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High temperature Seebeck coefficient metrology

J. Martin,1,a兲 T. Tritt,2 and C. Uher3
Materials Science and Engineering Laboratory, National Institute of Standards and Technology,
Gaithersburg, Maryland 20899, USA
Department of Physics and Astronomy, Clemson University, Clemson, South Carolina 29634, USA
Department of Physics, University of Michigan, Ann Arbor, Michigan 48109, USA
共Received 18 May 2010; accepted 27 September 2010; published online 22 December 2010兲
We present an overview of the challenges and practices of thermoelectric metrology on bulk
materials at high temperature 共300 to 1300 K兲. The Seebeck coefficient, when combined with
thermal and electrical conductivity, is an essential property measurement for evaluating the potential
performance of novel thermoelectric materials. However, there is some question as to which
measurement technique共s兲 provides the most accurate determination of the Seebeck coefficient at
high temperature. This has led to the implementation of nonideal practices that have further
complicated the confirmation of reported high ZT materials. To ensure meaningful interlaboratory
comparison of data, thermoelectric measurements must be reliable, accurate, and consistent. This
article will summarize and compare the relevant measurement techniques and apparatus designs
required to effectively manage uncertainty, while also providing a reference resource of previous
advances in high temperature thermoelectric metrology. © 2010 American Institute of Physics.

TABLE OF CONTENTS per and bismuth wires, then upon heating one end observed
the deflection of a magnetic needle, describing this observa-
tion as “the magnetic polarization of metals and ores pro-
I. INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
duced by a temperature difference”—thermomagnetism 共Fig.
A. Thomas Seebeck and thermoelectricity. . . . . . 1
1兲.2,3 This term was actually coined in 1823 after subsequent
B. TE materials and applications. . . . . . . . . . . . . 2
investigations by von Yelin,4 who observed a similar effect
COEFFICIENT. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 when heating open circuit single metal elements. It was Ye-
A. The Seebeck coefficient. . . . . . . . . . . . . . . . . . 3 lin’s intent to distinguish his observations from those of See-
B. Arrangement and general requirements. . . . . . 3 beck. However, the term became ubiquitous in describing the
C. The integral method. . . . . . . . . . . . . . . . . . . . . 4 range of phenomena. Seebeck concluded the effect was ex-
D. The differential method and its conditions. . . 5 plicitly magnetic, objecting to contemporaries who suggested
1. The steady-state condition. . . . . . . . . . . . . . 5 it was a pure extension of Hans Christian Ørsted’s electro-
2. The quasi-steady-state condition. . . . . . . . . 6 magnetic phenomenon. In March of 1823, Ørsted himself
3. The transient 共or ac兲 condition. . . . . . . . . . 7 redirected the conceptualization of those experiments: “See-
E. The absolute TE scale. . . . . . . . . . . . . . . . . . . 8 beck has discovered that one can establish an electric circuit
III. METHODS OF MEASURING RESISTIVITY. . . 8 in metals without the interposition of any liquid. One estab-
IV. INSTRUMENTATION. . . . . . . . . . . . . . . . . . . . . . . 9
V. SUMMARY. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
ACKNOWLEDGMENTS. . . . . . . . . . . . . . . . . . . . . . . . 11

A. Thomas Seebeck and thermoelectricity
The earliest thermoelectric 共TE兲 “measurement” was re-
ported at a session of the Berlin Academy of Sciences on
August 16, 1821, by Thomas Johann Seebeck 共b. 1770, d.
1831兲, a graduate of Göttingen University in medicine and
practical surgery.1 Seebeck formed a bimetallic loop of cop- FIG. 1. Drawing depicting Seebeck’s experimental instrumentation.From
Adolphe Ganot, Traité élémentaire de physique expérimentale et appliquée
et de meteorologie: illustré de 568 belles gravures sure bois intercalées dans
Electronic mail: le texte 共Paris: L’auteur-éditeur, 1859兲, p. 707.

0021-8979/2010/108共12兲/121101/12/$30.00 108, 121101-1 © 2010 American Institute of Physics

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B. TE materials and applications

