Thermoelectric effect

1
Thermoelectric effect
The thermoelectric effect is the direct conversion of temperature differences to electric voltage and vice-versa. A
thermoelectric device creates a voltage when there is a different temperature on each side. Conversely, when a
voltage is applied to it, it creates a temperature difference. At the atomic scale, an applied temperature gradient
causes charge carriers in the material to diffuse from the hot side to the cold side.
This effect can be used to generate electricity, measure temperature or change the temperature of objects. Because
the direction of heating and cooling is determined by the polarity of the applied voltage, thermoelectric devices are
efficient temperature controllers.
The term "thermoelectric effect" encompasses three separately identified effects: the Seebeck effect, Peltier effect
and Thomson effect. Textbooks may refer to it as the PeltierSeebeck effect. This separation derives from the
independent discoveries of French physicist Jean Charles Athanase Peltier and balt-German physicist Thomas
Johann Seebeck. Joule heating, the heat that is generated whenever a voltage is applied across a resistive material, is
related though it is not generally termed a thermoelectric effect. The PeltierSeebeck and Thomson effects are
thermodynamically reversible,
[1]
whereas Joule heating is not.
Seebeck effect
Diagram of the circuit on which Seebeck
discovered the Seebeck effect. A and B are two
different metals.
The Seebeck effect is the conversion of temperature differences
directly into electricity and is named for the balt-German physicist
Thomas Johann Seebeck, who, in 1821 discovered that a compass
needle would be deflected by a closed loop formed by two metals
joined in two places, with a temperature difference between the
junctions. This was because the metals responded differently to the
temperature difference, creating a current loop and a magnetic field.
Seebeck did not recognize there was an electric current involved, so he
called the phenomenon the thermomagnetic effect. Danish physicist
Hans Christian rsted rectified the mistake and coined the term
"thermoelectricity". The voltage created by this effect is of the order of
several microvolts per kelvin difference. One such combination,
copper-constantan, has a Seebeck coefficient of 41 microvolts per
kelvin at room temperature.
[2]
The voltage V developed can be derived from:
where S
A
and S
B
are the thermopowers (Seebeck coefficient) of metals
A and B as a function of temperature and T
1
and T
2
are the temperatures of the two junctions. The Seebeck
coefficients are non-linear as a function of temperature, and depend on the conductors' absolute temperature,
material, and molecular structure. If the Seebeck coefficients are effectively constant for the measured temperature
range, the above formula can be approximated as:
The Seebeck effect is used in the thermocouple to measure a temperature difference; absolute temperature may be
found by setting one end to a known temperature. A metal of unknown composition can be classified by its
thermoelectric effect if a metallic probe of known composition, kept at a constant temperature, is held in contact with
it. Industrial quality control instruments use this as thermoelectric alloy sorting to identify metal alloys.
Thermoelectric effect
2
Thermocouples in series form a thermopile, sometimes constructed in order to increase the output voltage, since the
voltage induced over each individual couple is small. Thermoelectric generators are used for creating power from
heat differentials and exploit this effect.
Thermopower
The thermopower or Seebeck coefficient, represented by S, of a material measures the magnitude of an induced
thermoelectric voltage in response to a temperature difference across that material, and the entropy per charge carrier
in the material.
[3]
S has units of V/K, though V/K is more common. Values in the hundreds of V/K, regardless of
sign, are typical of good thermoelectric materials. The term "thermopower" is a misnomer since it does not measure
power, but measures the voltage induced in response to a temperature difference. An applied temperature difference
causes charged carriers in the material to diffuse from the hot side to the cold side. Mobile charged carriers migrating
to the cold side leave behind their oppositely charged nuclei at the hot side thus giving rise to a thermoelectric
voltage. Since a separation of charges creates an electric potential, the buildup of charged carriers onto the cold side
eventually ceases at some maximum value since the electric field is at equilibrium. An increase in the temperature
difference resumes a buildup of charge carriers on the cold side, leading to an increase in the thermoelectric voltage,
and vice versa. The material's temperature and crystal structure influence S; typically metals have small
thermopowers because of half-filled bands caused by equal negative and positive charges cancelling each other's
contribution to the induced thermoelectric voltage. In contrast, semiconductors can be doped with excess electrons or
electron holes, causing the magnitude of S to be large. The sign of the thermopower determines which charged
carriers dominate the electric transport.
