Thermal Conductivity
The underlying approxima-
There are three different ways to exchange heat
between a hot and a cold point, surface, or body: i.e.,
through radiation, convection, or conduction (Callen
1985). Notice that thermal insulation is required to
control the three different routes. However, it seems
easier to conduct heat than to insulate bodies. It is
common knowledge that a metal conducts heat, but
wool insulates. However, to understand why, to build
adequate models, and to develop efficient technologies
is a challenge. It is therefore very relevant to relate
macroscopic features to microscopic parameters in
this particular field of science.
Many famous names are found in the history of
heat transfer: Joule, Helmholtz, Kelvin, Boltzmann,
Fourier, Debye, etc. Nowadays a few research centers
are specializing in obtaining accurate data in various
temperature regimes. The most widely used technical
ways to measure heat transfer by conduction are
found in the article by Bougrine and Ausloos (1995).
In this article, the theoretical aspects will be presented.
The three basic theoretical methods, or let us say
approximations, will be given. The ingredients of most
popular models will be outlined, and various features
illustrated for specific materials.
The classical way of defining thermal transfer
though a conduction process follows from the pro-
portionality equation, known as the Fourier equation,
relating the gradient of temperature between two
points to the heat flux J (r ) between them, i.e.:
J (r ) lkλ]T
where λ is the thermal conductivity (see Eqn. (45b) in
Boltzmann Equation and Scattering Mechanisms). It
should be pointed out immediately that the above
equation can be generalized for anisotropic systems,
since J (r ) and ]T are vectors and λ is a (3i3) tensor.
In so doing, the symmetry properties of the body can
be taken into account in order to simplify the number
of elements of λ to be calculated, and to reduce the
number of elements to be measured. Moreover, the
above equation is only valid in the so-called linear
regime, i.e., when both ]T and J (r ) are small.
1. Thermal Diffusivity
A priori it can be thought that heat conduction is due
to the energy transfer between the main particles of
the system: in solids it should be the atoms, and
dissipation should arise from the atomic vibra-
tion excitations, i.e., from phonons. However, it
was soon observed that metallic systems, being good
electrically conducting materials, were also good
thermal conductors. It was observed as long ago as
1853 that λ is proportional to σT, where σ is the
electrical conductivity.
tions are discussed in Boltzmann Equation and Scatter-
ing Mechanisms. This proportionality law is known as
the Wiedemann–Franz law. It indicates that electrons
are also carrying heat, i.e., λ $ λe. In fact in a thermal
current, it can be expected that the energy carried by
the electrons depends on the maximum amount of
energy at the temperature considered. This is nothing
other than the specific heat Ce, which for metals (at
low temperature, i.e., much below the Debye tem-
perature TD: see Magnetic Systems: Specific Heat) is
proportional to the absolute temperature Ce l γT.
The relation between σ and λe is often observed
through the Lorentz number:
λ
L l
! σT
It has a value 2.44i10−) (V\K)# for free electrons.
Therefore the basic coefficient is in fact the thermal
diffusion coefficient D:
λ
Dl
ρC
where ρ is the material density, which is the pro-
portionality coefficient occurring in the time-dependent
Fourier law describing the variation of temperature as
a function of time and space:
c#T cT
kD l
cx# ct
2. Representative Experimental Data and Scattering
Contributions
Since diamond, or ceramics like BN or Al O , conduct
# $
heat as well as metals like silver or gold (Grigoriev and
Meilikhov 1997), it can be imagined that the phonon
contribution, λph, to λ can be as large as the electronic
one, λe, in complex materials. Therefore the thermal
conductivity of solids is usually assumed to consist of
two terms λe and λph, such that λ l λejλph. The
temperature dependence of a few selected materials is
shown in Fig. 1. The case of amorphous silicon is
also shown, together with that of superconducting
cuprates.
Experimental measurements show that in metals,
λ(T ) is linear at low temperatures (see Fig. 1 and
Grigoriev and Meilikhov 1997). At intermediate tem-
peratures (20 T 100 K), it decreases with T #
and λ(T ) tends to become almost constant at high
temperatures.
For electrical insulators, the thermal conductivity
behaves as:
λ(T ) l T $ exp(TD\T )
1
Thermal Conductivity
Figure 1
Log–log plot of the thermal conductivity λ(T ) behavior
for characteristic materials: YBCO l superconducting
ceramics; diamond ; Cu l copper; am.Si l amorphous
silicon.
at intermediate temperatures, and λ(T ) $ T −" at high
temperatures. When a material undergoes a magnetic
or a superconducting transition, specific changes in
slope are observed near the transition temperature
(Ausloos and Houssa 1999). Much work is still needed
in such regions in order to obtain consistent results
which can be interpreted. Note that for amorphous
(and also polycrystalline) samples, the thermal con-
ductivity increases at high temperature. This indicates
that the electron and phonon heat carriers are de-
pendent on the defect structure, while the type of heat
carrier scattering is of crucial relevance in order to
explain the observed features.
