Overview of the Thermoelectric

Properties of Yb-filled
CoSb3 Skutterudites
Gary A. Lamberton, Jr.1
Terry M. Tritt2
R. W. Ertenberg3
M. Beekman3
George S. Nolas3
1
National Center for Physical Acoustics, University of Mississippi
2
Department of Physics and Astronomy, Clemson University
3
Department of Physics, University of South Florida
 Outline

• Introduction to Thermoelectric Materials

• Previous Skutterudite Research and
Promising Results
• Description of Measurements
• Research and Results
• Conclusions
 Thermoelectric Applications
• Power Generation
• Radioisotope Thermal Generators (RTGs)
• Cassini, Voyager missions
• Lifespan of more than 14 years
• Waste Heat Recovery
• Large scale – Power Plants
•Small scale - Automobiles
 Thermoelectric Applications
•Active Cooling/Warming
• Localized cooling
• CPUs
• Biological specimens
• Commercial Coolers/Warmers
• Luxury Vehicles – Cool/Warm Seats
Thermoelectric (TE) Effects
Seebeck Effect Material A

Differential
Thermocouple
T T + T

Vab
á= Material B Material B
ÄT
V
 TE Effects
Peltier Effect Electric Current

Difference in Material Heat

A
εF between Absorbed
or
Materials A and B Expelled
Material
B
 TE Couple and Module

Operating Modes of a
Thermoelectric Couple
Modules
T. M. Tritt, Science 31, 1276 (1996) www.marlow.com
 Thermoelectric Materials
2
Figure of Merit: α T
ZT =
() eg+
ρκκ
Seebeck Coefficient
Electrical Resistivity
 Thermal Conductivity
e – Electronic ≈ L0T/ρ (W-F relation)
g – Lattice
Current Materials

AgPbmSbTe2m

Terry M. Tritt & Mas Subramanian

MRS Bulletin TE Theme, March 2006
 ZT Requirements
For a ZT = 1, e.g. Optimized Bi2Te3 (300 K)
– Resistivity ~ 1.25 mΩ-cm
– Thermopower ~ 220 μV/K
– Thermal Conductivity ~ 1.25 Wm-1K-1
For a ZT > 2,
Assuming a hypothetical g = 0,
a Thermopower ≥ 220 μV/K is required
→ Semiconductors and Semi-metals
Skutterudite Structure

2M8Pn24
or M4Pn12
Metal Atom (Co, Rh, Ir)

Pnicogen Atom (P, As, Sb)

Void Space/Filler Ion

 History
• Discovered in Skutterud, Norway
• Studied in the 1950s-60s for potential
thermoelectric applications (binary)
• Sparse research until the early 1990s
– Slack’s Phonon Glass – Electron Crystal
Concept
2
α T
ZT =
(eg+
ρκκ )
 IrSb3 and Ir0.5Rh0.5Sb3

• Mass fluctuation
scattering reduces
the lattice thermal
conductivity to 58%
of the original value
• ‘Rattling’ ion
concept suggested
as a means to
reduce g

Slack et al., J. Appl. Phys 76, 1665 (1994)

 “Rattlers” Reduce g
• Order of Magnitude
Reduction

Lattice Thermal Conductivity

• Ge substitution could
only reduce to 30%
• CeFe4Sb12 has g 10%
of that of FeSb3
• “Rattling” of Void (mW/cmK)
Filling Ion is the source Temperature (K)
of the reduced g
G.S. Nolas, et al., J. Appl. Phys. 79, 4002 (1996)
 Previous Work
CeFe4-xCoxSb12: ZT ~ 1.4 (900 K) JPL

Fleurial, et al., Proc. 16th International Conference on Thermoelectrics,

IEEE Catalog Number 97TH8291, Piscataway, NJ, p. 1 (1997)
 Ce “Rattlers” in CoPn3

• Fe4Sb12 has
largest cage size
• More efficient
scattering with
heavier atoms in
the lattice

Watcharapasorn et al., J. Appl. Phys 91, 1344 (2002)

 Partial Void Filling

Lattice Thermal Conductivity (mW/cmK)

• Partial Filling La-filled
CoSb3
Yields Largest
Reduction
• Increased
Disorder
• Less Impact on
Band Structure Temperature (K)
G.S. Nolas, J. L. Cohn, and G. A. Slack, Phys. Rev. B 58, 164 (1998)
 Eu0.42Co4Sb11.37Ge0.50