If the temperature difference between the two ends of a material is small, then the thermopower of a material is
defined approximately
[4]
as:
and a thermoelectric voltage of V is seen at the terminals.
This can be written in relation to the electric field and the temperature gradient by the approximate
[4]
equation:
The absolute thermopower of the material of interest is rarely practically measured because electrodes attached to a
voltmeter must be placed onto the material in order to measure the thermoelectric voltage, inducing a thermoelectric
voltage across one leg of the measurement electrodes. The measured thermopower then includes the thermopower of
the material of interest and the material of the measurement electrodes and is written as:
Superconductors have S = 0 since the charged carriers produce no entropy. This allows a direct measurement of the
absolute thermopower of the material of interest, since it is the thermopower of the entire thermocouple. In addition,
a measurement of the Thomson coefficient , of a material yields the thermopower through the relation
S is an important material parameter that determines the efficiency of a thermoelectric material; a larger induced
thermoelectric voltage and a higher S mean a higher efficiency.
Thermoelectric effect
3
Charge-carrier diffusion
The Seebeck circuit configured as a
thermoelectric cooler
The same circuit configured as a generator
The Seebeck effect is caused by two things: charge-carrier diffusion
and phonon drag. Charge carriers in the materials will diffuse when
one end of a conductor is at a different temperature from the other. Hot
carriers diffuse from the hot end to the cold end, since there is a lower
density of hot carriers at the cold end of the conductor, and vice versa.
If the conductor were left to reach thermodynamic equilibrium, this
process would result in heat being distributed evenly throughout the
conductor (see heat transfer). The movement of heat (in the form of hot
charge carriers) from one end to the other is a heat current and an
electric current as charge carriers are moving.
In a system where both ends are kept at a constant temperature
difference, there is a constant diffusion of carriers. If the rate of
diffusion of hot and cold carriers in opposite directions is equal, there
is no net change in charge. The diffusing charges are scattered by
impurities, imperfections, and lattice vibrations or phonons. If the
scattering is energy dependent, the hot and cold carriers will diffuse at
different rates, creating a higher density of carriers at one end of the
material and an electrostatic voltage.
This electric field opposes the uneven scattering of carriers, and an
equilibrium is reached where the net number of carriers diffusing in
one direction is canceled by the net number of carriers moving in the
opposite direction. This means the thermopower of a material depends
greatly on impurities, imperfections, and structural changes that vary
with temperature and electric field; the thermopower of a material is a
collection of many different effects.
Early thermocouples were metallic, but many more recently developed
thermoelectric devices are made from alternating p-type and n-type
semiconductor elements connected by metallic connectors.
Semiconductor junctions are common in power generation devices, while metallic junctions are more common in
temperature measurement. Charge flows through the n-type element, crosses a metallic interconnect, and passes into
the p-type element. If a power source is provided, the thermoelectric device may act as a cooler by the Peltier effect
described below. Electrons in the n-type element move opposite the direction of current and holes in the p-type
element will move in the direction of current, both removing heat from one side of the device. When a heat source is
provided, the thermoelectric device functions as a power generator. The heat source drives electrons in the n-type
element toward the cooler region, creating a current through the circuit. Holes in the p-type element then flow in the
direction of the current. Therefore, thermal energy is converted into electrical energy.
Phonon drag
Phonons are not always in local thermal equilibrium; they move against the thermal gradient. They lose momentum
by interacting with electrons (or other carriers) and imperfections in the crystal. If the phonon-electron interaction is
predominant, the phonons will tend to push the electrons to one end of the material, hence losing momentum and
contributing to the thermoelectric field. This contribution is most important in the temperature region where
phonon-electron scattering is predominant. This happens for
Thermoelectric effect
4
where
D
is the Debye temperature. At lower temperatures there are fewer phonons available for drag, and at higher
temperatures they tend to lose momentum in phonon-phonon scattering instead of phonon-electron scattering. This
region of the thermopower-versus-temperature function is highly variable under a magnetic field.
