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Vijitha I
JRF, CSIR-NIIST
THERMOELECTRIC MATERIALS
1821
Thomas Johann Seebeck
1834
Jean-Charles-Athanase Peltier
1854
William Thomson( Lord Kelvin)
1928
Abram F. Ioffe
1947
Maria Telkes
1954
H. Julian Goldsmid
1930
Radio
1959
Home refrigerator,
General Electric,
Westinghouse
1959
Radioactive
Thermoelectric Generator
(RTG) "SNAP III"
1970
Cardiac pacemaker
1998
Seiko introduces the
Thermic watch
1999
Seat coolers in the
Lincoln Navigator and
Toyota's Lexus
36 years
Voyager 1
The First Thermoelectric….
Seebeck Effect
Peltier Effect
 In a thermoelectric material there are free carriers which carry both charge
and heat.
 In the steady state, the effect of the density gradient will exactly counteract
the effect of the temperature gradient so there is no net flow of molecules.
 If the molecules are charged, the buildup of charge at the cold end will also
produce a repulsive electrostatic force (and therefore electric potential) to
push the charges back to the hot end.
Seebeck Coefficient
Open circuit voltage produced per unit temperature difference (Thermo EMF)
T
V


H
CH
CH
T
T
ZT
ZT
T
TT



1
11

TZT

2

Thermoelectric Figure of Merit
Thermoelectric Efficiency
 High Seebeck coefficient
 High electrical conductivity
 Low thermal conductivity








 n
TK
EE
e
K
B
FCB

From transport calculations in nanoscale
LTe



Wiedemann-Franz Law
α σ
EC
EV
EF
N-type
α σ
phe  
Semiconductor
Semimetals &
highly doped
semiconductors Metals
Adapted from Heikes, R. R., and Ure, R. W., Jr. Thermoelectricity: Science and Engineering;
Interscience Publication: New York, 1961; p 20
 Quantum confined structures (α,  )
 Unusual band structures (α )
 Control over the disorder (α ,  )
The Breakthrough
Organic?
PEDOT:PSS - easy to handle, water-soluble, has high electrical
conductivity, and offers the possibility of achieving even higher
electrical conductivity.
Polypyrrole, Polyaniline,
Polycarbazol, Polythiophene,
Poly(3,4-ethylenedioxythiophene)
(PEDOT),
PEDOT:poly(styrenesulfonate) (PSS)
Cost effective
Low intrinsic thermal conductivity
High flexibility
Amenability to large area
applications
0.5 μm 10 nm 5 nm
The formation of the nanocrystalline structure of Te-PEDOT:PSS hybrids was
confirmed by transmission electron microscopy (TEM). The Te-PEDOT:PSS
hybrids consist of Te nanorods (diameter: 20–30 nm; length: ca. 800 nm) coated
with a thin PEDOT:PSS layer.
For the chemical treatment, the PEDOT:PSS and Te-PEDOT:PSS films were
immersed in H2SO4 solutions with various volume ratios (20–100%) for 10 min
under ambient conditions. The films were then washed in methanol and annealed at
160 °C for 10 min.
PEDOT:PSS
Te-PEDOT:PSS
aEstimated from the thermal
conductivity (0.20Wm−1K−1)
of PEDOT:PSS
bEstimated from the thermal
conductivity (0.22Wm−1K−1)
of Te-PEDOT:PSS
The improved
crystallinity of
PEDOT:PSS leads
to an increase in
the electrical
conductivity.
PEDOT:PSS
PEDOT:PSS
Te-PEDOT:PSS
Te-PEDOT:PSS
PSS:PEDOT = 2.23 PSS:PEDOT = 1.45
PSS:PEDOT = 1.28 PSS:PEDOT = 1.34
The decreased PSS/PEDOT ratio is
reflective of the structural
rearrangement induced by the decrease
in the PSS content of the composites. The
change in the PSS content also influences
the crystallinity of PEDOT:PSS and the
concentration of charge carriers.
600 nm 600 nm 600 nm
600 nm 600 nm 600 nm
SEM images of surface of Te-
PEDOT:PSS hybrid composite films
treated with various concentrations
of H2SO4: (a) 0, (b) 20, (c) 40, (d) 60,
(e) 80, and (f) 100 vol%
AFM images of surface of Te-
PEDOT:PSS hybrid composite films
treated with various concentrations
of H2SO4: (a) 0, (b) 20, (c) 40, (d) 60,
(e) 80, and (f) 100 vol%
The surface of the Te-PEDOT:PSS film before H2SO4 treatment consists of composite
nanorods that are densely packed together and interconnected with each other. The
surface of the composite nanorods was also smooth and clear. Therefore, the electrical
conductivity of the Te-hybrid increases, which arises from nanostructural rearrangement
of PEDOT:PSS which is interconnected on the surface of the Te nanorods.
12.75mV
10.59nW
5kΩ
A voltage of
over 2mV from
human body
heat
Enhanced the thermoelectric properties
by simply immersing the materials into H2SO4
Structural rearrangement of PEDOT:PSS
due to the removal of PSS, which induces
the formation of a more crystalline structure
and increases the number of charge carriers
Flexible TEG was successfully fabricated by
simple printing process using the treated
Te-PEDOT:PSS composite having a
high power factor of 284 μ W m−1 K−2
Electrical power generation capability
was demonstrated with a maximum
power output of 10.59 nW
Summary
Thank You

