nano-structures thermoelectric materals - part 1

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Nano-structured Thermoelectric Materials Nano-structured Thermoelectric Materials 8 th Diesel Engine Emissions Reduction Conference Loews Coronado Bay Resort San Diego, CA August 25, 2002 Rama Venkatasubramanian

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Page 1: Nano-structures Thermoelectric Materals - Part 1

Nano-structured Thermoelectric MaterialsNano-structured Thermoelectric Materials8th Diesel Engine Emissions Reduction Conference

Loews Coronado Bay Resort

San Diego, CA

August 25, 2002

Rama Venkatasubramanian

Page 2: Nano-structures Thermoelectric Materals - Part 1

OutlineOutline

• Introduction – Relevance to CFC-free Air-conditioning in Automobiles, Energy Conservation and Emissions Reduction

• Advantages of Technology and Thin-film Cooling Examples

• Thin-film Power Conversion Examples

• Major Outstanding Issues for Research

• Emerging Thin-film TE Technology Applications

Page 3: Nano-structures Thermoelectric Materals - Part 1

Why Thermoelectrics?• Converts electrical and thermal energy using a solid state

device with minimal moving parts• Chip-scale functionality with thin-film materials using

standard microelectronic processing• Computer Chip, Photonic Chip, Lab-on-a-Chip

• Green Technology – CFC-free refrigeration to waste-heat recovery for fuel efficiency

Page 4: Nano-structures Thermoelectric Materals - Part 1

Thermoelectric Effect

Ref : Nature, 413, 577 (2001)

• Cooling or Power Conversion Efficiency critically dependent on the material Figure of Merit (ZT)• ZT = (α2σ/K)T• Minimize thermal conductivity and maximize electrical conductivity

Page 5: Nano-structures Thermoelectric Materals - Part 1

ZT and COP of Refrigerator or Air-Conditioner

Figure-of-Merit (ZT)

Coefficient of Performance

of Refrigerator

THOT = 300 K∆T ~ 30 K

0

1

2

3

4

0.0 1.0 2.0 3.0 4.0 5.0

Bulk Bi2Te3-alloy Thermoelectric Devices

Bi2Te3/Sb2Te3 Superlattice Thermoelectric Devices

Typical large-scale mechanical system

Typical small-scale mechanical system

Higher ZT – Incentives for New Approaches to Implementing Higher COP Concepts

Page 6: Nano-structures Thermoelectric Materals - Part 1

• High-density, light-weight

• Higher efficiency

• Replace Batteries

Implications for Power

0

4

8

12

16

20

0 1 2 3 4

Figure of Merit (ZT)

The

rmal

-to-

Ele

ctri

cal

Eff

icie

ncy

(%)

∆Τ = 50 ∆Τ = 100 ∆Τ = 150 ∆Τ = 250

0

0.5

1

1.5

2

2.5

0 1 2 3 4

Figure of Merit (ZT)

The

rmal

-to-

Ele

ctri

cal

Eff

cien

cy (%

)

∆Τ = 5 ∆Τ = 10 ∆Τ = 15 ∆Τ = 20

Page 7: Nano-structures Thermoelectric Materals - Part 1
Page 8: Nano-structures Thermoelectric Materals - Part 1

THERMOELECTRIC TECHNOLOGIES in 1992 Fort Belvoir Workshop Organized by Dr. Stuart Horn

0.0

1 .0

2 .0

3 .0

4 .0

5 .0

1930 1940 1950 1960 1970 1980 1990 2000

ZT

With Advanced Semiconductor

Materials Technology?1960’s

Semiconductor MaterialsTechnology

• ZT - figure of merit - has been stagnant at about 0.8 to 1 for the last 40 years - cooling and power conversion efficiencies low -useful only in applications where you really need it

• ZT need to improve over 1.5 at 300K for a major impact in electronics and around 2 to 2.5 for a revolutionary impact in air-conditioning, and power from waste-heat

T=300K

Page 9: Nano-structures Thermoelectric Materals - Part 1

Cs Bi4Te6 (Michigan State University)Bulk Materials with a ZT~ 0.8 at 225K but less than 0.8 at

300K (Science 287, 1024-1027, 2000)Filled Skuterrudites (JPL)

Bulk materials with a ZT ~1.35 at 900K (Proc. Of 15th

International Conf. On Thermoelectrics, 1996)PbTe/PbTeSe Quantum-dots (MIT Lincoln Labs.)