Peltier effect
The Peltier effect is the presence of heat at an electrified junction of two different metals and is named for French
physicist Jean-Charles Peltier, who discovered it in 1834. When a current is made to flow through a junction
composed of materials A and B, heat is generated at the upper junction at T
2
, and absorbed at the lower junction at
T
1
. The Peltier heat absorbed by the lower junction per unit time is equal to
where
AB
is the Peltier coefficient for the thermocouple composed of materials A and B and
A
(
B
) is the Peltier
coefficient of material A (B). varies with the material's temperature and its specific composition: p-type silicon
typically has a positive Peltier coefficient below ~550 K, but n-type silicon is typically negative.
The Peltier coefficients represent how much heat current is carried per unit charge through a given material. Since
charge current must be continuous across a junction, the associated heat flow will develop a discontinuity if
A
and

B
are different. Depending on the magnitude of the current, heat must accumulate or deplete at the junction due to a
non-zero divergence there caused by the carriers attempting to return to the equilibrium that existed before the
current was applied by transferring energy from one connector to another. Individual couples can be connected in
series to enhance the effect. Thermoelectric heat pumps exploit this phenomenon, as do thermoelectric cooling
devices found in refrigerators.
Thomson effect
The Thomson effect was predicted and subsequently observed by Lord Kelvin in 1851. It describes the heating or
cooling of a current-carrying conductor with a temperature gradient.
Any current-carrying conductor (except for a superconductor) with a temperature difference between two points
either absorbs or emits heat, depending on the material. If a current density J is passed through a homogeneous
conductor, the heat production q per unit volume is:
where is the resistivity of the material, dT/dx is the temperature gradient along the wire and is the Thomson
coefficient. The first term is the Joule heating, which does not change in sign; the second term is the Thomson
heating, which follows J changing sign.
In metals such as zinc and copper, whose temperature is directly proportional to their potential, when current moves
from the hotter end to the colder end, there is a generation of heat and the positive Thomson effect occurs.
Conversely, in metals such as cobalt, nickel, and iron, whose temperature is inversely proportional to their potential,
when current moves from the hotter end to the colder end, there is an absorption of heat and the negative Thomson
effect occurs.
If the Thomson coefficient of a material is measured over a wide temperature range, it can be integrated using the
Thomson relations to determine the absolute values for the Peltier and Seebeck coefficients. This needs to be done
only for one material, since the other values can be determined by measuring pairwise Seebeck coefficients in
thermocouples containing the reference material and then adding back the absolute thermopower of the reference
material.
Thermoelectric effect
5
Lead is commonly stated to have a Thomson coefficient of zero; in fact, it is non-zero, albeit being very small.
[5]
In
contrast, the thermoelectric coefficients of all known superconductors are zero.
Thomson relations
The Thomson coefficient is unique among the three main thermoelectric coefficients because it is the only one
directly measurable for individual materials. The Peltier and Seebeck coefficients can only be determined for pairs of
materials; hence, no direct methods exist for determining absolute Seebeck or Peltier coefficients for an individual
material. In 1854, Lord Kelvin found relationships between the three coefficients, implying that only one could be
considered unique.
The first Thomson relation is
where T is the absolute temperature, is the Thomson coefficient and S is the Seebeck coefficient. The second
Thomson relation is
where is the Peltier coefficient. It predicted the Thomson effect before it was formalized.
Figure of merit
The figure of merit Z for thermoelectric devices is defined as
where is the electrical conductivity, is the thermal conductivity, and S is the Seebeck coefficient. The
dimensionless figure of merit ZT is formed by multiplying Z with the average temperature.
