
( )
1
1 4
2
2
a s
T T
A
m
Z
w
+
+
=
T
h
sh
k
w
TE
q
k
TE
module
+ = A m d |
Opt i mum l eg l engt h
T
c
sc
q
c
+ = A m d |
Smaller yields thinner element
+

c
37
K. Yazawa and A. Shakouri, Energy Payback Optimization of Thermoelectric Power
T
a
Maximum power output
Th l l t i l ti i ti
p
u
t
Thermal-electrical co-optimization
p
o
w
e
r

o
u
t
p
T Z m + = 1
o
r
m
a
l
i
z
e
d

Full optimization
of parameters m
and C.
P k i f d t
1.4
1.8
2.2
0 2
w
N
o
Peak is found at
m=1.4 & C=1.4
for ZT=1
0.2
0.6
1
0.2
0.6
1
1.4
1.8
2.2
C [(K/W)/(K/W)]
Thermal
resistance
ti
m [Ohm/Ohm]
Load resistanceratio
38
2.6
ratio
Load resistance ratio
K. Yazawa and A. Shakouri, 2010, Energy Payback Optimization of Thermoelectric Power
Fractional area factor
Substrate
Spreading thermal resistance,
Heat concentration => Less TE material use
|
Substrate
Substrate
A
E
=a
2
A
TE
leg
( ) | |

tan 2 1+
= =
a
s
sc sh
where angle | is,
s
A
|
Heat transfer
( )
> =
s < + =
1 048 . 6 45 . 46
1 0.0011 4 . 40 ln 86 . 5
969 . 0
|
|
and substrate thickness impact is,
Vermeersch et al, J of HT, 2008
Spreading
region Substrate
TE
a d
s
/ =
2
At Maximum square array packing,
p ,
ds
A
TE
leg
2
tan 2
1 |
.
|
\
|
=
a
d
F
s
|
a
F: fractional area factor
(Fill factor)
2
+ + + + = +
39
A a
( ) | | tan 2 1+
+ + + + = +
a
s
c h
K. Yazawa and A. Shakouri, Env. Science and Technology (accepted 2011)
Use of heat spreading inside TE
module (thermal concentration)
S b t t
Leg
Substrate
Heat losses at uncovered No heat loss at
Spreading region
40
spreading regions Maximum packing
Heat sink optimization
Mi cr o- channel heat si nk s
b b > o
|
|
.
|
\
|
+ =
BASE BASE
A U G C
A U
1
2
1
/ 1
b
o
b
BASE
H
b > o
Matched pumping power
|
.
\
fin fin p
A U G C 2
( )
( )( )
2
5
6
2
3 L
H b
H
C
k N
w
p
f u
pp
o o
o
+
+
|
|
.
|
\
|
=
D
b
BASE
Fluid passages
b
BASE
~2b
Matched pumping power
( ) / *
78 3
o
L:length of channel
Fluid passages
BASE
Nusselt number
( ) 98 . 2 / 1 * 52 . 4
78 . 3
+ = H Nu o
Optimum design: matched resistance based on
41
convection from fin surface and sensitive heat of fluid.
K. Yazawa and A. Shakouri, Int. Mechanical Engineering Congress Nov. 2010
Components of TE system (cost per
unit area)
1 E+04
TE i l TE i l
ZT=4, 1 ZT=4, 1
1.E+04
TE material
F=1
TE material
F=0.1
Cross
1.E+03
e
a

[
$
/
m
2
]
Air HS
Ch HS
Cross
over
e
r

u
n
i
t

a
r
e
TEsubstrates
Air HS
ZT=1
ZT=4
1.E+02
C
o
s
t

p
e
TE material
F=0.01
TE substrates
Poly-Si PV
1.E+01
42
1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 1.E+08
Heat flux [W/m
2
]
TE system optimization for waste heat
recovery
1.E+07 Air HS (Al)
ZT=4
F=1
F 0 1
1.E+06
Fan power
Cross
TEgenerate
power
ZT=4
F=0.1
F=0.01
1.E+05
a

