HOT SIDE

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COLD SIDE

University of California, Santa Barbara
IEE/CEEM Seminar
November 20, 2013

Personal Perspectives
on Advancing Energy Sustainability
Mildred Dresselhaus
Massachusetts Institute of Technology
Cambridge, MA

Collaborators
Gang Chen, MIT
Mona Zebarjadi, Rutgers
Zhifeng Ren, Boston College
Jos Heremans, Ohio State Univ.

Outline

2

• World energy outlook and sustainability
• Nanostructures and energy
– Why nanostructures?
– Challenges of materials
• Thermoelectrics
– Introduction
– Recent advances
– Strategies to increase ZT
• Conclusions

Population (Billions)

Demographic Expansion

Oceania
N. America
Africa
Europe

N. America

Oceania
Africa

Europe
S. America

S. America

2005
6.5 billion

2050
8.9 billion

3
Asia
Asia

Growing world energy needs
Energy demand and GDP per capita (1980-2002)
Primary energy per capita
(GJ)
4

2000: 13 TW
2050: 30 TW
2100: 46 TW

(Hoffert et al., Nature 395:883,1998)

GDP per capita (purchasing power parity)

40% of the world’s
population is in
the fast developing
regions.

The World Energy Demand Challenge
2100: 40-50 TW
2050: 25-30 TW
2000: 13 TW

25.00
World Energy Demand

total

20.00

energy gap
~ 14 TW by 2050
~ 33 TW by 2100

TW

15.00
industrial

10.00

developing

5.00

US
ee/fsu

50

0.00
1970

1990

2010

2030

40

EIA Intl Energy Outlook 2004
http://www.eia.doe.gov/oiaf/ieo/index.html

World Fuel Mix 2001

30
%

Hoffert et al. Nature 395:883,1998

oil

gas

coal

20

5

nucl renew

10
0

85% fossil

The Environmental Challenge

(ppmv) (ppmv)

325
300
275

800
700

CO2 in 2004: 380 ppmv

-- CO2

Relaxation time
+4

-- CH4
-- ΔT

0

600

250

-4

500
225
400

175

300

-8

100
400
200
300
0
Thousands of years before present (Ky BP)
Climate Change 2001: The Scientific Basis, Fig 2.22

6

J. R. Petit et al., Nature 399:429, 1999
Intergovernmental Panel on Climate Change, 2001
http://www.ipcc.ch
N. Oreskes, Science 306:1686, 2004
D. A. Stainforth et al., Nature 433:403, 2005

transport of CO2 or heat to deep
ocean: 400–1000 years

-1.5

380

-- CO2
-- Global Mean Temp

360
340

-1.0
-0.5

320

-0.5

300
280

-0.5

260

-1.0

240

1000

1200

1600
1400
Year CE

Concern about tipping points for ΔT and CO2 levels.
Attempts to reduce CO levels are a multi-year project.

1800

-1.5

2000

Temperature (°C)

200

Atmospheric CO2 (ppmv)

CH4

ΔT relative to present
(°C)

CO2

The Energy Source Challenge

45

45
40

40

35

35

14 Terawatts (world)

30

30 Terawatts (world)

30
25

25

20

20

15

15

10

ar
,w

in

he
rm
al

d,

ge

ot

oe

le

ct

ric

m
as
s
Bi
o

n
/F

iss

io

G
as
io
n

H
yd
r
So
l

Source: International Energy Agency

0

Fu
s

H
yd
So
ro
la
el
r,
ec
w
t ri
in
c
d,
ge
ot
he
rm
al

m
as
s
Bi
o

n
Fi
ss
io

G
as

Co
al

O
il

0

5

l

0.5%

Co
a

5

O
il

10

7

2050

50

TODAY

50

• Achieve sustainable energy through renewable energy
• Find substitute for gasoline (portable high density energy)
• Develop cost-efficient energy technologies

The Energy Alternatives
Fossil

Nuclear

Renewable

Fusion

solar, wind, hydroelectric,
ocean tides and currents
biomass, geothermal

energy gap
~ 14 TW by 2050
~ 33 TW by 2100

10 TW = 10,000 1 GW power plants
1 new power plant/day for 27 years

no single solution
diversity of energy sources required
8

Increased energy efficiency and energy conservation are important.
Shale oil sources adopted recently are becoming popular.