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Thermoelectrics

  • 2. 1821 Thomas Johann Seebeck 1834 Jean-Charles-Athanase Peltier 1854 William Thomson( Lord Kelvin) 1928 Abram F. Ioffe 1947 Maria Telkes 1954 H. Julian Goldsmid
  • 3. 1930 Radio 1959 Home refrigerator, General Electric, Westinghouse 1959 Radioactive Thermoelectric Generator (RTG) "SNAP III" 1970 Cardiac pacemaker 1998 Seiko introduces the Thermic watch 1999 Seat coolers in the Lincoln Navigator and Toyota's Lexus 36 years Voyager 1 The First Thermoelectric….
  • 6.  In a thermoelectric material there are free carriers which carry both charge and heat.  In the steady state, the effect of the density gradient will exactly counteract the effect of the temperature gradient so there is no net flow of molecules.  If the molecules are charged, the buildup of charge at the cold end will also produce a repulsive electrostatic force (and therefore electric potential) to push the charges back to the hot end.
  • 7. Seebeck Coefficient Open circuit voltage produced per unit temperature difference (Thermo EMF) T V   H CH CH T T ZT ZT T TT    1 11  TZT  2  Thermoelectric Figure of Merit Thermoelectric Efficiency
  • 8.  High Seebeck coefficient  High electrical conductivity  Low thermal conductivity          n TK EE e K B FCB  From transport calculations in nanoscale LTe    Wiedemann-Franz Law α σ EC EV EF N-type α σ phe  
  • 9. Semiconductor Semimetals & highly doped semiconductors Metals Adapted from Heikes, R. R., and Ure, R. W., Jr. Thermoelectricity: Science and Engineering; Interscience Publication: New York, 1961; p 20
  • 10.  Quantum confined structures (α,  )  Unusual band structures (α )  Control over the disorder (α ,  ) The Breakthrough
  • 11.
  • 12. Organic? PEDOT:PSS - easy to handle, water-soluble, has high electrical conductivity, and offers the possibility of achieving even higher electrical conductivity. Polypyrrole, Polyaniline, Polycarbazol, Polythiophene, Poly(3,4-ethylenedioxythiophene) (PEDOT), PEDOT:poly(styrenesulfonate) (PSS) Cost effective Low intrinsic thermal conductivity High flexibility Amenability to large area applications
  • 13. 0.5 μm 10 nm 5 nm The formation of the nanocrystalline structure of Te-PEDOT:PSS hybrids was confirmed by transmission electron microscopy (TEM). The Te-PEDOT:PSS hybrids consist of Te nanorods (diameter: 20–30 nm; length: ca. 800 nm) coated with a thin PEDOT:PSS layer. For the chemical treatment, the PEDOT:PSS and Te-PEDOT:PSS films were immersed in H2SO4 solutions with various volume ratios (20–100%) for 10 min under ambient conditions. The films were then washed in methanol and annealed at 160 °C for 10 min.
  • 14. PEDOT:PSS Te-PEDOT:PSS aEstimated from the thermal conductivity (0.20Wm−1K−1) of PEDOT:PSS bEstimated from the thermal conductivity (0.22Wm−1K−1) of Te-PEDOT:PSS The improved crystallinity of PEDOT:PSS leads to an increase in the electrical conductivity.
  • 15. PEDOT:PSS PEDOT:PSS Te-PEDOT:PSS Te-PEDOT:PSS PSS:PEDOT = 2.23 PSS:PEDOT = 1.45 PSS:PEDOT = 1.28 PSS:PEDOT = 1.34 The decreased PSS/PEDOT ratio is reflective of the structural rearrangement induced by the decrease in the PSS content of the composites. The change in the PSS content also influences the crystallinity of PEDOT:PSS and the concentration of charge carriers.
  • 16. 600 nm 600 nm 600 nm 600 nm 600 nm 600 nm SEM images of surface of Te- PEDOT:PSS hybrid composite films treated with various concentrations of H2SO4: (a) 0, (b) 20, (c) 40, (d) 60, (e) 80, and (f) 100 vol% AFM images of surface of Te- PEDOT:PSS hybrid composite films treated with various concentrations of H2SO4: (a) 0, (b) 20, (c) 40, (d) 60, (e) 80, and (f) 100 vol% The surface of the Te-PEDOT:PSS film before H2SO4 treatment consists of composite nanorods that are densely packed together and interconnected with each other. The surface of the composite nanorods was also smooth and clear. Therefore, the electrical conductivity of the Te-hybrid increases, which arises from nanostructural rearrangement of PEDOT:PSS which is interconnected on the surface of the Te nanorods.
  • 18.
  • 19.
  • 20. A voltage of over 2mV from human body heat Enhanced the thermoelectric properties by simply immersing the materials into H2SO4 Structural rearrangement of PEDOT:PSS due to the removal of PSS, which induces the formation of a more crystalline structure and increases the number of charge carriers Flexible TEG was successfully fabricated by simple printing process using the treated Te-PEDOT:PSS composite having a high power factor of 284 μ W m−1 K−2 Electrical power generation capability was demonstrated with a maximum power output of 10.59 nW Summary