Materials Physics and Technology for Nanoelectronics

Metals
Clement Merckling
clement.merckling@kuleuven.be
imec & KU Leuven (MTM)
Kapeldreef 75, B-3001 Leuven

Francisco Molina-Lopez
francisco.molinalopez@kuleuven.be
MTM Functional Materials
Kasteelpark Arenberg 44, B-3001 Leuven
Outline

• Conductivity & resistivity

• AC conductivity
• Transparent metals
• Resistivity of thin metal films
• Thermal conductivity
• Superconductors

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Metals
• Metals are ‘’good’’ electrical conductors. These solids have a partially filled single energy band.
• In certain metals, like Mg, the valence band overlaps with the conduction band, such that 𝐸𝐺 = 0.
• When an electric field is applied to the material, electrons can be easily exited towards upper energy
levels within the same band, where they become ‘’quasi’’ free to move in the electric field, giving rise to a
high electrical conductivity.

Metals Semiconductors Insulators

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Metals
• There are a few kind of metals. Their unifying characteristic is that the Fermi level sits in the middle of a
partially filled band.

• The alkali metals

• The alkaline earth
• The transition metals
(noble metals)
• The rare earth metals
• The metalloids (semimetal)
• The half-metal

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Metals
• The alkali metals come from the first column of the periodic table. Like their neighbors in the second column
(alkaline earth metals), the alkali metals are generally very reactive. Their conduction bands are built out of 𝑠-
orbitals, and exhibit weak spin-orbit effects.
• The transition metals include Ni, Fe, Co and Cu. Transition metals have partially filled 𝑑-orbitals. These 𝑑
electrons can be relatively localized to the ion core in the metal, or can have some itinerant character. Because
of unpaired 𝑑 electrons, the transition metals and their oxides often exhibit magnetic ordering (long range
correlations in the spin state of the 𝑑 electrons).
The noble metals, such as ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium
(Ir), platinum (Pt), and gold (Ag). They are much less reactive, and therefore resistant to corrosion. Strictly
noble metals have filled 𝑑-shells. Pd, Pt and Ru have partially filled d-shells in condensed form and are often
used as catalysts. The noble metals are generally heavier atoms and exhibit stronger spin-orbit interactions.
Noble metals generally do not exhibit superconductivity by themselves.
• The rare earth metals are the actinides and lanthanides. These materials generally contain partially filled 𝑓-
orbitals, and like transition metals can exhibit magnetic effects. They have very strong spin-orbit interactions,
meaning that relativistic corrections to their band structures are important.
• The metalloids present characteristics, which are a mixture of those of metals and non-metals.
• A particularly rare variety of metals is the half-metal, in which all of the electrons at the Fermi level are fully spin-
polarized. A half-metals acts as a conductor to electrons of one spin orientation, but as an insulator to those of
the opposite orientation. The simplest half-metal is CrO2.

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Conductivity & resistivity

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Materials interpretation of Ohm’s law
• A fundamental equation pertaining to electrical conduction of
materials is Ohm’s law, which has been extracted from
experimental observations: R A = r2
𝑉 L
𝑅 = = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝐼
• Most materials are Ohmic over at least a limited range of current.
I
• The resistance 𝑅 is proportional to the length 𝐿 of the sample and
inversely proportional to the cross-sectional area 𝐴 and 𝑹 = 𝝆𝑳Τ𝑨
where 𝝆 is a materials parameter i.e. specific resistivity (in m).
• In a uniform sample, the electric field is 𝐸 = 𝑉 Τ𝐿. The current
density is 𝐽 = 𝐼 Τ𝐴. As such, the materials scientist’s version of V
Ohm’s law becomes:
𝐸
𝜌 = = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 or also 𝐽 = 𝜎𝐸
𝐽
where 𝜎 = 1Τ𝜌 is the electrical conductivity

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Materials interpretation of Ohm’s law
• This equation is independent of the sample dimensions. It expresses a relation that is valid locally at
every point in the material. It is a vector relation showing the two vector quantities, the electric field 𝐸 and
the current density J, are parallel and proportional everywhere in the material (isotropic).
𝑱Ԧ = 𝝈𝑬

• For anisotropic materials, conductivity is not a simple scalar but is a nine-component tensor and Ohm’s
law becomes: 𝑱Ԧ = 𝝈
ෝ𝑬 →
𝐽1 = 𝜎11 𝐸1 + 𝜎12 𝐸2 + 𝜎13 𝐸3
𝐽2 = 𝜎21 𝐸1 + 𝜎22 𝐸2 + 𝜎23 𝐸3
𝐽3 = 𝜎31 𝐸1 + 𝜎32 𝐸2 + 𝜎33 𝐸3

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Conductivity
• The conductivity  of different materials spans about twenty-five orders of magnitude. This is the largest
known variation in a physical property.

Room-temperature conductivity of various materials, including insulators, semiconductors

and metals. Superconductors, having conductivities of many orders of magnitude larger
than copper, near 0 K, are not shown. The conductivity of semiconductors varies
substantially with temperature and purity.

• A satisfactory understanding of conductivity based on a classical atomistic basis was achieved by Drude.
• The understanding was later refined by quantum mechanics in the Sommerfeld model.

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Classical free electron theory of metals
• Drude assumed that in a metal one or more valence electrons per atom were completely delocalized and
were free to bounce around inside a metal like a free electron gas.
• Pursuing the analogy with gas kinetics, he assumed that the average kinetic energy 𝑚𝑣 2 Τ2 of the
electrons was 𝑘𝐵 𝑇Τ2 per degree of freedom, or 3𝑘𝐵 𝑇Τ2 in a three dimensional free-electron “gas”.

• In this model the randomly directed, fast moving free electrons in the metal can collide with each other,
the surfaces of the metal, and with the positive ions they left behind. Their average thermal velocity is:
1ൗ
3𝑘𝐵 𝑇 2
𝑉𝑡ℎ =
𝑚
where 𝑘𝐵 is Boltzmann’s constant and 𝑚 the electron mass.
• For a temperature 𝑇 of 300 K, this predicts that 𝑉𝑡ℎ is about 105 m/s.