A greater ZT indicates a greater thermodynamic efficiency, subject to certain provisions, particularly that the two
materials in the couple have similar Z. ZT is therefore a method for comparing the potential efficiency of devices
using different materials. Values of 1 are considered good; values in the 34 range are essential for thermoelectrics
to compete with mechanical devices in efficiency. To date, the best reported ZT values are in the 34 range.
Currently this goal of high ZT values is referred to as: "high-figure-of-merit"
[6][7][8]
Much of the research in
thermoelectric materials has focused on increasing S and reducing by manipulating the nanostructure of the
materials.
Device efficiency
The efficiency of a thermoelectric device for electricity generation is given by , defined as
The maximum efficiency
max
is defined as
where T
H
is the temperature at the hot junction and T
C
is the temperature at the surface being cooled. is the
modified dimensionless figure of merit, which takes into consideration the thermoelectric capacity of both
thermoelectric materials being used in the device and is defined as
Thermoelectric effect
6
where is the electrical resistivity, is the average temperature between the hot and cold surfaces and the
subscripts n and p denote properties related to the n- and p-type semiconducting thermoelectric materials,
respectively. Since thermoelectric devices are heat engines, their efficiency is limited by the Carnot efficiency, hence
the T
H
and T
C
terms in . Regardless, the coefficient of performance of current commercial thermoelectric
refrigerators ranges from 0.3 to 0.6, one-sixth the value of traditional vapor-compression refrigerators.
[9]
Applications
Seebeck effect
The Seebeck effect is used in the thermoelectric generator, which functions like a heat engine, but is less bulky, has
no moving parts, and is typically more expensive and less efficient. These have a use in power plants for converting
waste heat into additional power (a form of energy recycling), and in automobiles as automotive thermoelectric
generators (ATGs) for increasing fuel efficiency. Space probes often use radioisotope thermoelectric generators with
the same mechanism but using radioisotopes to generate the required heat difference.
Peltier effect
The Peltier effect can be used to create a refrigerator which is compact and has no circulating fluid or moving parts;
such refrigerators are useful in applications where their advantages outweigh the disadvantage of their very low
efficiency.
Temperature measurement
Thermocouples and thermopiles are devices that use the Seebeck effect to measure the temperature difference
between two objects, one connected to a voltmeter and the other to the probe. The temperature of the voltmeter, and
hence that of the material being measured by the probe, can be measured separately using cold junction
compensation techniques.
References
[1] As the "figure of merit" approaches infinity, the PeltierSeebeck effect can drive a heat engine or refrigerator at closer and closer to the
Carnot efficiency. DiSalvo, "Thermoelectric Cooling and Power Generation", Science 1999 (http:/ / dx. doi. org/ 10. 1126/ science. 285. 5428.
703). Any device that works at the Carnot efficiency is thermodynamically reversible, a consequence of classical thermodynamics.
[2] http:/ / www. bnl. gov/ magnets/ staff/ gupta/ cryogenic-data-handbook/ Section13. pdf
[3] Rockwood, Alan L. (1984). "Relationship of thermoelectricity to electronic entropy" (http:/ / link. aps. org/ doi/ 10. 1103/ PhysRevA. 30.
2843). Phys. Rev. A 30 (5): 28434. Bibcode1984PhRvA..30.2843R. doi:10.1103/PhysRevA.30.2843.
[4] Strictly speaking, these two expressions for the Seebeck coefficient are only approximate: The numerator of the first equation should be the
difference in (electrochemical potential divided by -e), not electric potential, and likewise the second equation should have the gradient of
electrochemical potential divided by e rather than the electric field. The chemical potential is relatively constant as a function of temperature,
so using electric potential alone is in these cases a very good approximation. Taylor, 1973 (http:/ / dx. doi. org/ 10. 1103/ PhysRevB. 7. 1197).
Although many textbooks use the approximate definition, a few give the exact expression; examples are Physics of transition metal oxides by
Sadamichi Maekawa (http:/ / books. google. com/ books?id=iyNzfufnkBgC), page 323 and Thermoelectrics: Basic Principles and New
Materials Developments by Nolas et al. (http:/ / books.google. com/ books?id=0q5mi2XKbFAC), page 38.