While the low conversion efficiency of TE devices cur-
rently limits their widespread commercial practicality to
niche applications, they remain an integral component in
NASA’s radioisotope TE generators for deep space power
generation, small-scale waste-heat recovery devices, tem-
perature measurement, and in electronic refrigeration. In ad-
FIG. 2. 共Color online兲 The Seebeck effect for two dissimilar materials A and dition, TE devices are environmentally friendly, require
B with the interfaces at temperatures T1 and T2, such that T1 ⬍ T2 and a minimal maintenance 共no moving parts兲, and reliably offer
proportional voltage is generated.
quiet and compact operation.
Higher efficiency TE materials would enable the practi-
lishes the current in this circuit by disturbing the equilibrium cal solid-state conversion of thermal and electrical energy.
of temperature.” Ørsted thus proposed a new terminology: “it The dimensionless figure of merit, ZT = S2␴T / ␬, defines the
will from now on doubtless be necessary to distinguish this effectiveness of these TE materials, where S is the Seebeck
new class of electric circuits by an appropriate term; and as coefficient, ␴ the electrical conductivity, T the absolute tem-
such I propose the expression TE circuit.”5 By the 1840s, it perature, and ␬ the total thermal conductivity 共␬ = ␬L + ␬e; the
was tacitly assumed Seebeck discovered thermoelectricity, lattice and electronic contributions, respectively兲.11–17 Opti-
although serendipitously. His first paper on the subject1 de- mizing these interdependent physical parameters to achieve
tailed “bismuthlike” behavior in many ores including PbS 共a acceptable efficiencies 共where the ZT ⬎ 1兲 requires materials
lead chalcogenide兲 and the skutterudite 共Co, Ni兲As3−x, mate- exhibiting a unique combination of properties. In addition,
rials that are still heavily investigated today. these materials must exhibit an optimal ZT within specific
TE phenomena enable the solid-state interconversion of target temperatures.
thermal and electrical energy. This conversion occurs Several approaches have been developed to identify
through two primary phenomena: the Seebeck and the Peltier these potential TE materials for high temperature energy
effect. The Seebeck effect describes the electric potential conversion applications.14–17 One approach, proposed by
emergent across a conductor within a thermal gradient. The Slack,18 suggests a phonon-glass electron-single-crystal
value of this ratio yields the Seebeck coefficient 共PGEC兲. An ideal PGEC material would possess thermal
properties similar to an amorphous material 共low thermal
⌬Vab conductivity with anomalous temperature dependence兲 and
Sab = lim , 共1兲
⌬T→0 ⌬T electrical properties similar to a good single crystal semicon-
ductor. This approach has proven successful in both the
where ⌬Vab is the electric potential across the interface of skutterudite19–22 and clathrate23–25 crystal structures, with
two dissimilar conductors within a thermal gradient ⌬T, as power factor 共S2␴兲 optimization provided by adjusting the
illustrated in Fig. 2. According to this definition, the mea- carrier concentration.
sured Seebeck coefficient Sab requires the correction Sab The recent progress in identifying several higher effi-
= Sb − Sa, where Sb is the second conductor’s contribution, to ciency 共ZT ⬎ 2兲 TE materials can be attributed to nanoscale
obtain Sa, the sample’s Seebeck coefficient. The terms “ther- enhancement. Many of these materials demonstrate increased
mopower” or “TE power,” while technically imprecise, are S2␴ and decreased thermal conductivity due to the phenom-
commonly substituted for the Seebeck coefficient. This latter enological properties of nanometer length scales, including
term was originally recommended by the joint AIEE-IRE quantum confinement effects 共increased density of states兲,
Task Group on TE Devices in the late 1950s for consistency enhanced phonon scattering, and charge carrier filtering.
with the Peltier and Thomson coefficients.6,7 In the corre- Candidate systems include thin films, heterostructures, super-
sponding Peltier effect, passing an electric current through lattices, nanowires, granular nanocomposites, and bulk ma-
the Ohmic interface of two dissimilar conductors results in terials with self-formed nanoinclusions.26–35
the liberation or the absorption of heat at the junction.8 This The continued development of novel TE materials in the
arises from the difference in Fermi energies 共EF兲 beyond the last two decades has given rise to interdisciplinary ap-
Ohmic interface, whereby heat is absorbed 共liberated兲 as an proaches, where solid-state chemistry, materials, and theoret-
electron passes from a lower 共higher兲 EF than that of the ical physics form a collaborative framework with measure-
connecting material. It is, therefore, dependent on the current ment science. This has led to the rapid incorporation of new
direction. The rate of thermal exchange at each junction is concepts and directions in materials synthesis and engineer-
given by ing. To fully evaluate the structure-property relationships and
to illuminate the underlying physics of these new systems
Q P = SabIT = ⌸abI, 共2兲 requires thorough characterization of the electrical and ther-
mal transport properties. Unfortunately, many of the mea-
where I is the current through the junction at temperature T surement techniques developed in the early part of the 20th
and ⌸ab is the Peltier coefficient of the junction. Methods of century and during the 1950s and 1960s are at risk of being
measuring the Peltier coefficient are described in overlooked by this new generation of researchers. We note
references.9,10 there are excellent general reviews on TE

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121101-3 Martin, Tritt, and Uher J. Appl. Phys. 108, 121101 共2010兲

coefficient generally comprises two components: one diffu-

sive, arising from the spatial redistribution of the charge car-
riers, and another arising from the interaction of the charge
carriers with the nonequilibrium portion of the phonon dis-
For metals in a thermal gradient, the contrasting thermal
diffusion of the charge carriers in each material relative to
their Ohmic interface establishes a voltage difference. This
electric potential provides the equilibrium necessary to pre-
vent further net charge transfer, resulting in the exclusive
FIG. 3. 共Color online兲 Ideal energy band diagrams representing electronic transport of kinetic energy.43–45 Thus, measurement of the
conduction for a metal and for n- and p-type semiconductors. The average Seebeck voltage requires the open circuit condition J = 0
energy of the carriers is illustrated by the brackets.
共where J is the electrical current density兲, such that the junc-
tions are isothermal and the electrochemical potential is
measurements.36–40 However, there are few reports specifi- continuous.43 In the Harman method 共or Z meter兲, the Ohmic
cally on Seebeck coefficient measurements, and fewer for voltage is measured under both isothermal and adiabatic con-
those at high temperature. ditions, such that J ⫽ 0 and the temperature difference forms
The Seebeck coefficient is an essential physical property due to the induced Peltier effect at the contacts. Here, the
in evaluating the potential performance of TE materials, as it Seebeck coefficient is obtained indirectly from the voltage
is highly sensitive to the electronic structure. However, the data under both conditions, provided the temperature differ-
deceptive simplicity of measuring the Seebeck coefficient ence is known.46–49 In n-type 共p-type兲 semiconductors, the
has often promoted poor apparatus design and the implemen- electric potential establishes in the opposite direction 共same
tation of inadequate measurement techniques, especially at direction兲 of the thermal gradient resulting in a negative
high temperature, where nonstandard practices have compli- 共positive兲 Seebeck coefficient. This convention ensures
cated the confirmation of reported high ZT materials. There- agreement between the Seebeck coefficient and the sign of
fore, this article will summarize and compare the methods of the carriers. However, the Seebeck coefficient is not explic-
measuring the Seebeck coefficient in an effort to stimulate a itly indicative of the majority carrier, and consequently, mea-
mindful approach to apparatus design and instrumentation. surements of n 共carrier concentration兲 and RH 共Hall coeffi-
To ensure meaningful interlaboratory comparison of data, cient兲 are required to fully evaluate the electronic
these measurements must be reliable, accurate, and consis- structure.15,36,38,50,51
tent. The following sections will summarize the relevant
measurement techniques, arrangement, and instrumentation
required to effectively manage uncertainty, while also pro-
viding a reference resource 共albeit nondefinitive兲 of previous B. Arrangement and general requirements
advances in high temperature Seebeck coefficient metrology.
While the Seebeck coefficient is not geometry dependent
Detailed apparatus descriptions will be left to the original
共for isotropic materials兲, the spatial arrangement of the
literary references. The bulk measurement of resistivity will
probes may affect the result. The two primary arrangements
also be introduced, as this characterization commonly ac-
developed in part from early thermal conductivity
companies Seebeck coefficient measurements.
measurements,52 as both quantities S and ␬ require the mea-
surement of ⌬T under an applied axial heat flux. By measur-
II. METHODS OF MEASURING THE SEEBECK ing the emergent electric potential, the Seebeck coefficient is
COEFFICIENT readily calculated. In the axial-flow technique 共two-probe兲,
A. The Seebeck coefficient the temperature difference and the electric potential are mea-
sured on the probes which are in direct contact with the ends
The Seebeck coefficient is essentially a measure of the of the specimen 共Fig. 4兲. This is the arrangement preferred
transport entropy per particle and is proportional to the av- by Goldsmid and Tritt for improved thermal and electrical
erage energy per carrier, relative to the Fermi energy EF, contact.38,53,54 However, many Seebeck coefficient apparatus
divided by charge per carrier 共⫾e兲 and temperature 共T兲 also concurrently measure resistivity, requiring additional
共Refs. 15, 16, 41, and 42兲 voltage contacts away from the ends of the sample. In the
1 potentiometric arrangement 共or four-probe兲, the temperature
S⬇ 具E − EF典. 共3兲 difference and the voltage difference are measured at two
points on the sample 共or inserted within the sample兲 equidis-
Metals typically exhibit smaller Seebeck coefficients since tant from the hot and cold sinks and on the axis parallel to
the charge carriers participating in electrical transport are the thermal gradient. To maintain accuracy, the diameter of
those with energies ⬇kBT, resulting in a small energy per each temperature/voltage probe must be much smaller than
carrier. Semiconductors typically exhibit larger Seebeck co- the effective distance between them.
efficients since carriers excited from dopant states within the There is some debate as to which method provides the
gap into the conduction band have a greater average energy most accurate determination of temperature and voltage dif-
per carrier 共Fig. 3兲. From a physical perspective, the Seebeck ference at the same points. These assertions are often stated