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Conductivity: classical approach
• Without an electric field, the individual velocities of the 𝑣𝐷
electrons cancel out and no net velocity results.
• If the electrons are accelerated by a force -q𝐸, a net
drift of the electrons results and can be expressed by
Newton’s law (𝐹 = 𝑚𝑎) as : e-
𝑑𝑣 e-
𝑚 = −𝑞𝐸
𝑑𝑡
• where -q is the charge of the electrons and 𝑚 is their E=0 E≠0
mass. We hence imply that the drift velocity of
electrons, caused by an external electric field, is The zig-zag line represent the motion of charge carrier
superimposed on the much larger random motion of with (a) thermal motion only: no net progress in any
the electrons. particular direction and (b) thermal motion and drift
motion: when a field is applied, the electron tends to drift
in direction opposite to the electric field.
• If the electron were totally free, as in vacuum, this
constant acceleration would lead to a steadily
increasing velocity, and the electron would gain more
and more kinetic energy from the field.
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Conductivity: classical approach
• In the metal the free electrons are interacting with the lattice ions. Considering the interactions between
the electrons and the lattice atoms, the above equation is modified as:
𝑑𝑣
𝑚 = −𝑞𝐸 −𝛾𝑣
𝑑𝑡

• The second term at the right of this equation is a damping or friction force which contains the velocity
of the electrons.

• If we focus on a single electron, it would be accelerated by a field until its drift velocity encounters a
collision. At this time, the electron has acquired the drift velocity 𝑣𝑚𝑎𝑥 which it may lose all or in part at the
collision.

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Conductivity: classical approach
• Each electron is thought to be accelerated until a (a) (b)
final average drift velocity 𝑣𝑓 is reached. 
f
• At that time, the electric field force and the friction - +
force are equal in magnitude. In other words, the
electrons are thought to move in a viscous
medium. t
Electron Path
• For steady state case 𝑣 = 𝑣𝑓 we obtain 𝑑𝑣Τ𝑑𝑡 = 0.
(a) Schematic representation of an electron path through a
• The previous equation then reduces to 𝛾𝑣𝑓 = −𝑞𝐸 conductor containing vacancies, impurity atoms and grain
which yields to : boundaries under the influence of an electric field. (b)
Velocity distribution of electrons due to an electrostatic
−𝑞𝐸 𝑞𝐸 force and a counteracting friction force. The electron
𝛾= (>0) → 𝛾=
𝑣𝑓 𝑣𝑓 eventually reaches the final velocity f.

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 Materials Physics and Technology for Nanoelectronics
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Conductivity: classical approach
• The complete equation for drifting electrons under the influence of an electric field becomes:
𝑑𝑣 𝑞𝐸
𝑚 = −𝑞𝐸 − 𝑣
𝑑𝑡 𝑣𝑓
• The solution to this equation is:
𝑞𝐸
𝑣 = 𝑣𝑓 1 − 𝑒𝑥𝑝 −
𝑚𝑣𝑓
𝑡 
f
(see solution in next slide)
• It is customary to define τ the relaxation time as:
𝑚𝑣𝑓 𝑚𝑣𝑓
t
τ= =
𝑞𝐸 𝑞𝐸 τ
which can be interpreted as the average time between two consecutive collisions.

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 𝑑𝑣 𝑞𝐸
• Solution of 𝑚 𝑑𝑡 = −𝑞𝐸 − 𝑣
𝑣𝑓

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Conductivity: classical approach
• When an electric field 𝐸 is applied the free-electron gas achieves an
average final drift velocity 𝒗𝒇 and a net current density 𝑱. (The drift
velocity will be much less than the randomly directed thermal
velocity). If the number of free electrons per unit volume, called
charge carrier density, is represented by 𝑁𝑒 , the current density will
be given by:
𝐽 = −𝑞𝑁𝑒 𝑣𝑓
• If 𝑁𝑒 is independent of E, Ohm’s law will be satisfied if the drift
velocity is proportional to the field. We define this proportionality
constant as the mobility e of free electrons such as 𝑣𝑓 = −𝜇𝑒 𝐸
(minus sign because electrons are moving in the opposite direction
than the electric field) and the conductivity is:
𝜎 = 𝑞𝑁𝑒 𝜇𝑒
• The units for mobility can be seen to be m2V-1s-1.

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Conductivity: classical approach
• From previous equations we obtain:
Atomic Mass Electron Conductivity Collision
τ𝑞 𝐸 τ𝑞(−𝐸) number Valence density m density n  time 
𝑣𝑓 = = Metal A z (103 kg/m3) (1029 m-3) (106 (.m)-1) (10-15 s)
𝑚 𝑚
Ag 107.9 1 10.5 0.585 62.1 37.6

• Together with 𝐽 = −𝑞𝑁𝑒 𝑣𝑓 = 𝜎𝐸 Al 26.98 3 2.70 1.81 36.5 7.17

Ba 137.3 2 3.59 0.315 2.6 2.93
• The equation for conductivity becomes: Be 9.012 2 1.82 2.43 30.8 4.50
Ca 40.08 2 1.53 0.460 27.8 21.5
𝑁𝑒 𝑞2 τ 𝑞τ
𝜎= , or μ = , Cd 112.4 2 8.65 0.927 13.8 5.29
𝑚 𝑚
Cs 132.3 1 2.00 0.091 5.0 19.5

• This teaches us that the conductivity is Cu 63.55 1 8.93 0.846 58.8 24.7

large for a material with a large number of In 114.8 3 7.29 1.15 11.4 3.53

free electrons and a large relaxation time. K 39.10 1 0.91 0.140 13.9 35.2
Li 6.939 1 0.54 0.469 10.7 8.11

• The latter is proportional to the mean free Mg 24.31 2 1.74 0.862 22.3 9.18

path between two consecutive collisions. Parameters of some metals at T=295K

The mean free path 𝒍 is defined to be :
𝑙 = 𝑣𝑓 τ

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Semi quantum mechanical approach
• In the Sommerfeld model it is assumed that when an electric field is applied to the metal, the electrons
occupying the highest energy level (𝐸𝐹 ) can be excited towards a higher energy level and be considered
as “quasi-free”, i.e. only those electrons will participate in the electrical conduction.
• From quantum mechanics, the electrons in a solid are filling energy bands (two electrons per energy
level, according to the Pauli principle). The highest occupied level, at 𝑇 = 0 𝐾, is the Fermi level 𝐸𝐹 ,
which can be calculated from the Schrödinger equation, and is given by:
2ൗ
ℏ2 3𝜋 2 𝑁 3
𝐸𝐹 =
2𝑚 𝑉
with 𝑁/𝑉 the electron concentration.
• The maximum velocity that the electrons can assume at 𝑇 = 0 𝐾 is the Fermi velocity, 𝑣𝐹 (i.e., the
velocity of the electrons at the Fermi energy):
1Τ
1 ℏ 3𝜋2 𝑁 3
2
(𝐸𝐹 = 𝑚𝑣𝐹 ) → 𝑣𝐹 =
2 𝑚 𝑉

• The sphere having 𝑣𝐹 as a radius represents, therefore, the Fermi surface.