2
Terrestrial Solar Spectrum (W/m m)

Solar Spectrum

9

1800
1600

AM1.5 Solar Spectrum

1400

Energy Usable for Silicon PV Cells

1200
1000
800

Bandgap of Silicon
(1.1 m)

600
400
200
0
0

0.5

1
1.5
2
Wavelength (m)

2.5

3

Thermal energy offers special opportunities

Outline

1
0

World energy outlook and sustainability
• Nanostructures and energy
– Why nanostructures?
– Challenges of materials
• Thermoelectrics
– Introduction
– Recent advances
– Strategies to increase ZT
• Conclusions

Why nanostructured materials are important
for energy-based applications
• New desirable properties are available at the nanoscale
but not found in conventional 3D materials, e.g.,
materials parameters depend on size in quantum limit.
• Independent control of nanomaterials parameters which
depend on each other for 3D materials.
• Higher surface area to promote catalytic interactions.

1
1

Special role of catalysts
• Development of efficient inexpensive catalysts will be key for new
materials for energy research.
• Modeling and simulation will play a significant role.

1
2

• Inspired by quantum chemical calculations, Ni surface-alloyed
with Au (black) is used to reduce carbon poisoning of catalyst, as
verified experimentally.
• Catalysis is important because of the exponential dependence
exp(Ebarrier/kT) of catalytic activity

Challenges of Materials

1
3

• How do complex phenomena emerge from
simple ingredients?
• What is the physics of life?
• What happens far from equilibrium and why?
• How will the energy demands of future
generations be met?
• How will the information technology revolution
be extended?
• What new discoveries await us in the
nanoworld?

Several challenges relate to nanoscience

www.nasonline.org

What happens far from
equilibrium and why?
Concept:
What are the common elements of
systems such as turbulence,
earthquakes, fracture, and life itself, all
of which only occur far from
equilibrium.
Characteristics:
•Subjecting materials to conditions far
from equilibrium leads to otherwise
unattainable properties.
•Many examples in daily life
•Many industrial applications now and
in the future
1
4

Studies include:
Materials under extreme conditions,
large fluctuations, and noise

Swarming schools of fish
(top) and galaxies (bottom)
are examples of systems
formed and evolving far from
equilibrium.

What happens far from
equilibrium and why?
To understand, predict and control systems
far from equilibrium and guide to scientific
Goals advances related to new materials
development, the economy, climate, and
the environment

1
5

Control of far-from-equilibrium
behavior can prevent materials
fatigue and eventual fracture.

Far-from-equilibrium processing
produces some of the highest strength
materials (glassy metal alloys).

How will the information technology
revolution be extended?
Goals

1
6

New opportunities are again emerging
for experimentalists and theoreticians to
develop new materials and device
concepts in support of the information
technology revolution

A single-molecule transistor
represents the ultimate limit in
small size of an active electronic
component

What new discoveries await us
in the nanoworld?
Concept:
“Nano” straddles the border between
the molecular and macroscopic: small
enough to exhibit characteristics
reminiscent of molecules, but large
enough to be designed and controlled
experimentally to meet our societal
needs.
Characteristics:
• Length scales of nanometers
• Exploiting properties of nano-materials
that differ from their macroscopic
counterparts

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7

Examples:
• New phenomena (catalysis, excitons)
• New materials (graphene)
• Strong interplay between theory and
experiment (carbon nanotubes)

{110}SL

rm

{110}SL

Well-ordered binary crystal
formed from two nanocrystal
subunits

Courtesy C.B. Murray, U. of Pennsylvania

How will the energy demands
of future generations be met?
The ever-increasing demand for energy coupled
with related concerns about climate change make
the supply and security of energy supply one of the
greatest challenges of this century.

US National Academy of Sciences Decadal Study (2010)

1
8

.

How will the energy demands
of future generations be met?
Priority research areas for
CMMP include:










1
9

Photovoltaic cells and solar technologies
Fuel cells and hydrogen storage
Biocatalysis for water splitting
Enhanced thermoelectric materials
Rechargeable batteries and supercapacitors
Solid-state lighting
New materials for nuclear energy
Catalytic processes for biofuel technologies
Functional nanoparticles for smart materials
New superconductors for power transmission
(Top) Example of a plastic sheet use for
Novel materials for low power computing

Nano composite
thermoelectric material
BixSb2-xTe3 with superior
conversion of thermal energy
to electricity

luminescent solar concentration
(Left) Atomic layer of QD solid state lighting
(Right) Solar water splitting for H2
generation

Energy is recognized as a
Challenge of the 21st century

Outline

2
0

World energy outlook and sustainability
• Nanostructures and energy
– Why nanostructures?
– Challenges of materials
• Thermoelectrics
– Introduction
– Recent advances
– Strategies to Increase ZT
• Conclusions

Thermoelectric Effect and Applications
• Seebeck effect
TH

Conductivity
Seebeck
coefficient

TC

+ V –

V
S 
T

• Thermoelectric cooling

2
1

Temperature

S 2 T
ZT 

Heat

Thermal
Conductivity

COLD

– No moving parts
p
n
– Can be integrated with electronic I
I
HOT
circuits (e.g., CPU)
– Environment friendly
Thermoelectric Refrigerator
– Localized cooling with rapid response

Waste heat recovery—for a sustainable technology

The Thermoelectric Figure of Merit (ZT)
S=S2
S2
S

Conductivity
Seebeck
coefficient

2
2

S 2 T
ZT 

Temperature

Thermal
Conductivity

For almost all materials, if doping is increased,
the electrical conductivity increases but the
Seebeck coefficient is reduced.