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FIG. 5. 共Color online兲 Graphical illustrations of the integral and the differ-
ential Seebeck coefficient measurement methods.

inconsistencies in the use of terms—e.g., steady-state, a lack

of consensus on time scale definition, poor estimations of
uncertainty, previous lack of Seebeck coefficient standards,
FIG. 4. 共Color online兲 Diagram comparing the potentiometric 共four-probe兲 and minimal detail in published high temperature apparatus
and the axial-flow 共two-probe兲 arrangements, where T1 ⬍ T2. descriptions, when they are published.
For material a whose junctions are Ohmic and isother-
mal with material b, both of which are chemically and physi-
arbitrarily with little comparative evidence to substantiate cally homogeneous and isotropic, the electric potential is de-
either arrangement. It would therefore be prudent to develop fined as41

冕 冕
an apparatus capable of in situ comparison. An apparatus T2 T2
developed by Bowers in 1959 共Ref. 6兲 averaged the results Vab共T1,T2兲 = Sab共T兲dT = 关Sb共T兲 − Sa共T兲兴dT, 共4兲
obtained by both of these arrangements. The Seebeck coef- T1 T1
ficients were consistent within 10% up to 800 ° C. However,
where Sa共T兲 is the absolute Seebeck coefficient of the sample
there was no estimation made of the overall measurement
being measured and Sb共T兲 is the known Seebeck coefficient
uncertainty, so this result may be regarded as preliminary.
of the reference leads. It is further assumed that materials a
Wood55 also compared the results of thermocouples pressed
and b are those in which the empirical Law of Magnus56 is
on the ends of a sample with those obtained by inserting
valid, such that Vab is explicitly a function of 共T1 , T2兲, and is
them in holes drilled in the sample. For the temperature and
independent of the temperature distribution between the in-
the material evaluated, the results were consistent within the
terfaces. This is invalid for chemically and/or physically in-
measurement uncertainty. It would be useful to evaluate
homogeneous materials. Despite some experimental efforts,
these arrangements over a broad temperature range and for a
notably by Benedicks,57 to prove otherwise, the Magnus Law
variety of materials. Considering the diversity of research
has been verified for extremely homogeneous metals.58 How-
materials in both geometry and contact resistance, the poten-
ever, both theoretical59 and experimental60 examination sug-
tiometric arrangement may benefit longer, lower cross-
gest steep thermal gradients in nondegenerate semiconduc-
sectional area specimens, while the axial-flow arrangement
tors may generate a nonequillibrium ⌬n共T兲 and therefore
may benefit shorter or disk-shaped specimens, provided the
influence Vab. See Domenicali43 for a complete discussion on
thermal resistance of the sample is larger than the thermal
anisotropic transport coefficients and volume and surface
resistance of the contact interface. Thus, a versatile and flex-
heating effects on the Seebeck coefficient.
ible apparatus would not only enable comparative measure-
ments on materials with different contact resistances, thermal
C. The integral method
conductivities, and heat capacities, but also expand the prac-
tical range of sample geometries. There are two primary techniques used to measure the
The primary requirements for “good” Seebeck coeffi- relative Seebeck coefficient: the integral and the differential
cient measurements are: 共1兲 the spatially synchronous mea- 共Fig. 5兲. In the integral method 共or large ⌬T兲, one end of the
surement of voltage and temperature, that is, the voltage and specimen is maintained at a fixed temperature T1 while the
temperature must be measured at the same location and at opposite end is varied through T2 = T1 + ⌬T, the temperature
the same time; 共2兲 probes in very good thermal and electrical range of interest.39,41,61,62 An appropriate analytic approxima-
contact with the specimen; and 共3兲 the acquisition of low tion is selected and applied to the entire data set Vab共T1,T2兲,
voltages 共microvoltages兲 with minimal extraneous contribu- then differentiated with respect to T2, where Eq. 共4兲 becomes
tions. Since at high temperature thermocouples are used to dVab共T1,T2兲
determine the temperature difference, where one pair of Sab共T2兲 = Sb共T2兲 − Sa共T2兲 = . 共5兲
identical wires probe the TE voltage, measurement of the
Seebeck coefficient is essentially a practice in low voltage The fitting method must comprise the data set with minimal
measurements. The various methods are best defined by the oscillations, as small random and biased errors will be am-
behavior of state variable T and by the gradient heating tech- plified in the derivative. To this end, various curve fitting
nique. However, a literature survey is challenging due to techniques have been explored. One common analytical rep-