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Semi quantum mechanical approach
Energy
increases 𝑘𝑧
• The Fermi sphere contains all occupied These states are NOT
outwards
occupied by electrons
electron states in the free electron gas.
• In equilibrium the valence electrons perform
random motions with no preferential velocity
in any direction. As a consequence, the
velocity vectors cancel each other pairwise at
equilibrium and no net velocity of the
electrons results. 𝑘𝑦
𝑘𝑥
• If no electric field is applied to the material,
the net momentum is zero. In this case, to all
the state with wave vector 𝑘 corresponds a These states are
occupied by electrons
state with wave vector −𝑘 in any direction.
This surface is the “Fermi Surface” which is the set of states that
are at the Fermi energy level. This separates the occupied states
from the empty ones.
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Semi quantum mechanical approach
• When an electric field is applied, the 𝑘-value (related to momentum 𝑝 = ℏ𝑘) changes, corresponding to a
displacement of the Fermi sphere by 𝛿𝑘. In this case, the electrons with energies near 𝐸𝐹 acquire a net
momentum, leading to the appearance of a net current in the material.

𝜉 (𝑥𝑖)
Velocity of electrons in two-
dimensional velocity space: (a)
equilibrium (no electric field) and
(b) when an electric field is
applied. The shaded areas to the
left and right of the 𝑣(𝑘)𝑦 -axis
are of equal size. They cancel
each other. The cross-hatched
area remains uncompensated.

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Semi quantum mechanical approach
• The Drude description of conduction thus needs a modification.
• In the classical picture one would assume that all electrons drift, under the influence of an electric field,
with a modest velocity.
• Quantum mechanics, instead, teaches us that only specific electrons participate in the conduction and
that these electrons drift with a high velocity which is approximately the Fermi velocity 𝑣𝐹 .
• The largest energy which the electrons can assume in a metal at 𝑇 = 0 𝐾 is the Fermi energy 𝐸𝐹 . A
large number of electrons actually possess this energy since the density of states and thus the
population density is highest around 𝐸𝐹 .
• Thus, only a little extra energy 𝐸 is needed to raise a substantial number of electrons from the Fermi
level into slightly higher states. Therefore, the energy (or the velocity) of electrons accelerated by the
electric field 𝜉 is only slightly larger than the Fermi energy 𝐸𝐹 (or the Fermi velocity 𝑣𝐹 ) so that for all
practical purposes the mean velocity can be approximated by the Fermi velocity.

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Semi quantum mechanical approach
• The displacement 𝑘 of the Fermi sphere in 𝑘-space under the influence of an electric field 𝜉 can be calculated
by:
𝑑𝑣 𝑑(𝑚𝑣) 𝑑𝑝 𝑑𝑘
𝐹=𝑚 = = =ℏ = −𝑞𝜉
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
which yields:
−𝑞𝜉 −𝑞𝜉 −𝑞𝜉
−𝑞𝜉
𝑑𝑘 = 𝑑𝑡 𝑜𝑟 Δ𝑘 = Δ𝑡 =
= 𝜏𝜏
ℏ ℏ ℏℏ
• Here 𝜏 is the time interval Δ𝑡 between two collisions or the relaxation time.
• Let us now calculate the current density 𝐽 following this approach.
𝐽 = −𝑞𝑣𝐹 𝑁 ∗
where 𝑁 ∗ is the number of electrons per volume displaced by the electric field as: 𝑁 ∗ = 𝑁 𝐸 Δ𝐸 𝐸𝐹

• This results in:

𝑑𝐸
𝐽 = −𝑞𝑣𝐹 𝑁 𝐸 Δ𝐸 𝐸𝐹 = −𝑞𝑣𝐹 𝑁 𝐸𝐹 Δ𝑘
𝑑𝑘 𝐸𝐹

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Semi quantum mechanical approach
• The 𝐸(𝑘) relationship for free electrons is given by:
ℏ2 𝑘 2
𝐸=
2𝑚
• For 𝑘 near 𝑘𝐹 (the Fermi wave vector):
𝑑𝐸 ℏ2 𝑘𝐹
≈ = ℏ𝑣𝐹
𝑑𝑘 𝐸𝐹
𝑚
N ~ E3/2
• This gives for the current:
𝐽 = −𝑞𝑣𝐹 2 𝑁 𝐸𝐹 ℏΔ𝑘

• Accounting for 𝑘 calculated above; one gets:

𝐽 = 𝑞 2 𝑣𝐹 2 𝑁 𝐸𝐹 𝜉𝜏

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Semi quantum mechanical approach
• One more consideration needs to be made. If the electric field-vector points into the negative 𝑣 𝑘 𝑥
direction, then only the components of those velocities which are parallel to the positive 𝑣 𝑘 𝑥 direction
contribute to the electric current.
• The 𝑣 𝑘 𝑦 components cancel each other pairwise. In other words, only the projections of the velocities
𝑣𝐹 on the positive 𝑣 𝑘 𝑥 axis (𝑣𝐹𝑥 = 𝑣𝐹 cos 𝜃) contribute to the current. Thus, we have to sum up all
contributions of the velocities in the first and fourth quadrant (see figure) which yields:
+𝜋Τ2
𝑑𝜃
𝐽= 𝑞2𝑁 𝐸 𝜉𝜏 න 𝑣𝐹 cos 𝜃 2
−𝜋Τ2 𝜋
𝑣𝐹 2 +𝜋Τ2
𝐽 = 𝑞 2 𝑁 𝐸 𝜉𝜏 න cos 𝜃 2 𝑑𝜃
𝜋 −𝜋Τ2
2 1 +𝜋Τ2
𝑣𝐹 𝜃
𝐽 = 𝑞 2 𝑁 𝐸 𝜉𝜏 sin 2𝜃 +
𝜋 4 2 −𝜋Τ2
1
𝐽 = 𝑞 2 𝑁 𝐸 𝜉𝜏𝑣𝐹 2
2
2D velocity space
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Semi quantum mechanical approach
• A similar calculation for a spherical Fermi surface yields:
1
𝐽 = 𝑞 2 𝑁 𝐸 𝜉𝜏𝑣𝐹 2
3
• Thus, the conductivity finally becomes with 𝜎 = 𝐽Τ𝜉
Remember from Drude model:
1 𝑁𝑒 𝑞 2 τ
𝜎 = 𝑞 2 𝑁 𝐸 𝜏𝑣𝐹 2 𝜎=
3 𝑚
• This quantum mechanical equation reveals that the conductivity depends on the Fermi velocity, the
relaxation time and the population density. The latter is as we know proportional to the density of states.
• The equation is more meaningful than the expression derived from the classical electron theory. Since it
contains the information that not all free electrons are responsible for conduction, that is the
conductivity in metals depends to a large extent on the population density near the Fermi
surface.