Indeed, by analogy with the electrical conductivity,
the first theoretical approximation consists in con-
sidering that various relaxation mechanisms contrib-
ute to the appropriate λ term, i.e., λe or λph, through a
sort of Mathiessen rule in terms of a scattering relax-
ation time τ (see Boltzmann Equation and Scattering
Mechanisms):
λ−" l λ−i " $ τ−i " l τ−"
where i indicates the type of scattering process which
either electrons or phonons experience, as heat car-
riers. The various types of scattering mechanisms are:
(i) point defects (impurities), (ii) grain boundaries, (iii)
dislocations, (iv) electrons, (v) phonons, (vi) magnons,
(vii) quasi particles, and, when a magnetic field is
present in superconductors, (viii) vortices. For the
corresponding scattering rates, see Ziman (1962).
In glasses and amorphous systems which have
anomalous properties at low (and also at high)
temperatures, contributions are due to structural and
orientational local disorder as well. Intriguing features
of various properties, e.g., sound attenuation, sound
2
velocity and thermal properties, suggest that one has
to consider scattering processes through so-called
tunneling states (Phillips 1972, Anderson et al. 1972).
This can lead to an explanation, for example, for the
presence of a T # term as due to phonon scattering by
vacancies in oxygen-deficient superconducting cer-
amics. Other explanations might also be put forward,
such as an electronic one due to unconventional order
parameter symmetry (Houssa and Ausloos 1997).
The complex character of λ appears also in magnetic
systems for which there is not only expectation of
scattering by localized spins and magnons, but also
through spin-level resonances induced by the internal
(crystalline) electric field and which are intrinsic to the
magnetic lattice symmetry (Rassili et al. 1998).
It is often necessary to consider the frequency ω and
wave vector k dependence of the scattering rates,
i.e. τ−i " (ω, k). The elementary kinetic formulation
considers that:
1
&
λi l  Ci(ω) Š#i (ω) τl(ω) dω
3
where Ci is the heat capacity, Ši the heat carrier
velocity and τi the appropriate scattering rate along
the wave vector k. For the phonon conductivity,
within the Debye approximation scheme for the
phonon spectrum this becomes:
$
&!
E G E G
kB kB TD/T x%ex
λph l T$ τ(x) dx
F
2π#Šs H F
h H
(exk1)#
where x l hω\kBT is the reduced phonon energy and
Šs the sound velocity.
The lattice thermal resistivity of metals and alloys is
mainly determined by the combined effect of the
phonon–phonon (v) Umklapp-processes (Ziman
1962) that lead to the T −" dependence in λ near TD and
to the (iv) contribution, well represented by the T #
term mentioned here above. It implies that λph $ T −" is
rather small for high and low temperatures in metallic
systems. At the same kinetic level, the contributions
from electrons are taken to be due to the superposition
of the (v) and ((i)–(iii)) terms. That leads to:
λ−e " l aT #jbT −"
Thus the ‘‘bump’’ in Fig. 1 is a key feature to be
explained from fundamental principles, depending on
the relative magnitude of the a and b coefficients in the
above formula.
3. Theoretical Methods of Analysis
The above elementary kinetic expressions contain the
relaxation time parameters which occur in the most

simple solution of the Boltzmann equation (see
Boltzmann Equation and Scattering Mechanisms). In
its general form, the Boltzmann equation is obtained
by combining the various changes in the distribution
function f (k) (of heat carriers here) due to the
diffusion (d) mechanism, external fields (f ), and
scattering (s), assuming a conservation law:
f (k) l fd(k)jff(k)jfs(k)
and requiring that f (k) vanishes in the steady state.
Then the α-component of the thermal current Jα due to
electrons is given, e.g., by:
&
Jα l (ε(k))kµ) Šα(k) f (k) d(k)
where µ is the chemical potential and εk the energy
spectrum for electrons. Similar expressions hold for
the phonon contributions.
The ff(k) term is proportional to a term ]T, which
allows the extraction of λ from the above definition
through the introduction of the relaxation time τ(k):
f (k)kf (!)(k)
fs(k) lk
τ(k)
since f (k) is supposed to behave like f (!)(k) exp
[kt\τ(k)], where f(!) (k) is the equilibrium heat carrier
distribution.