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resentation is to continuously approximate the data by a se- mal conditions were made by comparing the TE voltage of
ries of orthogonal coefficients with the order selected by an the copper–silicon and the copper-constantan interfaces. The
F test.62 The mathematical oscillations can be further mini- resulting curves were fit and differentiated in 20° intervals.
mized by approximating the derivative in Eq. 共5兲 directly and In a modern embodiment, Wood62 developed an appara-
evaluating the derivative at sliding partial intervals where the tus to measure the Seebeck coefficient up to 1200 K. The
standard deviation is a minimum. Kettler63 used this proce- sample is pressed between a molybdenum heater and a water
dure to calibrate Chromel and Constantan thermocouple ref- cooled copper plate, where springs external to the furnace
erence wires with a pure Pb reference. maintain the contacting pressure. The temperature of each
The integral method developed naturally from the prac- end is measured by a W–Nb thermocouple 共not welded兲 em-
tices of early TE experiments, where Seebeck’s techniques bedded within an alumina tube for the cold side and a sap-
were easily extended to higher temperatures. For example, in phire button for the hot junction. Measurements are con-
1865 Stefan64 measured the TE potential of some chalco- ducted under an inert atmosphere 共⬇10−5 Pa兲. The Seebeck
genides 共galenites兲 and cuprous oxide ore couples by heating coeffient is obtained by differentiating an analytical approxi-
one interface with an alcohol flame. Additional examples of mation of the measured voltages. An additional detailed ap-
these early experiments can be found in Ref. 65. paratus description of the integral method can be found in
The next notable advance to this form of measurement Ref. 70.
was the work of Tait, a friend and colleague of Thomson The integral method succeeds in approximating TE op-
共Lord Kelvin兲. It was Thomson who first devised the theo- erating conditions and in minimizing the influence of voltage
retical relations to relate the three fundamental TE offsets, due to the large thermal gradients and subsequently
phenomena.66 In effort to establish a graphical representation larger voltage signals. It is, therefore, most useful for longer
of these relationships, Thomson suggested a chart consisting samples, wires, metallic ribbons, semimetals, and some
of parallel columns, each ordering by temperature the rela- semidegenerate semiconductors. However, it is difficult to
tive position of a number of metals. Lines drawn between maintain T1 isothermal throughout the large ⌬T at high tem-
successive columns indicate how the relative position of peratures, requiring additional corrections, and even more
each material changes with temperature. Expanding on this difficult to obtain a satisfactory fit for complex Sab共T兲, where
suggestion, Tait then developed his well known TE diagram, the Seebeck coefficient may have many more components
in which the abscissa indicate absolute temperatures, and the than simple carrier diffusion. Furthermore, there are no ob-
TE voltage is given by the difference of the ordinates 共at a jective criteria to evaluate the accuracy of the obtained de-
specific temperature兲 of the lines for any two metals. There- rivative.
fore, a drawing made through experimental measurements
could graphically indicate the relative magnitude and direc- D. The differential method and its conditions
tion of the TE electric potential of the metals, their tempera-
For the reasons described above, the differential method
ture dependence, as well as representations of the specific 共or small ⌬T兲 comprises the majority of high temperature
heat of electricity and the magnitude of the Peltier effect.67 Seebeck coefficient characterizations. In this technique, a
Inspired by Tait’s analysis on the temperature dependent small thermal gradient ⌬T is applied across a specimen
behavior of TE voltage, Dewar and Fleming68 compiled an maintained at the mean temperature of interest To = 共T1
extensive experimental tabulation of the temperature depen- + T2兲 / 2, where T1 = To − ⌬T / 2 and T2 = To + ⌬T / 2.39,41 By ex-
dence of other couples 共⫺200 and 100 ° C兲. These include panding the Seebeck coefficient Sab共T兲 in a Taylor series
Pt, Au, Pd, Ag, Cu, Zn, Cd, Mg, Sn, Fe, Ni, Steel, Mn–Steel, with center To and integrating, Eq. 共4兲 becomes
Manganin, Bi, Sb, Al, and C, relative to Pb. These data en-

冉 冊

abled measurements throughout the next several decades as a ⌬Vab 1 d2nSab共T兲 ⌬T 2n

comparative reference for other semiconductors and oxides = Sab共To兲 + 兺 共2n兲

⌬T n=1 共2n + 1兲! dT0 2
at higher temperatures.
One early implementation of the integral technique at = Sab共To兲 + ⌬Sab共To兲. 共6兲
higher temperature was given by Wick in 1907.69 The See-
Therefore, in the differential technique, the Seebeck coeffi-
beck coefficient of silicon rods 30 cm long and 3 mm in
cient is given exclusively by the ratio of the electric potential
diameter were measured from ⫺190 to 350 ° C relative to
and the temperature difference, provided ⌬T / To Ⰶ 1 and
copper. In an effort to establish good electrical and thermal
⌬Sab / Sab Ⰶ 1, when Vab ⬀ To and the latter term in Eq. 共6兲 can
interfaces, contacts to copper and constantan wires 共compris-
be neglected. In addition, the linearity in Sab共T兲 observed for
ing the thermocouple兲 were made to each sample end by the
typical metals cannot be expected in semiconductors, where
formation of an electroplated copper bridge. Copper wires
larger thermal gradients would effectively average the struc-
were then soldered to each of these wires and the terminals
ture in Sab共T兲 and reduce measurement resolution in T. The
submerged in an isothermal mercury bath for connection to a
following sections describe the different embodiments of the
potentiometer. One end of the rod was maintained isothermal
differential method.
at 0 ° C by inserting it within a metal tube submerged in a
Dewar bulb filled with a freezing mixture 共ice, “liquid air,”
or liquid oxygen were available at the time兲. The other end 1. The steady-state condition
was enclosed within an iron wire coil wrapped around an Differential methods can be categorized into three con-
asbestos covered porcelain tube. Corrections for nonisother- ditions: steady-state 共dc兲, quasi-steady-state 共qdc兲, and tran-

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FIG. 6. Early Seebeck coefficient apparatus described by Bidwell 共Ref.