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Scattering phenomena
• The electrical resistivity 𝜌 = 1Τ𝜎 of a material increases
(a)
when the relaxation time  decreases.
• The relaxation time is related to the electron scattering
phenomena, i.e. the more scattering, the shorter is .
• Two major scattering mechanisms are encountered in solids: (b)
• Scattering by lattice vibrations - phonons, becomes
important at high temperature. When the temperature
increases, the lattice vibrations increase, and the (c)
resistance becomes higher.
• Scattering by impurities is dominant at low temperature.
When the amount of impurities increases, the electrons Movement of an electron through:
encounter more collisions, and the resistance is higher. (a) a perfect crystal
(b) a crystal heated to a high temperature
(c) a crystal containing atomic level defects.

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Scattering phenomena
• The rates of these collisions are often independent to a good approximation, so that if the electric field were
switched off, the momentum distribution would relax back to its ground state with the net relaxation time:
1 1 1
= +
𝜏 𝜏𝐿 𝜏𝑑
where 𝜏𝐿 and 𝜏𝑑 are the relaxation times for scattering by phonons and by imperfections/defects respectively.
• The net resistivity is given by:
𝜌 = 𝜌𝐿 + 𝜌𝑑
• Where 𝜌𝐿 is the resistivity caused by thermal phonons and 𝜌𝑑 is the resistivity caused by scattering of the
electron waves by static defects that disturb the periodicity of the lattice.
• This empirical observation expresses Mathiessen’s rule. According to this rule, resistivity arises from
independent scattering processes which are additive.
• In general 𝜌𝐿 is independent of the number of defects when their concentration is small, and 𝜌𝑑 is independent
of temperature.

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Temperature dependence of resistivity
• The electrical resistivity of a metal is composed
of a constant defect contribution 𝝆𝒅 and a
variable temperature contribution 𝝆𝑳 .

Defects
ρL contribution

Temperature dependence of the resistivity

of copper and various copper-nickel alloys.

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 Temperature dependence of resistivity
Room Temperature Temperature coefficient
• The resistivity of metals increases with the Metal resistivity  (.cm) of resistivity R (°C-1)
temperature due to increasing scattering by Be 4.0 x 10-6 0.0250
phonons. The slope of the electrical resistivity Mg 4.45 x 10-6 0.0037
curve vs. temperature curve is the temperature
Ca 3.91 x 10-6 0.0042
coefficient of resistivity (valid for a limited
Al 2.65 x 10-6 0.0043
temp range).
Cr 12.90 x 10-6 (@ 0°C) 0.0030
(Normalized to ρ0)

Fe 9.71 x 10-6 0.0065

Co 6.24 x 10-6 0.0053
Ni 6.84 x 10-6 0.0069
Cu 1.67 x 10-6 0.0043
Ag 1.59 x 10-6 0.0041
Au 2.35 x 10-6 0.0035
Pd 10.8 x 10-6 0.0037
The effect of temperature on the electrical resistivity of a W 5.3 x 10-6 (@ 27°C) 0.0045
metal with a perfect crystal structure. The slope of the curve
Pt 9.85 x 10-6 0.0039
is the temperature coefficient of resistivity (see table).

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Temperature dependence of resistivity
Room Temperature Temperature coefficient
Metal resistivity  (.cm) R (°C-1)
Be 4.0 x 10-6 0.0250
Mg 4.45 x 10-6 0.0037
Ca 3.91 x 10-6 0.0042
Al 2.65 x 10-6 0.0043
Cr 12.90 x 10-6 (@ 0°C) 0.0030
Fe 9.71 x 10-6 0.0065
Co 6.24 x 10-6 0.0053
Ni 6.84 x 10-6 0.0069
Pt100 RTD, the most used thermometer in industrial Cu 1.67 x 10-6 0.0043
processes, consists of a Pt stripe with 100 Ω @ 0°C.
Ag 1.59 x 10-6 0.0041
This device is famous for its accuracy, repeatability,
Au 2.35 x 10-6 0.0035
and stability. The sensitivity is 0.385 Ω/°C
Pd 10.8 x 10-6 0.0037
W 5.3 x 10-6 (@ 27°C) 0.0045
Pt 9.85 x 10-6 0.0039

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Resistivity
• Solute atoms are usually randomly distributed in
the alloy, leading to the increase of the resistivity
with increasing amount of solute element.
• The solute behaves like an impurity that
increases the scattering of electrons.
• When the valence charge of the impurity
increases, the scattering probability increases,
due to the electron-impurity Coulomb potential,
and the effect on the resistivity increases:
𝑍𝑒 2 1
𝑉 𝑟 = ⟹𝜏∝
4𝜋𝜀𝑟 𝑁𝑖𝑚𝑝 𝑍 2 Resistivity of various silver alloys (schematic). Solvent and
solute are all from the fifth period. (a) Resistivity versus atomic
% solute, (b) resistivity change due to 1 atomic % of solute.

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Resistivity 𝝆
disordered

• When the solute atoms are not

randomly distributed and ordering
occurs, i.e. if solute atoms are ordered
periodically arranged in the matrix, the
electrons are coherently scattered,
causing a reduction of the resistivity.

Cu Cu3Au CuAu Au
• This is e.g. the case in some Cu-Au
alloys, shows chemical ordering into
defined phases (e.g. Cu3Au or CuAu)
with lower resistivity. Disordered Ordered Ordered Disordered
structure structure structure structure
(FCC) (FCC) (BCT) (FCC)

Schematic representation of the resistivity of ordered

and disordered copper-gold alloys.