In practice, one should express each τ(k) contri-
bution in terms of a heat current–heat current cor-
relation function through the linear response for-
malism of Green and Kubo (Robertson 1993). In this
formalism:
&! dt
_
1
λ(T ) l δJ (t) δJ (o)
2kBT #V
where V is the volume of the system and δJ the
longitudinal component of the heat flux along the
temperature gradient. The current J(t) is obtained
from a microscopic evolution equation:
E G
δH
J(t) l d
F
δt H
in terms of the system Hamiltonian H and for a
characteristic length d $ Šτ; the notation δJ indicates
Thermal Conductivity
the fluctuation contribution to J as measured from the
steady state.
In doing so, each scattering term can be described
by a given term in the Hamiltonian, each one con-
taining a specific parameter characterizing the in-
teraction. Let us recall a few of these: the electron–
phonon coupling constant, the electron–electron
(Coulomb) interaction, the Yukawa potential for
electron-localized ionized defects, etc.
The interpretation of experimental data then follows
from a reverse application of the superposition rule,
starting from the most probable scattering mechanism
in the temperature range of interest, and searching for
a description of the remaining feature from the
difference between the raw data and the assumed first
level approximation.
The case of the thermal conductivity of super-
conducting cuprate ceramics is a typical example in
this respect (Houssa et al. 1996). The bump below the
superconducting transition temperature can be attrib-
uted to a change in the mean free path of either
electrons or phonons, as obtained after subtracting
from the raw data the phonon contribution extrapo-
lated from high temperature. Such a change in the
mean free path is supposed to occur because of the
superconducting condensed phase influence.
Notice that the electron scenario seems more prob-
able, since the bump position and height in λ(B) also
vary with an externally applied magnetic field B. It
should not be influenced much by B if it were of only
a phonon origin, while B is of extreme relevance for
the electronic contribution, the more so in uncon-
ventional superconductor systems like heavy fermions
(Houssa and Ausloos 1997).
Let us finally recall that the Boltzmann equation
formalism allows one to introduce the electrical
conductivity on the same footing as λ , but also the
thermoelectric power (or Seebeck coefficient) and the
Peltier coefficient (see Thermoelectric Power: Theo-
retical Concepts and Durczewski and Ausloos 1996).
The relaxation time approximation leads to defining λ
as:
A C
1 Λ#
λl Λk "
T # Λ
B ! D
where
&
E G
δf (!)
Λm l Š#(k) (ε(k)kµ)m τ(k) k dk
F
δε H
Another method consists in solving the Boltzmann
equation by the variational method (Callen 1985,
Ziman 1962, Durczewski and Ausloos 1996). The final
3
Thermal Conductivity

expression for λ is very cumbersome. We write it below Table 1

for cubic systems only, in which λ is a scalar, i.e.: Exponent values for the ratio of electron scattering
relaxation times for two-dimensional (2D) and three-
dimensional (3D) systems.
A
Ji[Pij]Uj
C
#
1 A C B D β γ δ η µ ν
λl Ui[Pij]−"Uj k i,j
T B i D
Ji[Pij]−"Jj 2D 2 0 3\2 4 0 1
ik 3D 3\2 0 3\2 5 1\2 1

where (i, j l 1, 2)
where TF is the Fermi temperature ( l εF\kB). The β,
J lk(3\2)Jo(kBT )$/#F / (z) γ, δ, η, µ, ν exponent values are given in Table 1 for
" "#
J lkJo(kBT )&/# Φ(z) two- and three-dimensional systems.
#
U l jUo(kBT )&/# Φ(z) l J \e
" #
U l jUo(kBT )(/# Ψ(z)
#
5. Summary
with z l µ\kBT.
F / (z) is the Fermi–Dirac integral of index n l 1\2, In conclusion, the thermal conductivity is an ex-
the "general
# definition being: perimental parameter rich in microscopic information.
It can be treated theoretically on the basis of (i) kinetic
theory, (ii) the Boltzmann equation, or (iii) linear
&! 1je
_ n
dxx response theory. The Boltzmann equation can be
Fn(z) l .
x−z solved in the relaxation time approximation to obtain
a phenomenological description, but theoretical work
output is rather powerful if the variational method is
The other functions }(z) and ψ(z) are defined by: used to solve the Boltzmann equation. It is useful to
work in regimes in which the Matthiessen rule holds;
}(z) l (5\2)F / (z)k(3\2)zF / (z) otherwise the extraction of parameters is not always
$# "#
ψ(z) l (7\2)F / (z)k2(5\2)zF / (z)j(3\2)z#F / (z) straightforward.
&# $# "#
and Jo and Uo are positive constants whose ratio Jo\Uo
is equal to the elementary charge e. The Pij are
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4
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Encyclopedia of Materials : Science and Technology
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