72兲.Reprinted with permission from C. C. Bidwell, Phys. Rev. 19, 447
共1922兲. Copyright 1922 by the American Physical Society.

sient 共ac兲, assuming the observation time scale. Here, obser-

vation time is defined as the interval required to acquire one
voltage measurement 共assuming T1, T2, and Vab are mea-
sured simultaneously兲 and is therefore instrumentation de-
Perhaps the earliest implementation of the differential
steady-state method is that of Wold in 1916,71 who measured
simultaneously the Seebeck coefficient, the Nernst effect,
and the Hall effect in tellurium. The temperature differences
共between 2 to 10 ° C兲 were measured using platinum/
platinum–rhodium thermocouples. Bidwell72 then measured
the Seebeck coefficient 共and resistivity兲 of germanium rods
2.4 cm long between ⫺191 and 675 ° C 共Fig. 6兲. Platinum/
platinum–rhodium 共10%兲 thermocouples measured the tem-
perature differences in grooves at the ends of the sample and
were pressed on by nickel spring-loaded graphite rods. Dis-
tance adjustments within the heating profile of a vertical
chromel wire furnace varied the thermal gradient between 5 FIG. 7. Seebeck coefficient apparatus described by Burkov 共Ref. 77兲.Re-
printed with permission from A. T. Burkov, A. Heinrich, P. P. Konstantinov,
to 60 ° C. Middleton and Scanlon73 also describe a similar
T. Nakama, and K. Yagasaki, Meas. Sci. Technol. 12, 264 共2001兲. Copyright
apparatus with attention to thermocouple contacts. Other de- 2001 by the Institute of Physics.
tailed apparatus descriptions can be found in Refs. 74 and
2. The quasi-steady-state condition
Under steady-state conditions, differential methods often
calculate the Seebeck coefficient from the linear fit of mul- Although the steady-state condition succeeds in reducing
tiple electric potential/temperature difference data points the contribution of offset voltages, the time burden to prop-
rather than one. This practice avoids the assumption that the erly stabilize each increment of ⌬T may be impractical and
curves intersect the ordinate 共Vab = 0 , ⌬T = 0兲, effectively inefficient. To enable rapid measurements of the Seebeck co-
eliminating the offset voltages arising from thermocouple in- efficient the quasi-steady-state condition was introduced in
homogeneities and nonequilibrium contact interfaces 共the en- 1961 by Testardi and by Ivory in 1962.79–81 This condition
tire series of interfaces between thermocouple wires and the simultaneously measures multiple electric potential/
voltmeter兲. However, the selected temperature differences
must be acutely incremental, such that the total range satis-
fies the assumption of linearity in Sab共T兲. In addition, the
temperature for Sab共Tavg兲 must represent the average for the
collection of steady-state To. In 1956, Weiss76 implemented
the multiple gradient method to eliminate offset voltages.
The sample 共InAs兲 was clamped between graphite rods, us-
ing nickel/chromium thermocouples to measure thermal gra-
dients between 5 and 20 ° C between room temperature and
1000 ° C. The resulting slope of each line was used to calcu-
late the Seebeck coefficient, estimated to be accurate within
⫾5 ␮V / C. Two recent articles, one by Burkov77 共Fig. 7兲,
and the other by Zhou and Uher78 共Fig. 8兲, provide detailed
descriptions of the apparatus and instrumentation suggested
FIG. 8. Seebeck coefficient apparatus described by Zhou and Uher 共Ref.
for high temperature implementation of the differential 78兲.Reprinted with permission from Z. Zhou and C. Uher, Rev. Sci. Instrum.
steady-state method. 76, 023901 共2005兲. Copyright 2005, American Institute of Physics.

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121101-7 Martin, Tritt, and Uher J. Appl. Phys. 108, 121101 共2010兲

temperature difference data points but employs a continu-

ously increasing heat flux rather than multiple static, steady-
state ⌬T’s. However, to properly implement these dynamic
共or gradient sweep兲 techniques requires multiple high imped-
ance nanovoltmeters 共voltage meters with uncertainty
⬍100 nV兲. Voltage channel switchers, while economical,
should not be used to obtain data when continuously ramping
the thermal gradient. During the finite time required to
switch and measure the next voltage channel there will likely
be sufficient thermal drift to distort the temperature-voltage
correspondence, essentially smearing the Seebeck coeffi-
cient. This error is proportional to the thermal and voltage
drift during the time interval between each channel acquisi-
tion, usually compounded over three voltage measurements
per data point 共provided a differential thermocouple is not
used兲. One solution to minimize these distortions is to fit the
time dependence of the temperature gradient and interpolate
the values corresponding in time to the electric potentials.82
Furthermore, the physical switching of voltage channels may
cause brief transient signals or thermal offsets from the re-
lays. Additional time must then be introduced before acquir-
ing a voltage reading to obviate these effects. There is also a
question of how to select the appropriate time rate of change
in ⌬T. Unfortunately, this is rarely stated in the literature
making comparison of data quality a challenge.
One modern embodiment of the differential technique
under the quasisteady-state condition is given by Wood.55
The apparatus measures the Seebeck coefficient up to 1900
K by compressing a sample between two fused-quartz light FIG. 9. Seebeck coefficient apparatus described by Wood 共Ref. 55兲.Re-
pipes. W–Nb thermocouples are inserted into drilled holes printed with permission from C. Wood, D. Zoltan, and G. Stapfer, Rev. Sci.
near the ends of each light pipe 共Fig. 9兲. A dynamic tempera- Instrum. 56, 719 共1985兲. Copyright 1985, American Institute of Physics.
ture impulse 共⬇5 K兲 is generated by illuminating the light
pipes using 600 W tungsten filaments at each end. These are nated more rapidly and using smaller ⌬T values as compared
inversely toggled in such a way as to maintain a constant to those under steady-state conditions. These features can
average sample temperature. This apparatus was further sharpen the structural resolution in Sab共T兲.
modified to concurrently measure the Seebeck coefficient Nonsteady-state conditions are more sensitive to the
and electrical resistivity up to 1300 K.83 thermal diffusivity, heat capacity, mass, and geometry of the
In another example, Ponnambalam and Tritt84 developed materials measured, requiring adjustments to the positioning
an apparatus to measure resistivity and the Seebeck coeffi- of the thermocouples, the sample thickness, and the fre-
cient between 300 and 1000 K in the axial flow arrangement. quency of sinusoidal variation. The frequency should scale
Samples are compressed between silver blocks spring-loaded with the material’s thermal diffusivity or the sample length
external to the furnace for consistency 共Fig. 10兲. Type K 共thermocouple position兲 adjusted to ensure proper attenua-
thermocouples silver epoxied to these silver blocks measure tion of the ⌬T toward the cold end.87 However, the values of
the gradient sweep 共3 to 5 ° C兲 and platinum wires measure ⌬T can trace a slight frequency dependence above ⬇1 Hz. In
the electric potential. The base temperature of the furnace is addition, the magnitude of ⌬T is greatest at lower frequen-
also increasing at a steady rate rather than stabilized at each cies, where the signal-to-noise ratio yields a more accurate
temperature of interest. measure of the Seebeck coefficient. To avoid frequency de-
pendence in the Seebeck coefficient, the sample thickness d
must be significantly smaller than the thermal diffusion
3. The transient „or ac… condition
length ␭ = 共D / ␲ f兲1/2, where D is the thermal diffusivity of
To eliminate the rigorous thermal stability demands of the material and f is the frequency, to satisfy the relation
steady-state conditions, Freeman and Bass85 and Hellenthal 共d / ␭兲 Ⰶ 1. This promotes a homogenous, one-dimensional
and Ostholt86 introduced the transient condition in 1970. This temperature distribution. If these criteria are not met, the
condition is characterized by a sinusoidal temperature differ- Seebeck coefficient will increase with frequency and differ
ence ⌬T sin共␻t兲, where ⌬T is between 10 to 500 mK and from results obtained in the dc method, especially for lower
␻ / 2␲ is between 0.1 to 60 Hz. Lock-in amplifiers then con- thermal diffusivity materials.88 The required thickness 共0.1
tinuously extract the corresponding voltage and temperature mm to 0.2 mm兲 may be impractical for many brittle TE
amplitudes to obtain the Seebeck coefficient. By modulating materials. In addition, there are no objective criteria in which
the temperature difference, extraneous voltages are elimi- to choose the appropriate frequency.