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Metals
Skin effect

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AC conductivity
• For Direct Current (DC) through a wire, the
resistance of the wire can be calculated from its
length, diameter and resistivity since it may be
assumed that the electric current is essentially
uniform over the cross-section of the wire.
• However, for Alternating Current (AC), the
interaction of electric and magnetic fields in the
conductor distributes the current preferentially to
the outside of the wire. The electric current flows
mainly at the "skin" of the conductor, between
the outer surface and a level called the skin
depth. This skin effect increases with frequency
so that for high Radio Frequencies (RF) a thin
outside layer of the conductor carries essentially
all the current.
36
δ
d
(a) (b)
DC (a) and AC (b) flow in a conductor; illustrating the
concept of the skin effect
• The AC current density 𝐽 drops exponentially
from the outside radius in a way that can be
quantified in terms of a parameter called the
"skin depth“ represented as 𝛿 :
𝐽 = 𝐽𝑆 𝑒 −𝑑Τ𝛿
where 𝐽𝑆 is the current density at the surface and
𝑑 is the depth beneath the surface.
• The skin effect causes the effective resistance of
the conductor to increase at higher frequencies
where the skin depth is smaller, thus reducing
the effective cross-section of the conductor.
Materials Physics and Technology for Nanoelectronics
Metals
Skin effect: electrical engineering view
• The skin effect can be understood by looking at the
magnetic fields generated by the current flow.
Consider a cylindrical conductor which is carrying a
current 𝐼 into the paper (×). The magnetic field 𝐵 of 𝐼
is clockwise. Consider two magnetic field values 𝐵1
and 𝐵2 , which are shown in the figure. 𝐵1 is inside the
core and 𝐵2 is just outside the conductor.

• Assume that the conductor is divided into two

conductors. The hypothetical cut is taken just outside
of 𝐵1 . The conductor is now cut into a hollow cylinder
and a smaller solid cylinder. The currents 𝐼𝑖 and 𝐼𝑜 in
the solid and hollow cylinders sum to 𝐼 . We can
arrange things and choose 𝐵1 such that our cut gives
𝐼𝑖 = 𝐼𝑜 = 1Τ2 𝐼.
Illustration of the skin effect. A hypothetical cut
produces a hollow outer cylinder and a solid inner
cylinder. Cut is placed where it would give equal
current in each section. The two sections are in
parallel so that the currents in (b) and (c) sum to
that in (a).

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Skin depth: electrical engineering view
• Obviously, 𝐼𝑖 flowing in the inner conductor is threaded (or
linked) by both 𝐵1 and 𝐵2 . On the other hand, the outer
conductor is only threaded by 𝐵2 , simply because 𝐼𝑜 flows in the
hollow cylinder, which means that 𝐼𝑜 is not threaded by 𝐵1 .
Clearly, 𝐼𝑖 is threaded by more magnetic field than 𝐼𝑜 and thus
has a higher inductance.
• Recall that inductance is defined as the total magnetic flux
threaded per unit current. Consequently, an AC current will
prefer paths near the surface where the inductive impedance is
smaller. As the frequency increases, the current is confined
more and more to the surface region.

At high frequencies, the core region

exhibits more inductive impedance than
the surface region, and the current flows in
the surface region of a conductor defined
approximately by the skin depth, 𝛿.

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Skin depth: electromagnetic view
• Each current line creates a magnetic field around itself, which in turns creates Eddy currents that partially
opposed the original current. The inner currents experience the opposing Eddy currents from outer and
inner magnetic fields, being cancelled more efficiently.

• For a given conductor, we can assume that most of the current flows in a surface region of depth 𝛿,
called the skin depth, as indicated in the figure. In the central region the current will be negligibly small.
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Metals
Electromagnetic waves in conductors
• The skin depth obviously depends on the
frequency 𝜔. We will study this by calculating the
absorption of an electromagnetic wave that
enters perpendicular into the conductor.
• To find 𝛿, we must solve Maxwell’s equations in a
conductive medium. These equations describe
what happens when an electromagnetic wave
enters a conductor.
40
• To translate Maxwell’s equations from vacuum to
a material, we need to replace the permittivity
and permeability of vacuum 𝜀0 and 𝜇0 by 𝜀 and 𝜇,
the permittivity and permeability of the material.
Together with Ohm’s law, the Ampere-Maxwell
equation becomes:
𝜕 2𝐸 𝜕𝐸
2
∇ 𝐸 = 𝜇𝜀 2 + 𝜇𝜎
𝜕𝑡 𝜕𝑡
which is known as the damped wave equation.
• We will assume that a plane electromagnetic
wave of the form 𝐸 = 𝐸0 𝑒 −𝑖 𝜔𝑡−𝑘𝑧 is traveling in
the 𝑧-direction inside this conducting material.
• A wave will be a solution of the damped wave
equation if:
𝑘 2 = 𝜔2 𝜇𝜀 + 𝑖𝜔𝜇𝜎
Materials Physics and Technology for Nanoelectronics
Metals
Electromagnetic waves in conductors (extra)
• Maxwell equations:
1. Gauss’ law for electricity:

2. Gauss’ law for magnetism:

3. Faraday’s law of induction:

4. Ampere’s law:

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Metals
Electromagnetic waves in conductors (extra)

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Metals
 Materials Physics and Technology for Nanoelectronics
43
Metals
Electromagnetic waves in conductors
• A wave will be a solution of the damped wave equation if: 𝑘 2 = 𝜔2 𝜇𝜀 + 𝑖𝜔𝜇𝜎

• For a good conductor and in the case that 𝜔 is not too high, the second term will be dominant. In this limit and
using 𝑖 = ± 1 + 𝑖 Τ 2 we get:
𝑒 −𝑧Τ𝛿
1+𝑖 1+𝑖 (k is complex)
1Τ2 1Τ2 𝜹↓
𝑘 ≈ 𝑖𝜔𝜇𝜎 =± 𝜔𝜇𝜎 =±
2 𝛿
1Τ2
2
𝛿=
𝜔𝜇𝜎
• The solution for the damped wave equation than becomes:
𝜔𝑡−𝑧Τ𝛿
𝐸 = 𝐸0 𝑒 −𝑖 𝑒 −𝑧Τ𝛿
• This is an oscillatory wave, for which the amplitude declines exponentially. The factor that indicates an
exponential decay arises from the imaginary part of the wave number 𝑘. The parameter 𝛿 defines the scale of
the decline. Therefore, 𝜹 is the skin depth. It decreases with increasing σ and increasing frequency.