Advances in Thermoelectrics
PbSeTe/PbTe
Quantum-dot
Superlattices
(Lincoln Lab)

F IG U R E O F M E R IT (Z T ) m a x

3.0

2
3

AgPbmSbTe2+m
(Kanatzidis)

1.5

Nano

Bulk

S2 (W/cmK2)
k (W/mK)

40
0.6

50.9
1.45

ZT (T=300K)
2.4
1.0
Venkatasubramanian et al.,
Nature, 2002.

2.5
2.0

Bi2Te3/Sb2Te3

Bi2Te3/Sb2Te3
Superlattices
(RTI)

1.0

PbTe/PbSeTe Nano

Bi2Te3 alloy
PbTe alloy

0.5
0.0
1940

S2 (W/cmK2)
k (W/mK)

Skutterudites
(Fleurial)

1980
YEAR

28
2.5

ZT (T=300K)
1.6
0.3
Harman et al., Science, 2003

Si0.8Ge0.2 alloy
1960

32
0.6

Bulk

2000

2020

Motivation for Nanotech Thermoelectricity
(2D quantum wells, 1D nanowires, 0D quantum dots)
Conductivity

Seebeck
Coefficient

Difficulties in increasing ZT in bulk materials:
Temperature

S    

2

S T
ZT 

ZT ~ 3 for desired goal

   S  and 
Thermal
Conductivity

 A limit to Z is rapidly obtained in
conventional materials
 So far, best bulk material (Bi0.5Sb1.5Te3)
has ZT ~ 1 at 300 K

Low dimensional physics gives additional control:
2
4

 Enhanced density of states due to quantum confinement effects
 Increase S without reducing 
 Boundary scattering at interfaces can reduce  more than 
 Possibility of materials engineering to further improve ZT

Why Low Dimensional or
Nanotech Thermoelectricity

3D

E

D. O. S.

D. O. S.

D. O. S.

D. O. S.

• Electronic properties may be dramatically modified due to the electron
confinement in nanostructures which exhibit low-dimensional behaviors

2D

E

1D

E

0D

E

• Thermal conductivity can be significantly reduced by preferential
S 2 T
ZT 
scattering of phonons relative to electrons at the interfaces

insulator

conductor

2
5

electron
e
dW < dB

phonon
ph
dW > lmfp

Effect of Nano on ZT for many materials

2
6

Nanocomposites Approach
(a)

Nanoparticle

(b)

– Increase interfacial scattering by mixing nano-sized particles.
– Enable batch fabrication for large scale application.

2
7

S 2 T
ZT 

Strategy to lower the thermal conductivity (

– Implementation of nanocomposite approach to many systems
– M.S. Dresselhaus et al., Adv. Mater. 19:1043 (2007)

Sample Preparation
Techniques
MIT/BC sample preparation: ball milling and hot pressing
Small grains lead to both high S and low  to enhance ZT

MIT/BC approach Ball-milling + Hot-pressing

Goals: Smaller grains aiming at more boundary phonon scattering
2
8

Simple, quick, cost effective
Scalable (large quantity) production for practical use

Superior Thermoelectric Properties
are Achieved by Nano

2
9

Nano allows  to increase while reducing 
Poudel et al., Science 320: 634 (2008)

Thermal conductivity
reduction is key to increasing ZT

3
0

Poudel et al., Science 320:634 (2008)

Nano reduces
thermal conductivity

Cooling Test of Thermoelectric Device
• Laboratory tests of the
thermoelectric device follows
theoretical predictions
• The next challenge is
commercialization of the
device/concept

3
1

• Cooling test results
(comparison of
experiment and
theory) are for the hot
side fixed at 100°C
• Inset is a comparison
to a state of the art
bulk ingot
Poudel et al., Science 320:634 (2008)

Strategies to Increase ZT
• Decrease thermal conductivity through
interface scattering (used starting 1992)
• Increase Seebeck coefficient
through increasing electronic density
of states near the Fermi level (Heremans, 2008)
• Increase electronic conductivity through
modulation doping (Zebarjadi, 2011)
3
2