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121101-8 Martin, Tritt, and Uher J. Appl. Phys. 108, 121101 共2010兲

perature range of interest. The most common reference ma-

terials at high temperature are platinum and copper. There
are two techniques to obtain the absolute Seebeck coeffi-
cient. In some low temperature measurements, it is possible
to use a superconducting material as the reference, since S
= 0 in the Meissner state.96 While limited to T ⬇ 120 K and
below, this technique can also provide calibration for Cu or
other reference materials at higher temperatures. However, at
high temperature an additional technique is required. The
Seebeck coefficient can be calculated for pure materials by
measuring the Thomson heat ␮T 共or Thomson coefficient兲
directly and using the relation

S共T兲 = 冕0
dT, 共7兲

where T is the temperature. This technique established the

absolute scales of thermoelectricity for common reference
materials in TE measurements.
Early measurements of the Thomson effect of copper
were conducted by Borelius97 and Lander.98 Combined with
these results, higher temperature measurements by
Nyström99 extended the absolute TE scale for Cu and Pt up
FIG. 10. 共Color online兲 Seebeck coefficient apparatus described by Ponnam- to 1023 K. Cusack and Kendall100 further extended this range
balam and Tritt 共Ref. 84兲.Reprinted with permission from V. Ponnambalam, to 1300 K for Cu and 2000 K for Pt by compiling the avail-
S. Lindsey, N. S. Hickman, and T. M. Tritt, Rev. of Sci. Instrum. 77, 073904 able data. However, the most accurate reference data has
共2006兲. Copyright 2006, American Institute of Physics. been obtained more recently by Roberts for Pb between ⬇0
and 550 K,101,102 for W between 273 and 1800 K,103 and for
A variety of techniques have been employed to initiate Pt between 273 and 1600 K.103 Roberts estimates the uncer-
the periodic heat pulse. Freeman and Bass85 used a tungsten tainty at the highest temperatures for Pt at ⫾0.2 ␮V / K.
lamp chopped at 21 Hz. Using this technique, they were able Burkov77 provides an empirical interpolation function for the
to obtain temperature differences as low as 0.03 K, measured Seebeck coefficient of Pt between 70 and 1500 K, by cor-
with aluminum/gold thermocouples. Goto et al.88 used a recting low temperature data104 according to the TE scale of
semiconductor laser to periodically heat one end of the Roberts101 for consistency with the higher temperature data
sample, and measure the temperature difference with R-type by Roberts.103 Bentley105 also provides similar absolute TE
thermocouples attached with silver paste. Kawai89 and data for Pt between 5 and 2041 K but using different low
Zhen-Jun90 also describe a laser modulated ac technique. temperature data than Burkov.77
However, light modulated heating should not be applied to
lightly-doped semiconductors, as photo-TE effects are likely III. METHODS OF MEASURING RESISTIVITY
to affect the result. Chen91 describes a slightly modified ac
measurement technique, in which two resistive heaters gen- Many of the apparatus described above concurrently
erate orthogonal sinusoidal temperature waves. This tech- measure resistivity and the Seebeck coefficient, therefore, a
nique has been modified with square wave pulses in opposite brief discussion on electrical resistivity measurements is ben-
phase for a toggled or bipolar heating.92 The ⌬T produced by eficial to apparatus design and instrumentation. Resistivity
each heater must be identical, rather than the power, because measurements in TE materials present unique challenges due
of sample differences in heat capacity and thermal conduc- to enhanced Seebeck voltage contributions and Peltier effects
tivity. Maldonado employed a similar technique but with at the probe contacts. These can be largely overcome through
only a single heat current pulsed with a square wave.93 This four-probe bipolar or ac resistance bridge techniques with
technique has been extended to higher temperatures 共475 K兲 adequate considerations. In the four-probe method 共potentio-
by Hogan.94 Fujimoto95 also describes a Peltier heating based metric兲, one pair of lead wires sources current through a bulk
transient technique. parallelopiped and a separate pair measures the correspond-
ing voltage drop. This effectively eliminates discrete voltage
contributions from measurement wires and sample contacts.
Combined with dimensional measurements, the resistivity is
E. The absolute TE scale given by
The measured value of a TE couple is proportional to the VA
difference between the Seebeck coefficient for the material ␳= , 共8兲
I lo
of interest and that for the reference wires 关Eq. 共1兲兴. There-
fore, the Seebeck coefficient of the reference material must where V is the measured voltage drop, I the current sourced
be determined in a separate experiment throughout the tem- through the sample, A the cross-sectional area, and lo the