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Electromagnetic waves in conductors (extra)

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Metals
Electromagnetic waves in conductors
• The electromagnetic radiations are thus
attenuated as they penetrate in the conductor,
due to the oscillating currents produced in
response to the applied oscillating electric field.

• Skin depths are of the order of centimeters at

low frequencies (100 Hz), few microns at 100
MHz, and only a few nanometers for visible light
(~1014 Hz).

Skin depth vs. frequency for a few materials.

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Metals
Transparent metals
• Can a metal be transparent to radiation then?
• A wave will be a solution of the damped wave equation if: 𝑘 2 = 𝜔2 𝜇𝜀 + 𝑖𝜔𝜇𝜎

• For a good conductor and in the case that 𝜔 is also high, both terms survive. But σ must be revisited…
• For very high frequency, rather than experiencing many collisions in each cycle of the field as is the case
in the low frequency regime, the electrons will now experience many cycles of the field in-between
collisions.
• In the low frequency regime, the electrons will reach a steady-state due to the energy loss by the
collisions.
• In the high frequency range, this is no longer true and in this limit the electrons will start to behave
like electrons in free space.
E @ t1 E @ t1
For low ω: -
For high ω:
e
e-

E @ t2 E @ t2

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Metals
Transparent metals
• Between collisions, Newtonian mechanics will apply, and an oscillating electric field 𝐸 = 𝐸0 𝑒 −𝑖𝜔𝑡 will give
the electrons an acceleration such as :
𝑑𝑣
𝑚 = −𝑞𝐸0 𝑒 −𝑖𝜔𝑡
𝑑𝑡
• Integrating this acceleration to get the drift velocity yields an oscillatory drift velocity of :
𝑞𝐸0 −𝑖𝜔𝑡
𝑣𝑓 = 𝑒
𝑖𝜔𝑚
• Then the current density 𝐽 = −𝑞𝑁𝑒 𝑣𝑓 becomes:
𝑁𝑒 𝑞 2 𝐸0 −𝑖𝜔𝑡
𝐽=− 𝑒
𝑖𝜔𝑚
• The AC conductivity 𝜎𝐴𝐶 = 𝐽Τ𝐸 then reads:
𝐽 𝑁𝑒 𝑞 2 𝑖𝜎𝐷𝐶 𝑁𝑒 𝑞 2 𝜏
𝜎𝐴𝐶 = = − = where 𝜎𝐷𝐶 =
𝐸 𝑖𝜔𝑚 𝜔𝜏 𝑚

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Transparent metals (extra)

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Metals
Transparent metals
• 𝜎𝐴𝐶 = 𝐽Τ𝐸 is imaginary, meaning that 𝐽 and 𝐸 are 𝜋Τ2 out-of-phase

• We then obtain, using the Ampere-Maxwell equation:

−𝑖 𝜔𝑡−𝑘𝑧 2 2 2
𝑁𝑒 𝑞 2 𝜇
𝐸 𝑧 = 𝐸0 𝑒 with 𝑘 = 𝜔 𝜇𝜀 + 𝑖𝜔𝜇𝜎𝐴𝐶 = 𝜔 𝜇𝜀 −
𝑚
• This equation can be re-written as:
2 (k can be real or
𝜔𝑝 𝑁𝑒 𝑞 2
𝑘 2 = 𝜔2 𝜇𝜀 1 − 2 where 𝜔𝑝 = imaginary depending
𝜔 𝑚𝜀 on the frequency!)
• Where we have introduced the plasma frequency 𝜔𝑝 .

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Metals
Transparent metals
𝜔𝑝 2
• From the equation 𝑘2 = 𝜔2 𝜇𝜀 1− 𝜔2
, 𝑘 is real (i.e. 𝑘 2 is positive) when 𝜔 > 𝜔𝑝 .

• In this case, there is no attenuation of the amplitude of the oscillating electric field,
the conductor becoming transparent.
• Calculating 𝜔𝑝 for most metals gives plasma frequencies above the frequencies of
visible light.

1 Metal 𝜔𝑝 (s-1)
𝑅, Reflectivity

Opaque Transparent
Li 1.1 x 1016
Na 8.7 x 1015
K 5.7 x 1015
Mg 1.6 x 1016
0 𝜔𝑝 𝜔 Al 2.3 x 1016
Angular frequency

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Resistivity of thin metal films

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Resistivity of thin metal films
• The resistivity of a material, as listed in materials tables and in our analysis of conduction, refers to the
resistivity of the material in bulk form; that is, any dimension of the specimen is much larger than the
mean free path for electron scattering.
• In such cases resistivity is determined by scattering from lattice vibrations and, if significant,
scattering from various impurities and defects in the crystal.
• In many applications, especially in microelectronics, we are interested in the resistivity of a metal film in
which the thickness of the film or the average size of the grains is comparable to the mean distance
between scattering events 𝑙𝑏𝑢𝑙𝑘 (the mean free path) in the bulk material.
• In such cases, the resistivity of the metal film is greater than the corresponding resistivity of the bulk
crystal.
• A good example is the resistivity of interconnects and various metal films used in the “shrinking”
world of microelectronics, in which more and more transistors are packed into a single Si crystal,
and various device dimensions are scaled down.

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Resistivity of thin metal films
Polycrystalline Films and Grain Boundary Scattering

• In a highly polycrystalline
sample the conduction
electrons are more likely
to be scattered by grain
boundaries than by other
processes.

