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Semiconductor thermodynamics: Peltier effect at a p-n junction

Research · December 2015

DOI: 10.13140/RG.2.1.4982.9203

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 Semiconductor thermodynamics:
Peltier effect at a p–n junction
(corrected and extended version)

Jan-Martin Wagner, Hilmar Straube, Otwin Breitenstein

• Motivation: Peltier effect in lock-in thermography investigations of

photovoltaic devices
• General theory: basics of thermoelectricity and of the Peltier effect
• Microscopic interpretation of the local Peltier coefficient
• p–n junction: spatially varying, bias dependent Peltier coefficients
• Recent example: quantitative interpretation of Peltier contributions
in a LIT measurement
• Summary

1 Retreat 2009, Weimar

 Motivation: Peltier effect in lock-in thermography (LIT)
investigations of photovoltaic devices
a) LIT image of a shunted mc-Si cell

1 mK
Simple quantitative interpretation
possible: local heating power directly
proportional to the current strength,
P = UbiasIlocal (energy conservation)
2a Retreat 2009, Weimar
 Motivation: Peltier effect in lock-in thermography (LIT)
investigations of photovoltaic devices
a) LIT image of a shunted mc-Si cell b) LIT image of a CSG module showing
strong edge recombination and cooling
at the contacts
0

100

200

300

400

0 125 250 375 500

1 mK Pixel

cooling heating
Simple quantitative interpretation -0.75 -0.50 -0.25

0
0.00

_350mV_dat
0.25 0.50 0.75

possible: local heating power directly Quantitative interpretation only possible

proportional to the current strength, after correction for the Peltier effect:
P = UbiasIlocal (energy conservation) heat transfer from contacts to edge
2b Retreat 2009, Weimar
 General theory: thermoelectricity basics
Peltier effect: “heat current” (not: “flow”!) accompanying an electric current,
not directly observable (in contrast to temperature-gradient-driven heat flow)

3a Retreat 2009, Weimar

 General theory: thermoelectricity basics
Peltier effect: “heat current” (not: “flow”!) accompanying an electric current,
rnot directly observable (in contrast to temperature-gradient-driven
r
heat flow)
jQ – heat current density, ! – Peltier coefficient, j – electric current density,
" – heat conductivity (all local quantities, i.e., dependent on position)
r r
Generalized Fourier law: jQ = ! j " #$T (!: heat energy per charge carr.)

3b Retreat 2009, Weimar

 General theory: thermoelectricity basics
Peltier effect: “heat current” (not: “flow”!) accompanying an electric current,
rnot directly observable (in contrast to temperature-gradient-driven
r
heat flow)
jQ – heat current density, ! – Peltier coefficient, j – electric current density,
" – heat conductivity (all local quantities, i.e., dependent on position)
r r
Generalized Fourier law: jQ = ! j " #$T (!: heat energy per charge carr.)

Temperature change caused by local heating or a change in heat current

c – specific heat capacity, # – mass density, p – heating power density
!T r
Heat conduction equation: c " = p # $ % jQ “heat tone”
!t

3c Retreat 2009, Weimar

 General theory: thermoelectricity basics
Peltier effect: “heat current” (not: “flow”!) accompanying an electric current,
rnot directly observable (in contrast to temperature-gradient-driven
r
heat flow)
jQ – heat current density, ! – Peltier coefficient, j – electric current density,
" – heat conductivity (all local quantities, i.e., dependent on position)
r r
Generalized Fourier law: jQ = ! j " #$T (!: heat energy per charge carr.)

Temperature change caused by local heating or a change in heat current

c – specific heat capacity, # – mass density, p – heating power density
!T r
Heat conduction equation: c " = p # $ % jQ “heat tone”
!t
Seebeck effect (electric field caused by a temperature gradient):
$ – electric conductivity, E – (applied) electric field, % – Seebeck coefficient
r r
Generalized Ohm’s law: (
j = ! E " #$T ) (%: voltage per kelvin)

3d Retreat 2009, Weimar

 General theory: thermoelectricity basics
Onsager relation (thermodynamics of irreversible processes)
for symmetrical coupling in linear description ! Kelvin relation: ! = "T

4a Retreat 2009, Weimar

 General theory: thermoelectricity basics
Onsager relation (thermodynamics of irreversible processes)
for symmetrical coupling in linear description ! Kelvin relation: ! = "T
“Pure” Peltier effect: isothermal transport of heat
(usually well approximated by LIT measurement)
r r
Isothermal conditions (stationary): !T = 0 " j = # j $ %!T
Q
0
r r r r
( )
! “Heat tone” (observable effect): !" # jQ = !" # $ j = ! j # "$ ! $" # j