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121101-9 Martin, Tritt, and Uher J. Appl. Phys. 108, 121101 共2010兲

effective distance between the centers of circular voltage tional Institute of Standards and Technology or an interna-
contacts 共midpoint to midpoint兲.106 Positioning these voltage tional standard when possible. Systematic uncertainties are
contacts away from the planar current contacts according to generally reduced or eliminated by design while some ran-
l − lo ⱖ 2w 共where l is the sample length and w is the sample dom errors may be eliminated by statistical methods.110 The
thickness兲 promotes a homogeneous current density where physical parameters that comprise the ZT values are gener-
the voltage is measured. These contacts must also be small to ally measured separately, requiring a fit of the temperature
avoid perturbations in the sample’s electric field. The geo- dependence of either the electrical or thermal properties to
metric factor 共A / lo兲 is the most dramatic source of uncer- ensure correspondence in temperature. However, the contri-
tainty in the resistivity measurement, therefore, extreme care bution of this temperature correspondence error to the total
should be given to parallel sample cutting 共using a wire saw兲 uncertainty in ZT is rarely discussed or estimated. In addi-
and polishing in addition to characterizing the geometry. tion, the Seebeck coefficient should be measured along the
As mentioned above, the measurement of resistivity in same direction as the resistivity and thermal conductivity,
TE materials presents unique difficulties. Finite thermal gra- and on the same sample if possible. This final section will
dients arising from Joule heating or the Seebeck measure- further discuss some of the sources of error previously de-
ment superimpose a TE voltage ⌬V = S⌬T onto the resistive scribed, while also providing a practical guide to designing a
voltage drop. Alternating current polarity and averaging the modern high temperature Seebeck coefficient apparatus. In
subsequent voltage measurements 共with no measurement po- addition to choosing an appropriate measurement technique,
larity change兲 eliminates these Seebeck voltage contributions one must consider the instrumentation required to effectively
关V共I+兲 + S⌬T兴 − 关V共I−兲 + S⌬T兴 manage uncertainty. This includes the voltmeters, the ther-
VIR = , 共9兲 mocouples, the probe design, and the cumulative series of
interface connections between the sample and the voltmeter.
as well as inhomogeneous current flow. In addition, the cur- Since at high temperature thermocouples are used to
rent through the sample is often calculated by measuring the measure the temperature difference, measurement of the See-
voltage drop across a precision resistor. Both of these tech- beck coefficient is essentially a practice of low voltage mea-
niques have been common practice since at least Bidwell’s surements. Therefore, the voltmeter must be sensitive to the
1922 TE characterization of germanium.65 range of voltages characteristic to the selected thermo-
A more challenging problem arises from the Peltier ef- couples, be able to detect small changes in the signal, and to
fect. The passage of current through the metal/semiconductor complete the measurement within the time scale appropriate
measurement interfaces result in the liberation of heat at one for the measurement technique. When selecting a voltmeter,
current contact and the absorption at the other. Depending one common mistake is to confuse instrument resolution
upon the direction of the current flow, attempts to measure with the uncertainty. The resolution of a voltmeter is defined
the resistivity contribute to standing temperature gradients as the ratio of the smallest count to the largest count on the
across the sample and consequently increase the apparent display. Physically, resolution represents the smallest change
Seebeck voltage. Unfortunately, the reversal of current re- in the signal that can produce a change in the display. A 5-1/2
verses the direction of both the temperature gradient and its digit display has the values 0-199,999 共0-9 + half digit of 0 or
corresponding Seebeck voltage, nullifying any benefit in- ⫾1兲, with a resolution of 1/200,000, or 0.0005%. However,
curred by averaging the two readings. While the resistive this does not include every source of error in the meter, and
voltage can be measured nearly instantaneously, the imposed is, therefore, not representative of the total uncertainty. For
Peltier thermal gradient requires a finite time to propagate. example, the stated uncertainty of a standard commercial
The time for thermal energy to diffuse from a contact to voltmeter, given in ⫾ 共ppm of reading+ ppm of range兲, is
distance x is proportional to x2 / D, where D is the thermal 50+ 6. The first term, 50 ppm of reading 共50/ 106兲 is negli-
diffusivity.87 Experimentally,107 this time has a maximal du- gible, but for the lowest range 共200 mV range兲, the second
ration of 1.1 to 1.3 s for common TE materials. Therefore, to term is 6 / 106 ⫻ 0.2 V or 1.2 ␮V. Therefore, measuring a
negate the Peltier effect requires fast switching of current small ⌬T of 1 K with an R-type thermocouple near room
polarity. These requirements have recently led to the use of temperature would have an uncertainty approaching 20%.
ac resistance bridges. However, similar results can be ob- Often the resolution of this voltmeter, 0.01 ␮V, is substi-
tained using nanovoltmeters and low ripple current sources. tuted for the uncertainty, giving a vastly different represen-
Colinear four-probe and van der Pauw techniques for thin tation of the instrument’s error. Other sources of voltmeter
disks and films are covered in the literature.38,40,108,109 uncertainty include: temperature dependence of the meter,
internal thermal offsets, channel relay self-heating, time drift,
IV. INSTRUMENTATION noise/rf interference, and improper zeroing of the channels.
Details of how to regulate or eliminate these parameters can
To aid in the verification in reported high ZT materials be found in Ref. 111.
and to effectively interpret the physics between comparative The thermocouple is probably the most overlooked com-
sample data, researchers must provide an estimation of the ponent of any measurement apparatus. It is generally treated
measurement uncertainty. Any measurement lacking this es- as a “black box” device, where the thermocouple is expected
timate is essentially incomplete. Uncertainty is the limit of to behave according to “calibration,” where the temperature/
measurement accuracy characteristic to the apparatus and the voltage correspondence is identical to an established stan-
contributing processes. This estimate can be traceable to Na- dard. However, there are a variety of other sources of error