(a) Grain boundaries cause scattering of the electron and therefore add to the
resistivity by Matthiessen’s rule. (b) For a very grainy solid, the electron is scattered
from grain boundary to grain boundary and the mean free path is approximately equal
to the mean grain diameter. (c) TEM (transmission electron microscope) image of an
annealed polycrystalline Cu thin film of thickness 41.7 nm. The films structure is
composed of grains with an average size 87.7 nm. The resistivity of this film is 30 nΩ
m, higher than the bulk resistivity of Cu (17 nΩ m).
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Metals
Resistivity of thin metal films
Polycrystalline Films and Grain Boundary Scattering
• Consider the resistivity due to scattering from grain boundaries alone. The conduction electron is free within a
grain but becomes scattered at the grain boundary. Its mean free path 𝑙𝑔𝑟𝑎𝑖𝑛 is therefore roughly equal to the
average grain size 𝑑. If  = 𝑙𝑐𝑟𝑦𝑠𝑡𝑎𝑙 is the mean free path of the conduction electrons in the single crystal (both due
to phonons and impurities), the total mean free path in a polycrystalline material (single crystal+boundaries) is:
1 1 1 1 1
= + = + (Matthiessen’s rule)
𝑙 𝑙𝑐𝑟𝑦𝑠𝑡𝑎𝑙 𝑙𝑔𝑟𝑎𝑖𝑛 𝜆 𝑑

• The resistivity is inversely proportional to the mean free path which means that the resistivity of the bulk single
crystal 𝜌𝑐𝑟𝑦𝑠𝑡𝑎𝑙 ∝ 1Τ𝜆 and the resistivity of the polycrystalline 𝜌𝑝𝑜𝑙𝑦 ∝ 1Τ𝜆 + 1Τ𝑑 . Thus,
𝜌𝑝𝑜𝑙𝑦 𝜆
=1+
𝜌𝑐𝑟𝑦𝑠𝑡𝑎𝑙 𝑑
• Polycrystalline metal films with a smaller grain diameter 𝑑 (i.e., more grainy films) will have a higher resistivity.

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Resistivity of thin metal films
Polycrystalline Films and Grain Boundary Scattering
• In a more rigorous theory, we have to consider a number of effects. It may take more than one scattering
at a grain boundary to totally randomize the velocity, so we need to calculate the effective mean free path
that accounts for how many collisions are needed to randomize the velocity.
• There is a possibility that the electron may be totally reflected back at a grain boundary (bounce back).
• Suppose that the probability of reflection at a grain boundary is 𝑅 and 𝑑 is the average grain size
(diameter), then the resistivity can be calculated by the Mayadas–Shatzkes formula:
−1
𝜌𝑝𝑜𝑙𝑦 3 1
= 1 − 𝛽 + 3𝛽 2 − 3𝛽 3 ln 1 +
𝜌𝑐𝑟𝑦𝑠𝑡𝑎𝑙 2 𝛽
in which the quantity 𝛽 is defined by:
𝜆 𝑅
𝛽=
𝑑 1−𝑅

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Resistivity of thin metal films
Polycrystalline Films and Grain Boundary Scattering
• The 𝛽 in this equation represents the 𝜆Τ𝑑 ratio adjusted for the reflection to transmission ratio of the
electron at the grain boundary.
• When the grain size is large, 𝛽 is small and the equation simplifies to:
𝜌𝑝𝑜𝑙𝑦 3
≈1+ 𝛽
𝜌𝑐𝑟𝑦𝑠𝑡𝑎𝑙 2
• For highly polycrystalline films, the grain size would be small and 𝛽 ≫ 1:
𝜌𝑝𝑜𝑙𝑦 4
≈ 𝛽
𝜌𝑐𝑟𝑦𝑠𝑡𝑎𝑙 3
• These equations implies that the Matthiessen’s rule is reasonably well obeyed when the grains are larger
than the mean free path 𝜆.

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Resistivity of thin metal films (extra)

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Resistivity of thin metal films (extra)

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Resistivity of thin metal films
Surface Scattering (a)
• Consider the scattering of electrons from the
surfaces of a conducting film.
• The mean free path 𝑙𝑠𝑢𝑟𝑓 of the electron will depend
on its direction right after the scattering process. (b)
For example, if the angle 𝜃 after surface scattering
is zero, (the electron moves transversely to the film
length), then 𝑙𝑠𝑢𝑟𝑓 = 𝐷. In general, the mean free
path 𝑙𝑠𝑢𝑟𝑓 will be 𝐷 Τcos 𝜃 as illustrated in the figure.

(a) Conduction in thin films may be controlled by

scattering from the surfaces. (b) The mean free path of
the electron depends on the angle 𝜃 after scattering.

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Resistivity of thin metal films
Surface Scattering • However, the electron’s direction right after the
surface scattering is not totally random because
• Consider the surface scattering example where
we know that the electron cannot leave the film;
the electron is scattered from the bottom surface.
thus, 𝜃 is between −𝜋Τ2 and +𝜋Τ2 and cannot
If the scattering of the electron were truly
be between −𝜋 and +𝜋. The electron’s velocity
random, then the probability of being scattered in
after the first surface scattering must have a y
a direction back into the film, that is, in the +𝑦
component along +𝑦 and not along − 𝑦. The
direction, would be 0.5 on average.
electron can only acquire a velocity component
along − 𝑦 again after the second surface
scattering at the bottom interface.

• It therefore takes two collisions to randomize the

velocity, which means that the effective mean
free path must be twice as long, that is 2𝐷 Τcos 𝜃.

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Resistivity of thin metal films
Surface Scattering
• To find the overall mean free path 𝑙 for calculating the resistivity we must use Matthiessen’s rule. If 𝜆 is
the mean free path of the conduction electrons in the bulk crystal (no surface scattering), then
1 1 1 1 cos 𝜃
= + = +
𝑙 𝜆 𝑙𝑠𝑢𝑟𝑓 𝜆 2𝐷
• We have to average for all possible 𝜃 values per scattering, that is, 𝜃 from −𝜋Τ2 to +𝜋Τ2. Once this is
done, we can relate 𝑙 to 𝜆 as follows: 1 2
𝜋
2
1 1 1 න 𝑐𝑜𝑠𝜃𝑑𝜃 =
𝜋 −𝜋 𝜋
= + 2
𝑙 𝜆 𝜋𝐷
• The resistivity of the bulk crystal is 𝜌𝑐𝑟𝑦𝑠𝑡𝑎𝑙 ∝ 1Τ𝜆, and the resistivity of the film is 𝜌 ∝ 1Τ𝑙. Thus,

𝜌 1 𝜆
= 1+
𝜌𝑐𝑟𝑦𝑠𝑡𝑎𝑙 𝜋 𝐷

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Resistivity of thin metal films
Surface Scattering
• A more rigorous calculation modifies the numerical factor 1Τ𝜋 and also considers what fraction P of
surface collisions is specular and results in what is known as the simplified Fuchs-Sondheimer
equation
𝜌 3𝜆 𝜆
=1+ 1 − 𝑃 which is valid for > 0.3
𝜌𝑐𝑟𝑦𝑠𝑡𝑎𝑙 8𝐷 𝐷
• This equation is in Matthiessen’s rule format, which means that the second term is the fractional
contribution of the surfaces to the resistivity. The parameter 𝑃 is called the specularity parameter.
• For elastic or specular scattering 𝑃 = 1 and there is no change in the resistivity.
• When 𝑃 = 0, the scattering at the surface is called diffusive, and represents the case when the
momentum gained from the field is fully lost upon scattering; and the contribution of surface
scattering is maximum.
• The equation involves scattering from the two interfaces of the film. In general, the two interfaces will not
be identical and hence will have different 𝑃 coefficients. Further, if the surface is rough, then the
scattering will be more severe at the surfaces and the equation needs to be adapted accordingly.