[5] Roberts, R.B. (1977). "Absolute scale of thermoelectricity". Nature 265 (5591): 2267. Bibcode1977Natur.265..226R.
doi:10.1038/265226a0
[6] Katie Walter (May 2007). "A Quantum contribution to Technology" (http:/ / www. llnl. gov/ str/ May07/ Williamson. html). Lawrence
Livermore National Laboratory. .
[7] R. Venkatasubramanian, E. Siivola, T. Colpitts, and B. OQuinn, Nature 413, 597 2001.
[8] [8] T. C. Harman, M. P. Walsh, B. E. Laforge, and G. W. Turner, J. Electron. Mater. 34, L19 2005
[9] Solar refrigeration options a state-of-the-art review. D.S. Kim, C.A. Infante Ferreira. 2008, International Journal of Refrigeration, pp. 315.
DOI web link (http:/ / dx. doi. org/ 10.1016/ j.ijrefrig.2007. 07. 011)
Thermoelectric effect
7
Besanon, Robert M. (1985). The Encyclopedia of Physics, Third Edition. Van Nostrand Reinhold Company.
ISBN0-442-25778-3.
Rowe, D. M., ed. (2006). Thermoelectrics Handbook:Macro to Nano. Taylor & Francis. ISBN0-8493-2264-2.
Ioffe, A.F. (1957). Semiconductor Thermoelements and Thermoelectric Cooling. Infosearch Limited.
ISBN0-85086-039-3.
Thomson, William (1851). "On a mechanical theory of thermoelectric currents". Proc.Roy.Soc.Edinburgh: 9198.
External links
Thomson Effect Interactive Java Tutorial (http:/ / www. magnet. fsu. edu/ education/ tutorials/ java/
thomsoneffect/ index. html) National High Magnetic Field Laboratory
International Thermoelectric Society (http:/ / www. its. org/ )
General (http:/ / www. tf. uni-kiel. de/ matwis/ amat/ elmat_en/ kap_2/ backbone/ r2_3_3. html)
Explanation of carrier diffusion and phonon drag components of thermopower (http:/ / www. insa-lyon. fr/
Laboratoires/ GEMPPM/ TEP/ index. htm)
Good explanation of thermo-electric cooler design (http:/ / www. tellurex. com/ 12most. html#top)
BSST Technical Papers on thermoelectric devices (http:/ / www. bsst. com/ technical_papers. php)
A brief explanation (http:/ / www. coolworksinc. com/ about_thermoelectric_technology. htm)
An introduction to thermoelectric coolers (http:/ / www. electronics-cooling. com/ articles/ 1996/ sep/ sep96_04.
php)
The origin of the thermoelectric potential (http:/ / www. uni-konstanz. de/ FuF/ physik/ Jaeckle/ papers/
thermopower/ index. html)
The 8th European Conference on Thermoelectrics, ECT 2010, to be held Sept. 2224, 2010 in Como, Italy,
organized by the Lecco unit of the Institute of Energetics and Interphases (IENI) of the Italian National research
Council (CNR) (http:/ / www. centrovolta. org/ ECT2010/ )
A news article on the increases in thermal diode efficiency (http:/ / www. trnmag. com/ Stories/ 2001/ 121901/
Chips_turn_more_heat_to_power_121901. html)
A fan for putting on top of stoves and other hot items, powered by the Peltier-Seebeck effect. (https:/ / www.