[
W
/
m
2
]
Cross
over
Solar Photo Voltaics
power
F=1
1.E+04
e
r

p
e
r

a
r
e
Ch HS (Cu)
Solar Photo Voltaics
q varies 10-20%
ZT=1
F=0.1
F=0.01
1.E+02
1.E+03
P
o
w
e
Pump power
1.E+01
1 E+02 1 E+03 1 E+04 1 E+05 1 E+06 1 E+07 1 E+08
43
1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 1.E+08
Heat flux [W/m
2
]
Material cost per power output
S t [TE H t i k]
10000
100000
ZT=1,
ZT=1,
ZT=1
FillFactor
F=1
System [TE + Heat sink]
ZT=1, |=1.5 W/mK,
100
1000
$
/
W
]
ZT=1,
ZT=4,
ZT=4,
ZT 4
Cross over
F=0.1
F 1
ZT=1
|
sub
=100 W/mK,
t
sub
=0.2mm,
10
100
e
r

o
u
t
p
u
t

[
$
ZT=4,
ZT=1
ZT=4 T
s
=900K, T
a
=370K,
Fan efficiency 30%,
0.1
1
s
t

p
e
r

p
o
w
e
F=0.01
TE $500/kg,
Substrate-AlN: $100/kg,
0.001
0.01
C
o
s
Al: $8/kg,
Cu: $20/kg
44
0.001
1.E+03 1.E+04 1.E+05 1.E+06 1.E+07
Heat flux [W/m2]
K. Yazawa and A. Shakouri, Int. Mechanical Engineering Congress Nov. 2010
Huge energy challenge potential of waste
Summary
Huge energy challenge, potential of waste
heat recovery
S b k/ d i i d ff h l Seebeck/conductivity trade off, hot electron
filtering (potential ZT>5 in metal/semicond. SLs)
ErAs:InGaAs thermoelectrics (ZT~1.6)
Coupled energy/charge transport p gy g p
Thermoelectric material cost vs. efficiency
(role of thermal contacts with reservoirs) (role of thermal contacts with reservoirs)
A. Shakouri and M. Zeberjadi, "Chapter 9: Nanoengineered Materials for
Thermoelectric Energy Conversion," in: Thermal Nanosystems and
Nanomaterials ed by S Volz Springer pp 225-299 (2009)
45
Nanomaterials, ed. by S. Volz, Springer, pp. 225 299 (2009)
A. Shakouri, Annual Review of Materials Research (July 2011)
K. Yazawa and A. Shakouri, Environmental Science and Technology (2011)
Acknowledgement
Senior Researchers: Zhixi Bian Kaz Yazawa James Christofferson Senior Researchers: Zhixi Bian, Kaz Yazawa, James Christofferson
Postdocs/Graduate Students: Kerry Maize, Hiro Onishi, Tela Favaloro,
Paul Abumov, Phil Jackson, Oxana Pantchenko, Amirkoushyar Ziabari,
Bj V h Gill P J H B hk D id H Bjorn Vermeersch, Gilles Pernot, Je-Hyeong Bahk, David Hauser
Collaborators: John Bowers, Art Gossard, Chris Palmstrom (UCSB), Tim
Sands (Purdue), Rajeev Ram (MIT), Venky Narayanamurti (Harvard), Arun ( ), j ( ), y y ( ),
Majumdar (Berkeley/ARPA-E), Josh Zide (Delaware), Lon Bell (BSST),
Yogi Joshi, Andrei Federov (Georgia Tech), Kevin Pipe (Michigan), Stefan
Dilhaire (Bordeaux), Natalio Mingo (CEA), Sriram Shastry, Nobby
Kobayashi, Joel Kubby, Ronnie Lipschutz, Melanie Dupuis, Steve
Gliessman, Ben Crow, Steve Kang (UCSC), Bryan Jenkins, Susan
Kauzlarich (Davis)
Alumni: Younes Ezzahri (Prof. Univ. Poitier), Daryoosh Vashaee (Prof.
Oklahoma State), Zhixi Bian (Adj. Prof. UCSC), Yan Zhang (Tessera),
Rajeev Singh (Sun Power), James Christofferson (Microsanj), Kazuhiko
46
Fukutani (Canon), Je-Hyoung Park (Samsung) , Javad Shabani (postdoc,
Harvard), Mona Zebarjadi (postdoc, MIT), Xi Wang (InterSil), Helene
Michel (CEA), Ramin Sadeghian (start up), Tammy Humphrey, Shila Alavi

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