4b Retreat 2009, Weimar

 General theory: thermoelectricity basics
Onsager relation (thermodynamics of irreversible processes)
for symmetrical coupling in linear description ! Kelvin relation: ! = "T
“Pure” Peltier effect: isothermal transport of heat
(usually well approximated by LIT measurement)
r r
Isothermal conditions (stationary): !T = 0 " j = # j $ %!T
Q
0
r r r r
( )
! “Heat tone” (observable effect): !" # jQ = !" # $ j = ! j # "$ ! $" # j

Effect: heat exchange at inhomogeneities of ! (e.g. jump at interfaces);

both signs (heating / cooling) are possible

4c Retreat 2009, Weimar

 General theory: thermoelectricity basics
Onsager relation (thermodynamics of irreversible processes)
for symmetrical coupling in linear description ! Kelvin relation: ! = "T
“Pure” Peltier effect: isothermal transport of heat
(usually well approximated by LIT measurement)
r r
Isothermal conditions (stationary): !T = 0 " j = # j $ %!T
Q
0
r r r r
( )
! “Heat tone” (observable effect): !" # jQ = !" # $ j = ! j # "$ ! $" # j

Effect: heat exchange at inhomogeneities of ! (e.g. jump at interfaces);

both signs (heating / cooling) are possible

Important: Redistribution of heat only, no global heat generation or

consumption

To obtain !" , we need to know !(x)! ! Microscopic view?

4d Retreat 2009, Weimar
 Microscopic interpretation of the local Peltier coefficient
Peltier heat transfer mechanisms:

– Thermal energy (excited states) of charge carriers ! !cc

– Stream of phonons being dragged along by the electric current ! !ph

5a Retreat 2009, Weimar

 Microscopic interpretation of the local Peltier coefficient
Peltier heat transfer mechanisms:

– Thermal energy (excited states) of charge carriers ! !cc

– Stream of phonons being dragged along by the electric current ! !ph

(n-type semicond.: “electron drag”, p-type semicond.: “hole drag”)
free
vLph
Roughly: ! ph " (long-wavelength phonons ! sample size!)
µcc

5b Retreat 2009, Weimar

 Microscopic interpretation of the local Peltier coefficient
Peltier heat transfer mechanisms:

– Thermal energy (excited states) of charge carriers ! !cc

– Stream of phonons being dragged along by the electric current ! !ph

(n-type semicond.: “electron drag”, p-type semicond.: “hole drag”)
free
vLph
Roughly: ! ph " (long-wavelength phonons ! sample size!)
µcc

Thermal energy of charge carriers:

Intuitively: 3kBT/2 above band edge (free electron/hole gas) – too simple!
Transport theory: conductivity-weighted average of band-structure energy
relative to the Fermi energy
1 % (EF $ E) "(E) f (E) dE
!
# cc =
e % "(E) f !(E) dE
5c Retreat 2009, Weimar
 Microscopic interpretation of the local Peltier coefficient
Non-degenerate semiconductor:
Boltzmann distribution, scattering time approximation (& ~ Er)
(r depends on scattering mechanism; r = –! for acoustic phonon scattering)
eff
! effective band-structure energy contribution: Eband = ( 52 + r)k B T above the
band edge,

6a Retreat 2009, Weimar

 Microscopic interpretation of the local Peltier coefficient
Non-degenerate semiconductor:
Boltzmann distribution, scattering time approximation (& ~ Er)
(r depends on scattering mechanism; r = –! for acoustic phonon scattering)
eff
! effective band-structure energy contribution: Eband = ( 52 + r)k B T above the
band edge, the latter relative to EF: !e / h = EC / V " EF , qe/h = ±e

! ( eff
! e / h = "e / h + Eband )q
e/h

eff
!e Eband !e EC

n-type EC p-type EF
EF EV
eff
EV !h Eband !h

6b Retreat 2009, Weimar

 Microscopic interpretation of the local Peltier coefficient
Non-degenerate semiconductor:
Boltzmann distribution, scattering time approximation (& ~ Er)
(r depends on scattering mechanism; r = –! for acoustic phonon scattering)
eff
! effective band-structure energy contribution: Eband = ( 52 + r)k B T above the
band edge, the latter relative to EF: !e / h = EC / V " EF , qe/h = ±e

! ( eff
! e / h = "e / h + Eband )q
e/h

eff
!e Eband !e EC

n-type EC p-type EF
EF EV
eff
EV !h Eband !h
Interpretation: EF is the free energy F; isothermal condition: Eint = F + TS
! The excess energy is heat; % = !/T: entropy per charge carrier

6c Retreat 2009, Weimar

 Microscopic interpretation of the local Peltier coefficient

Degenerate semiconductor: (e.g. solar cell emitter!)