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121101-10 Martin, Tritt, and Uher J. Appl. Phys. 108, 121101 共2010兲

that are erroneously eliminated through an assumption of 共low兲, thermal conductivity 共high兲, coefficient of thermal ex-
their absence. The actual process of negating these errors is pansion 共low and matched to the ceramic supports兲, heat ca-
called the “standard practice of thermocouples.” Bentley105 pacity 共low for ac or ballistic cycles; high for enhanced ther-
provides a through discussion of thermocouple theory, error mal stability兲, maximum operating temperature, high
reduction, and methods to estimate the total uncertainty. temperature strength, thermal shock resistance for the probe
Other references also discuss the theory and use of supports, diffusion/interface/chemical reaction properties
thermocouples.112–115 with candidate TE materials, oxidation resistance, machin-
By definition, a thermocouple is a relative measure of ability, and cost. Common probe materials are W 共excellent
temperature. The thermocouple transfers measurement of physical properties but difficult to machine兲, Mo 共can be
temperature from a difficult location to a more practical one, used in an oxidizing atmosphere兲, Pt 共good physical proper-
the reference 共cold兲 junction. This junction is an isothermal ties but very expensive兲, Ni 共a ferromagnet with a curie tem-
region serving as the interface between the thermocouple perature near 631 K, near which the resistivity and yield
wires and the copper wires to the voltmeters. Thermocouple strength can change by a factor of 5兲,116 Ag 共prone to
extension wires are invariably inhomogeneous and should diffusion/interaction with TE materials兲, Cu 共lower maxi-
rarely be used, since they are made from lower purity alloys mum operating temperature兲, Al 共lower operating tempera-
to mimic the TE properties of more expensive and pure ther- ture兲, and graphite 共resistive兲.
mocouple wire.105 All of the connections between the refer- One final consideration is contacts. These include both
ence junction and the voltmeter should be Cu-to-Cu to re- electrical and thermal contacts to the sample and also to the
duce the emergence of TE voltages at the interfaces, using instrumentation. Seebeck coefficient measurements are fur-
oxygen free copper or the more pure Ohno continuous cast ther complicated at high temperature by the possibility of
wire. Traditionally, the reference junction is an ice-water chemical reactions within the sample and/or with the sample
bath at 0 ° C, such that the temperature is stable to within probes or thermocouples. These reactions may give rise to
0.01 ° C. Where this is impractical, the temperature of the systematic voltage offsets. It is, therefore, prudent to repeat
reference junction can be measured directly using a precision the measurement cycle, especially when confirming mea-
platinum resistance thermometer. Another option is to use a surements on high ZT materials. There are many references
cold junction compensation circuit that provides a calibrated that describe the challenges of forming Ohmic contacts be-
voltage correction to the thermocouple voltage. However, tween metal and semiconductor interfaces.117,118 One reliable
this is less reliable with lower accuracy and should be and consistent method of forming good electrical and ther-
avoided where high accuracy is desired. The contributing mal contacts at high temperature for a variety of materials
magnitude of this error depends on the variation in S共T兲 has been pressure contacts.77–84 Often low pressure, pure he-
around 0 ° C for the specific thermocouple. lium gas is used as an intermediary to enhance thermal con-
Real thermocouples are not chemically or physically ho- tact between the thermocouple and the sample. However,
mogenous, especially since one wire is usually an alloy. there are reports suggesting low pressure gases such as he-
Physical inhomogeneity includes variation in crystallite size lium and nitrogen may affect the thermal contact and thus the
and macroscopic strains 共cold-working兲. This error repre- measured Seebeck coefficient value.119,120 Due to the ever
sents the variation in signal output dependent on the longi- evolving nature of TE materials research, the method and
tudinal temperature profile. That is, if the immersion depth of nature of forming good contacts must continually be evalu-
the thermocouple is varied while the tip and the reference ated and tested. To this end, the apparatus and methodologies
junction are constant, the change in voltage would reflect this implemented must be compared with materials previously
inhomogeneity 共⫾0.02% for Pt-based thermocouples兲. measured and/or to well characterized standards.121,122
Physical strain can often be removed by a proper annealing
procedure.115 This depends on the thermocouple type. For V. SUMMARY
high temperature measurements up to 1300 K, the recom-
mended types are platinum-base 共R, S兲 or single element The continued development of new TE materials for
thermocouples, which are not commercially available. Single high temperature power conversion applications requires re-
element thermocouples such as Pt–Au, have minimal effects liable and accurate characterization of the electrical and ther-
from lattice ordering or selective volatilization and oxida- mal transport properties. The Seebeck coefficient is an essen-
tion. Due to the higher purity materials and homogeneity, tial physical property in evaluating the potential performance
accuracy can approach 0.01 ° C with a drift ⬍0.1 ° C after of these TE materials, as it is sensitive to the electronic struc-
1000 h.105 The wire diameter must minimize heat sinking ture. However, the deceptive simplicity of measuring the
without significantly increasing contamination susceptibility Seebeck coefficient has led to the implementation of non-
or drift. Common diameters in TE measurements are 0.125 ideal practices that have further complicated the confirmation
to 0.25 mm. In addition, the thermocouple tips must be of reported high ZT materials. Therefore, researchers must
shielded from thermal radiation and the entire length embed- practice caution in order to accurately measure the Seebeck
ded in a ceramic sheathing to avoid strain and contamination. coefficient. While it may be experimentally uncertain which
Another important consideration is the probe material. arrangement provides the most accurate determination of
The probe provides the sample interface for electric current temperature and voltage difference at the same location, or
共resistivity measurements兲 and for the hot and cold sinks. which method and condition provides the most accurate de-
Selection criteria for probe materials include: resistivity termination of the Seebeck coefficient at high temperature,

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121101-11 Martin, Tritt, and Uher J. Appl. Phys. 108, 121101 共2010兲

the primary requirements remain the same: 共1兲 the voltage 21

demic, New York, 2000兲, Vol. 69, p. 139.
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