gyroscope. com/ d. asp?product=ECOFAN2)
Generating useful voltages (and powering radio transmitters) from Peltier devices (http:/ / www. tdc. co. uk/
index. php?key=ect100)
Article Sources and Contributors
8
Article Sources and Contributors
Thermoelectric effect Source: http://en.wikipedia.org/w/index.php?oldid=523200482 Contributors: 2over0, Alejo2083, Alksentrs, Almazi, Ap, Aranymalinko, Arkrishna, Arnero, Arturj,
Atlant, Backeby, BasBloemsaat, Blueyoshi321, Borislav Dopudja, C Cullen, Camw, CaptainFecehead, Chessofnerd, Chrisjohnson, CiaPan, Cookie4869, Coppertwig, Crapface Bob, Curps,
Cutler, DHN, Daleh, Darklilac, Dblandford, Deco Da Man, Dgrant, Dhollm, Dirac66, Divyeshdoddapaneni, Dkevanko, Dr.K., E090, EE et al, Elyada, Emanuel.Blei, Faramarz.M, Feezo,
Fioravante Patrone, Firien, Firsfron, Fisting, Fleet Pete, Flerhun, Fram, Frdayeen, Freddy011, Freywa, Gene Nygaard, Giftlite, Gioto, Giraffedata, GoingBatty, Grandonia, Gsmcolect, H
Padleckas, HEL, Hadger, HarryMetcalfe, Heron, HornColumbia, Hsmith254, HughRandolph, Icairns, Isofilm, Jake Wartenberg, Jakob.scholbach, Jaraalbe, JarahE, Jheald, Joechuck, John of
Reading, Jynus, K Eliza Coyne, KDS4444, Kaktus Kid, Karol Langner, Keilana, Keith P Walsh, Ken g6, Klaser, Kr5t, Kukini, Kyng, L3p3r, Larryisgood, Laurentseries, Lear's Fool, Lfstevens,
Lixy, Llightex, Lou Agnew, Lyctc, Mac, Mass-man, Materialscientist, Mentifisto, Mesposit, Mgiganteus1, MiG, MikkoMikkola, Mild Bill Hiccup, Mindmatrix, Mmm, Mpfiz, Mtrisk, Mwarren
us, Napy1kenobi, NawlinWiki, Neparis, NewName, Nezdek, Nicola.Manini, Nikai, Nodekeeper, Nothra, NuclearEnergy, Oatmeal batman, Oedipusturannos, Oliviosu, Omegatron,
Omicronpersei8, Onlyscience, Osquar F, Oysteinp, POcca, PV=nRT, Pakaran, PatrickSalsbury, PaulLowrance, Phooto, Pinethicket, Pion, Poiuyqwerty, Proteus, QuantumSquirrel, Quibik,
RSRScrooge, RSido, Radagast83, RadicalBender, RedEye2063, Rhadamante, Robert K S, Robprain, Rorro, RussellBell, SGBailey, Sbyrnes321, Scott Dial, Shalomwt, Shanes, Shyland,
SimonDeDanser, Sloggerbum, Snoyes, Sommacal alfonso, Sornthep, Spinningspark, Stan J Klimas, Stephan Leeds, Stevertigo, Stuhacking, Suspekt, Tarchon, That Guy, From That Show!,
Theresa knott, Thingg, Thorseth, Timefly, Tushar.bhatnagar, Tvoz, Ulrich67, Uncle Milty, Vercalos, Vgy7ujm, Voidxor, Wavelength, Wbm1058, Wes Hermann, Wikiborg, Wtshymanski, Xareu
bs, Ynsark Navi, Ypark5, ZeroOne, Zs, sgeir IV., 05, 322 anonymous edits
Image Sources, Licenses and Contributors
File:Seebeck effect circuit 2.svg Source: http://en.wikipedia.org/w/index.php?title=File:Seebeck_effect_circuit_2.svg License: GNU Free Documentation License Contributors: derivative
work: Ken g6 (talk) Seebeck_effect_circuit_2.png: Omegatron
File:Thermoelectric Cooler Diagram.svg Source: http://en.wikipedia.org/w/index.php?title=File:Thermoelectric_Cooler_Diagram.svg License: Creative Commons Attribution-Share Alike
Contributors: Ken Brazier
File:Thermoelectric Generator Diagram.svg Source: http://en.wikipedia.org/w/index.php?title=File:Thermoelectric_Generator_Diagram.svg License: Creative Commons Attribution-Share
Alike Contributors: Ken Brazier
License
Creative Commons Attribution-Share Alike 3.0 Unported
//creativecommons.org/licenses/by-sa/3.0/