– Large doping:
Fermi level inside the band (impurity deionization relevant)

7a Retreat 2009, Weimar

 Microscopic interpretation of the local Peltier coefficient

Degenerate semiconductor: (e.g. solar cell emitter!)

– Large doping:
Fermi level inside the band (impurity deionization relevant)

– Charge carrier contribution !cc small but not negligible (very roughly:
a few kBT/e); only band-structure energy relative to EF relevant

7b Retreat 2009, Weimar

 Microscopic interpretation of the local Peltier coefficient

Degenerate semiconductor: (e.g. solar cell emitter!)

– Large doping:
Fermi level inside the band (impurity deionization relevant)

– Charge carrier contribution !cc small but not negligible (very roughly:
a few kBT/e); only band-structure energy relative to EF relevant

– Phonon contribution !ph negligible:

(i) reduced free path (more dopants ! more scattering centers)
(ii) back-transfer of momentum from phonons to electrons (“phonon drag”,
as for Seebeck coefficient)

7c Retreat 2009, Weimar

 Microscopic interpretation of the local Peltier coefficient

Degenerate semiconductor: (e.g. solar cell emitter!)

– Large doping:
Fermi level inside the band (impurity deionization relevant)

– Charge carrier contribution !cc small but not negligible (very roughly:
a few kBT/e); only band-structure energy relative to EF relevant

– Phonon contribution !ph negligible:

(i) reduced free path (more dopants ! more scattering centers)
(ii) back-transfer of momentum from phonons to electrons (“phonon drag”,
as for Seebeck coefficient)

Metal: ! ! 0 (compared to semiconductors)

7d Retreat 2009, Weimar

 p–n junction: spatially varying Peltier coefficients
Zero bias, no illumination: ! min
e
ohmic contact

Consider also minority carriers!

ohmic contact
!e Udiff metal

EC
EF EF

metal
!h
EV
! min
h

eff
Eband = ( 52 + r)k B T constant ! !min determined by !e / h = EC / V " EF
! Minority carrier Peltier coefficient increased by Udiff compared to maj. carrier
8a Retreat 2009, Weimar
 p–n junction: spatially varying Peltier coefficients
Zero bias, no illumination: ! min
e
ohmic contact

Consider also minority carriers!

ohmic contact
!e Udiff metal

EC
EF EF

metal
!h
EV
! min !" # 0
h
at the contacts and at the junction

! Heat exchange at junction: cooling for “forward” current (carriers “go up”),
heating for “reverse” current (carriers “go down”)
8b Retreat 2009, Weimar
 p–n junction: bias-dependent Peltier coefficients
Diode operation: forward bias, no illumination ohmic contact
min
! Carrier injection and recombination ! e

ohmic contact
!e
EC
metal
EF,e
EF
bias voltage; net heating
EF
metal EF,h

EV !h

! min
h

9a Retreat 2009, Weimar

 p–n junction: bias-dependent Peltier coefficients
Diode operation: forward bias, no illumination ohmic contact
min
! Carrier injection and recombination ! e

ohmic contact
!e
EC
metal
EF,e
EF
bias voltage; net heating
EF
metal EF,h

EV !h

! min !" # 0 also in recombination regions

h
Minority carrier Peltier coefficients close to the junction change with bias
Recombination heat (non-radiative or radiative) contains Peltier heat

9b Retreat 2009, Weimar

 CSG module: interpretation of Peltier contributions in LIT image

CSG (crystalline silicon on glass) module: many long (module width) but narrow
stripes (6 mm) of polycrystalline p–n Si layers (2 "m) connected in series

LIT image: – Peltier heat exchange

0
proportional to local current
100

– Contacs: Peltier cooling

6 mm

– Edge:
200

300
a) p–n junction, but no Peltier
cooling visible!
400
b) Defects, leading to
0 125 250 375 500
recombination (heating)
Pixel

cooling -0.75 -0.50 -0.25 0.00 0.25 0.50 0.75 heating ! combined effect
0
_350mV_dat