• Reduced Thermal
Conductivity
• Increased Carrier
Mobility
• Maintained
favorable electronic
properties
Lamberton et al., Appl. Phys. Lett. 80, 598 (2002)
 Sample Synthesis
Dr. George S. Nolas (USF/Marlow)
• Stoichiometric amounts of high purity
elements mixed and reacted at 800 ˚C
under Ar atmosphere for 2 days, ground,
and reacted at 800 ˚C for 2 additional days
• Resulting polycrystalline powders were
densified using a HIP at 600 ˚C for 2 hours
• Compositional analysis by Electron
Microprobe
Measurement of Electrical Resistivity
and Seebeck Coefficient (10 – 300 K)
• Helium flow cryostat
and closed-cycle
refrigerator
• High Density of Data
2 samples simultaneously
– 24 hours per experiment
•Typical sample size:
2-4 mm x 2-4 mm
x 6-10 mm
•Mounted on chip that
Pope et al, Rev. Sci. Instrum. 72, 3129 (2001) plugs into system
 Resistivity and Thermopower
Heater Heater Power,
IHeater
P = I2R, creates ΔT
I+ Cu block for Thermopower
VTEP + Measurement
VR+ 4-probe Resistivity
Measurement:
Sample
T Current Reversed to
Subtract Thermoelectric
VR-
VTEP - Contribution

TEPTEP( )
I- IRVIRV
+−−−
VR =
2
Cu block
High Temperature Resistivity and
Seebeck Measurement
Cu Block

PRT • Operating Range of

100 – 700 K
• Standard 4-probe
Resistivity
Sample
Measurement
• Voltage vs. ΔT
Ceramic Posts Sweeps at Each
Temperature
Cartridge Heater
 Thermal Conductivity
Closed Cycle
Helium Cryostat
Strain 12 – 300 K
Gauge
Solid State Heat
Differential Flow Method
Sample Thermocouple
Cu block (1(1mil)
mil) P = KΔT
L
ê= K
A
A. L. Pope et al., Cryogenics 41, 725 (2001)
 W
(

y Thermal Conductivity
t
i
v
Analysis
i
t Thermal Conductivity Extrapolation
1c) 3.5
-
1uK
- 3.0 • TC Measured
d
n from 10 – 300 K
o 2.5
C •  measured from
2.0 10 – 300 K and
l from 100 – 700 K
1.5
a Measured Κ
Total
Curve Fit
Κ
g
m 1.0 Wiedemann- FranzΚ Wiedemann-Franz Κ • e calculated
e e
r LatticeΚ= -Κ Curve Fit Κ + WFΚ
e Total g g e using Wiedemann-
0.5
h Franz relation from
T 0.0 10 – 700 K
0 100 200 300 400 500 600 700 800
Temperature (K)
YbxCo4GeySb12-y
 Dilley et al.
• Intermediate valence detected in
YbFe4Sb12 between 2+ and 3+
• Heavy Fermion behavior at low
temperature
• Low carrier density leads to relatively high
resistivity, ~ 3 m-cm at 300 K
• ZT < 0.02 at 300 K Dilley et al., Phys. Rev. B 58, 6287 (1998)

Dilley et al., Phys. Rev. B 61, 4608 (2000)

 Motivation for YbxCo4Sb12
• RE-filled Skutterudites have shown relatively large
Figures of Merit
– Reduced Lattice Thermal Conductivity
• Yb – Large Mass, Small Atomic Radius
– Electronic Properties Sensitive to Doping Level
• Reported Mixed Valence in YbFe4Sb12
– Heavy Fermion Behavior
• Increased Seebeck Coefficient

Reduce g + Increase  High ZT

 High Figure of Merit

• Suggests rigid-
band behavior
(maintain electronic
properties) with
varying Yb
concentration
(x = 0.066, 0.19)
• HF behavior leads
to high power factor
Nolas et al., Appl. Phys. Lett. 77, 1855 (2000)
 Concurrent Research
• Anno et al – ZT ~ 1 (700 K) in Yb0.25Co4Sb12 and
Yb0.25Co3.88Pt0.12Sb12
• UCSD and GM: YbyCo4Sb12-xSnx
– x > 0.8 reduces Seebeck Coefficient
• p-type if x > 0.83
– Lattice Thermal Conductivity reduced
• Dependent upon Yb concentration
• Unaffected by Sn compensation
m
(
YbyCo4Sb12-xGex
y)
tm
i Yb Co Sb
c 0.066 4 12
• Different
v- 20
Yb Co Sb
0.19 4 12