ZT~2 at 550K and ZT~0.8 at 300K based on estimated thermal conductivity values (J. Electronic Materials, 29, L1 , 2000)

Bi2Te3/Sb2Te3 Superlattices (RTI)ZT~2.4 at 300K in devices with all properties measured at the

same place, same time, with current flowing and verified by two independent techniques (Nature, 597-602, 2001)

Some of the Bulk Material and Thin-film Developments

Page 10: Nano-structures Thermoelectric Materals - Part 1

MultipleApplications

MultipleApplications

Thermoelectrics Research

Thermoelectrics Research Breakthrough

NanotechnologyBreakthrough

Nanotechnology

Page 11: Nano-structures Thermoelectric Materals - Part 1

RTI’s 40-Year Breakthrough

0.0

1.0

2.0

3.0

4.0

1930 1940 1950 1960 1970 1980 1990 2000

Efficiency of Thermoelectric

Material (ZT)

Potential withThin-Film

Technologies

Industry Progress –Semiconductor Materials Technology

2010

RTI’s Thin-Film SuperlatticeTechnology

Page 12: Nano-structures Thermoelectric Materals - Part 1
Page 13: Nano-structures Thermoelectric Materals - Part 1

10Å/50Å Bi2Te3/Sb2Te3Structure

Optimized for disrupting heat transport while enhancing electron transport perpendicular to the superlattice interfaces

RTI’s Nano-structured Superlattice Material

Applied Physics Letters, 75, 1104 (1999)

Page 14: Nano-structures Thermoelectric Materals - Part 1

MOCVD Growth of Superlattices

Low-temperature technology and scaleable for large areas

In-situ ellipsometry for nanometer-scale control of deposition

Page 15: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice Material

COLD

HOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 16: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice Material

COLD

HOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 17: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice Material

COLD

HOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 18: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice MaterialHOT

COLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 19: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice MaterialHOT

COLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 20: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice MaterialHOT

COLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 21: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice MaterialHOT

COLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 22: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice MaterialHOT

COLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 23: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice MaterialHOT

COLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 24: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice Material

COLD

HOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 25: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice Material

COLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

HOT

Page 26: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice MaterialHOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 27: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice Material

COLD

HOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 28: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice MaterialHOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 29: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice MaterialHOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 30: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice MaterialHOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 31: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice MaterialHOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 32: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice MaterialHOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 33: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice MaterialHOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 34: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice MaterialHOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 35: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice MaterialHOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

Page 36: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice Material

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

HOT

Page 37: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice Material

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

HOT

Page 38: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice Material

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

HOT

Page 39: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

RTI’s Superlattice Material

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

HOT

Page 40: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

RTI’s Superlattice MaterialHOT

Page 41: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

RTI’s Superlattice MaterialHOT

Page 42: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

RTI’s Superlattice MaterialHOT

Page 43: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometerCOLD

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

RTI’s Superlattice MaterialHOT

Page 44: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice Material

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

COLD

HOT

Page 45: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

COLD

RTI’s Superlattice MaterialHOT

Page 46: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

COLD

RTI’s Superlattice MaterialHOT

Page 47: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

COLD

RTI’s Superlattice MaterialHOT

Page 48: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

COLD

RTI’s Superlattice MaterialHOT

Page 49: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

COLD

RTI’s Superlattice MaterialHOT

Page 50: Nano-structures Thermoelectric Materals - Part 1

Bi2Te3

Sb2Te3

12 nanometer

RTI’s Superlattice MaterialHOT

The RTI breakthrough arises from reducing heat transmission without disrupting electron flow

COLD