SiGe-Based Materials
Ball milling used to make SiGe nanocomposites
P-Type SiGe

N-type SiGe

Joshi et al., Nano Letters (2008)

X.W. Wang, APL (2008)

3
3

Implementation of Hicks, Dresselhaus, PRB (1993)

3
4

High-abundance, low-cost
thermoelectric materials

3
5

Emphasis is now also given to naturally abundant
lower-cost materials: PbS
L-D Zhao, S-H Lo, J He, H Li, K Biswas, J Androulakis, C-I Wu, T P Hogan, D-Y Chung, V P Dravid, M G
Kanatzidis. High performance thermoelectrics from Earth-abundant materials: Enhanced figure of merit in PbS by
second phase nanostructures. J. Am. Chem. Soc. 133:20476-20487 (2011)

High thermoelectric figure of merit
using heavy hole dominated PbTe

3
6

Materials engineering is used to involve a valence band
usually below the Fermi level—sodium is added as dopant
Y Pei, X Shi, A LaLonde, H Wang, L Chen, G J Snyder. Convergence of electronic bands for high performance bulk
thermoelectrics. Nature 473:66 (2011)

Bandgap engineering
used to enhance ZT

p-type PbTe:Na

3
7

Sodium-doped PbTe is used to populate
heavy-hole pockets
Y Pei, A LaLonde, S Iwanaga, G J Snyder. High thermoelectric figure of merit in heavy hole dominated PbTe. Energy
and Environmental Science 4:2085 (2011)

Strategies to Increase ZT
• Decrease thermal conductivity through
interface scattering (used starting 1992)
• Increase Seebeck coefficient
through increasing electronic density
of states near the Fermi level (Heremans, 2008)
• Increase electronic conductivity through
modulation doping (Zebarjadi, 2011)
3
8

Increasing the Seebeck coefficient
2
To maximize the ZT value, we can either
S
the thermal conductivity κ through
ZT 
T reduce
nanostructuring or increasing the thermopower

S by band gap engineering.
Mott Relation:

 d  ln    E   
 2 kB

S
k BT  

3 e
dE



E  EF

 1 dn( E ) 1 d  ( E)
 2 kB

kB T


3 e
n
dE

dE

E  EF

J. Heremans et al., Science 321: 554 (2008) (Band structure engineering)

Additional dopant level
Local increase in the DOS
n (E) = g (E) * f (E)
Enhanced thermopower S
3
9

Strategies to Increase ZT
• Decrease thermal conductivity through
interface scattering (used starting 1992)
• Increase Seebeck coefficient
through increasing electronic density
of states near the Fermi level (Heremans, 2008)
• Increase electronic conductivity through
modulation doping (Zebarjadi, 2011)
4
0

Improving Carrier Mobility
by Modulation Doping
Separate carriers from their parent atoms

In 2D thin-films
N-type configuration-3D

In 3D bulk
nanocomposites

Dopant is located inside
nanoparticles but donates
carriers to host semiconductor
to enhance carrier mobility
4
1
Dingle, Stormer, Gossard, Wiegmann, Appl. Phys. Lett. (1978)
Schaffler, Semicond. Sci. Tech. 12 (1997)

Zebarjadi, Giri, et al, Nanoletters (2011)

Practical implementation

Modulation-doped

Intrinsic host grains

Si95Ge5
+Si70Ge30P3

Si95Ge5
Heavily doped grains
Si70Ge30P3

4
2

65%
35%

Equivalent -uniformly doped
Si86.25Ge13.75P1.05

Ball milled
sample with
same average
component
Zebarjadi, Giri, et
al., Nanoletters
(2011)

Electrical and thermal conductivity
We were able to
increase the
electrical
conductivity while
maintaining the
same thermal
conductivity

4
3

Yu, Zebarjadi, Wang, Lukas, Wang, Opeil, Dresselhaus, Chen, Ren, Nanoletter (2012)

ZT enhancement
ZT of the two phase composite
is higher than:
1. The average
2. Each of the components
3. Optimally doped individual
components
ZT of the two-phase composite is
the same as the best ever
achieved SiGe composite (i.e.,
Si80Ge20 optimally doped with GaP
and P) but with much less Ge
4
4

Conclusions
• Nano provides size as a parameter to control
materials properties
• New properties can be achieved in nanosystems
that are not observed in bulk materials
• New strategies for implementation of nano effects
have had significant success
• Emphasis now is being given to new concepts to
enhance ZT
4
5

Acknowledgment
• DOE/S3TEC Grant DE-SC000 1299
(MIT Energy Frontiers Research Center)

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6

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