! Cooling at the p–n junction observable by LIT only if laterally separated

from recombination heat sources
10 Retreat 2009, Weimar
 Shunts in solar cells: Peltier-enhanced recombination heat
Si solar cell operation: asymmetric doping (n+–p) and BSF (p+), full illumination
! Photocurrent in reverse direction min –
!e
ohmic contact EC
!e EF,e
EF metal
generated
voltage EF,h
metal EF

base
EV !h recomb. +
photo-gen. e–h pair

11a Retreat 2009, Weimar

 Shunts in solar cells: Peltier-enhanced recombination heat
Si solar cell operation: asymmetric doping (n+–p) and BSF (p+), full illumination
! Photocurrent in reverse direction min –
!e
ohmic contact EC
!e EF,e
EF metal
defect generated
level voltage EF,h
metal EF

base
EV !h recomb. +
depletion
region recombination photo-gen. e–h pair

Additional forward current due to generated voltage

! additional recomb. losses at nonlinear shunts in the depletion region

11b Retreat 2009, Weimar

 Shunts in solar cells: Peltier-enhanced recombination heat
Si solar cell operation: asymmetric doping (n+–p) and BSF (p+), full illumination
! Photocurrent in reverse direction min –
!e
ohmic contact EC
!e EF,e
EF metal
effective defect generated
shunt level voltage EF,h
metal heating EF
voltage
base
EV !h recomb. +
depletion
region recombination photo-gen. e–h pair

Additional forward current due to generated voltage

! additional recomb. losses at nonlinear shunts in the depletion region
Shunt heating at the p–n junction larger than due to generated voltage!
11c Retreat 2009, Weimar
 Recent example: quantitative interpretation
of Peltier contributions in a LIT measurement
Sample: bifacial Si solar cell (surface measurement, 4-point probe)
Idea: separate Joule and Peltier contributions by reversing the current
Integration method:

! = –U "QP / " QJ
p region (1016 cm–3): ! # 350 mV, ca. 1/3 from !ph
n region (1020 cm–3): ! # –70 mV, no !ph part

12 Retreat 2009, Weimar

 Summary
– The Peltier effect leads to a redistribution of heat (isothermally)
– Heat exchange occurs at inhomogeneities of the Peltier coefficient !
– ! = !cc + !ph

– For a diode, the Peltier coefficient changes (heat exchange occurs)

at the contacts, at the p–n junction, and in recombination regions
– Cooling at the p–n junction observable by LIT only if laterally separated
from recombination heat sources
– For a solar cell, the “internal heating” at shunts is larger than according to
the generated voltage
– For the quantitative interpretation of measured Peltier values of Si, the
“electron drag” effect must be taken into account even at room temp.

Outlook: direct observation of junction cooling in cross-section geometry;

Peltier coefficients for reverse bias?
Thanks for your attention!
13 Retreat 2009, Weimar
 References
– Peltier effect at a p–n junction:
K. P. Pipe et al., “Bias-dependent Peltier coefficient and internal cooling in bipolar devices”,
Phys. Rev. B 66, 125316 (2002)
– Contributions to the Peltier coefficient (! = !cc + !ph):
G. S. Nolas et al., “Thermoelectrics: basic principles and …” (Springer, 2001);
C. Herring, “Theory of the thermoelectric power of semiconductors”, Phys. Rev. 96, 1163
(1954)
– Phonon drag in Si at room temperature:
L. Weber et al., “Transport properties of silicon”, Appl. Phys. A 53, 136 (1991)
– General theory:
Solar cells: P. Würfel, “Physics of Solar Cells” (Wiley, 2005);
Transport: M. Lundstrom, “Fundamentals of carrier transport” (Cambridge, 2000);
Irreversible thermodynamics: H. B. Callen, “Thermodynamics …” (Wiley, 1985);
Radiation: C. E. Mungan, “Radiation thermodynamics …”, Am J. Phys. 73, 315 (2005)
– “Internal heating” at shunts (but Eband missing):
M. Kaes et al., “Light-modulated Lock-in Thermography …”, Prog. Photovolt: Res. Appl. 12,
355 (2004)
– Sum/difference imaging and integration method:
H. Straube et al., “Measurement of the Peltier coefficient by lock-in thermography”
(manuscript in preparation)

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Retreat 2009, Weimar