iΩ Yb Co Ge
0.49 4 1.00
Sb
10.92
Temperature
t Yb Co Ge
0.65 4 0.96
Sb
11.21 Dependence
Yb Co Ge Sb
s 0.46 4 0.79 11.21
• Magnitude
Yb Co Ge Sb
i 10 0.46 4 0.86 11.13
Scales with Ge
s
e Concentration
R • Decreased
0 Mobility
0 200 400 600 800
Temperature (K)
 t
n
e
i
c
YbyCo4Sb12-xGex
i)
fK
0 nnpp +
σασα
f/
0 α Total =
eV σσnp+ Yb
Yb
0.066
Co Sb
Co
4 Sb
12
o
μ 0.066 4 12
Yb Yb CoCoSbSb
-100 C-100 0.190.19 4 4 1212

Yb Yb0.20
CoCoSbSb (Sales)
(Sales)
0.20 4 124 12
k Yb CoCoGe Ge Sb Sb
Yb0.49
c -200 0.49
4
4 1.00
1.00
10.92
10.92
-200 Yb Co Ge Sb
e Yb
0.65
Co Ge
0.65 4
4
0.96
0.96
Sb 11.21
11.21
b Yb
Yb
0.46 4
Co Ge
Co Ge
0.79
Sb
Sb 11.21
e -300 0.46
Yb 4
Co 0.79
Ge Sb11.21
-300 e Yb
0.46
Co Ge
4 0.86
Sb
11.13

0.46 4 0.86 11.13

S 0 200 400 600 800
0 200 400 600(K)
Temperature 800
n
o
C
YbyCo4Sb12-xGex
l
a
m
r
• Reduction over
e y = 0.066
h 5 Parent CoSb3
SK181
T 1) ~ 8 Wm-1K-1
Sk193
SK281
-
@ 300K
Sk282
1K SK283

e -m
SK284

c W3 • Varies More
i ( Than Sn
t
t y > 0.19 Compensated
a 1 Samples
0 100 200 300
L (Yang et al)
Temperature (K)
YbXCo4GeYSb12-Y
Figure of Merit – Yb-filled CoSb3

Yb Co Sb
0.066 4 12

Yb Co Sb
0.19 4 12

Yb Co Sb (Sales)
0.2 4 12

Yb Co Pt Sb (Anno)
0.25 3.88 0.12 12

Yb Co Sb (Anno)
0.25 4 12

Yb Co Ge Sb
0.49 4 1.00 10.92

Yb Co Ge Sb
0.65 4 0.96 11.21

Yb Co Ge Sb
0.46 4 0.79 11.21

Yb Co Ge Sb
0.46 4 0.86 11.13

Sales, B., March APS (2002)

H. Anno et al., Mat. Res. Soc. Symp. Proc. Vol. 691, 49 (2002)
G. S. Nolas, M. Kaeser, R. T. Littleton IV, and T. M. Tritt, Appl. Phys. Lett. 77, 1855 (2000)
 ZT vs. Yb Concentration
)
K
1.2
0
0 1.0 •Sensitive to Yb
6 0.8
Concentration
(
Yb Solubility Limit

0.6 •Maximum
T Figure of Merit
Z 0.4
~ 0.20 Yb
0.2
Concentration
0.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Yb Concentration
 Conclusions
• Yb-doped skutterudites show significant
promise for thermoelectric applications
• Figure of Merit - Sensitive to Yb
concentration
• Ge Charge Compensation
– Reduces Seebeck Coefficient at Elevated
Temperatures
– Reduces Carrier Mobility Leading to
Increased Resistivity
 Future Direction
• Yb ~ 0.20 concentrations
• High temp YbxCo4Sb12-ySny data
y  0.80
• Focus on keeping large magnitude
thermopower while incorporating ‘rattling’
atoms
– Beware of charge compensating
– Perhaps Co site
 Acknowledgements
• Dr. Terry M. Tritt (Dissertation Advisor)
• Dr. George S. Nolas – Synthesis
• NASA South Carolina Space Grant
• Project Supported through:
– Clemson - DOE EPSCoR Partnership
Grant No. DOE-DE-FG02_00ER45850