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Thermal conductivity

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Thermal conductivity of metals
• Experience tells us that metals are both good electrical and
good thermal conductors. We may therefore surmise that the
free conduction electrons in a metal must also play a role in heat
conduction.
• The transport of heat in a metal is accomplished mostly by the
electron gas, whereas in nonmetals, the conduction is due
mostly to lattice vibrations.
• When a metal piece is heated at one end, the amplitude of the
atomic vibrations, and thus the average kinetic energy of the Thermal conduction in a metal involves
electrons, in this region increases. transferring energy from the hot region to
the cold region by conduction electrons.
• Electrons gain energy from energetic atomic vibrations when the More energetic electrons (shown with longer
two collide. By virtue of their increased random motion, these velocity vectors) from the hotter regions
energetic electrons then transfer the extra energy to the colder arrive at cooler regions, collide with lattice
regions by colliding with the atomic vibrations there. Thus, vibrations, and transfer their energy. Lengths
electrons act as “energy carriers.” of arrowed lines on atoms represent the
magnitudes of atomic vibrations.

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Thermal conductivity of metals
• The thermal conductivity of a material measures the ease
with which heat, that is, thermal energy, can be transported
through the medium. Consider a metal rod which is heated
at one end. Heat will flow from the hot end to the cold end.
The rate of heat flow, 𝑄′ = 𝑑𝑄Τ𝑑𝑡, through a thin section of
thickness 𝛿𝑥 is proportional to the temperature gradient
𝛿𝑇Τ𝛿𝑥 and the cross-sectional area 𝐴, so:
𝑄 ′ = −𝐴𝜅 𝛿𝑇Τ𝛿𝑥
where 𝜅 is a material-dependent constant of proportionality Heat flow in a metal rod heated at one end.
that we call the thermal conductivity [W m-1 K-1] Consider the rate of heat flow, 𝑑𝑄 Τ𝑑𝑡, across a
thin section 𝛿𝑥 of the rod. The rate of heat flow
is proportional to the temperature gradient
𝛿𝑇Τ𝛿𝑥 and the cross-sectional area A.
• The negative sign indicates that the heat flow direction is
that of decreasing temperature. The driving force for the
heat flow is the temperature gradient 𝛿𝑇Τ𝛿𝑥.

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Thermal conductivity of metals Low α

• The thermal conductivity depends on the thermal

diffusivity α, the specific heat capacity cp and the
density ρ [kg/m3] as:

𝜅 = 𝛼𝑐𝑝 𝜌

• The thermal diffusivity α in [mm2/s] describes how

quickly a material reacts to a change in temperature.
It can be seen also as the conductivity divided by the
energy that the system can store per volume and High α
kelvin.
• The specific heat capacity cp [ in J/K/kg] is the
amount of heat required to raise the temperature of 1
kilogram of a substance by 1 kelvin.

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Thermal conductivity of metals
• If we compare the expression for 𝑄 ′ with Ohm’s law for the
electric current 𝐼, we see that:
𝐼 = −𝐴𝜎 𝛿𝑉Τ𝛿𝑥
which shows that in this case, the driving force is the potential
gradient is the electric field.
• In metals, electrons participate in the processes of charge and
heat transport, which are characterized by 𝜎 and 𝜅, respectively.
Therefore, it is not surprising to find that the two coefficients are
related by the Wiedemann–Franz– Lorenz law, which is:
𝜅 = 𝐿𝜎𝑇 (*) Thermal conductivity 𝜅versus electrical conductivity 𝜎
for various metals (elements and alloys) at 20 °C.
where L= 𝜋 2 𝐾𝐵 2 Τ3𝑞2 = 2.44 × 10−8 𝑊Ω𝐾 −2 is a constant called the The solid line represents the WFL law. These
Lorenz number (or the Wiedemann-Franz-Lorenz coefficient). experimental results on a wide variety of metals,
(*)Thisrelationship refers to thermal transport by electrons. For materials ranging from pure metals to various alloys, show that
other than metals where the thermal conductivity presents also a phonon the WFL law is reasonably well obeyed at close to
contribution, κ becomes κe. room temperature and above.

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 Thermal conductivity of metals
• Since the electrical conductivity in pure metals is
inversely proportional to the temperature, we can
immediately conclude that the thermal conductivity of
these metals must be relatively temperature
independent at room temperature and above.
𝜌 ≈ 𝛼𝑅 𝑇
(Normalized to ρ0)

Thermal conductivity versus temperature for two

pure metals (Cu and Al) and two alloys (brass
and Al–14% Mg). It can be seen that for Cu and
1 𝐿 Al, above ∼100 K, the thermal conductivity
𝜅=𝐿 𝑇≈ → 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 becomes temperature independent.
𝜌 𝛼𝑅

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Thermal conductivity of nonmetals
• Non-metals do not have any free conduction electrons inside the crystal to transfer thermal energy from
hot to cold regions of the material. In non=metals, the energy transfer involves lattice vibrations, that is,
atomic vibrations of the crystal (phonons).

Conduction of heat in insulators involves the generation and propagation of

atomic vibrations through the bonds that couple the atoms (an intuitive figure).

• As we know from the kinetic molecular theory, all the atoms would be vibrating, and the average
vibrational kinetic energy would be proportional to the temperature. Intuitively, as depicted in the figure,
when we heat one end of a crystal, we set up large-amplitude atomic vibrations at this hot end. The
springs couple the vibrations to neighboring atoms and thus allow the large-amplitude vibrations to
propagate, as a vibrational wave, to the cooler regions of the crystal.
• In general: κ= κe + κph
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Superconductors

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Superconductors
• Superconductors are materials whose resistivities become immeasurably small or actually become zero
below a critical temperature, 𝑻𝒄. The superconducting transition is reversible.
• The superconducting state has to be considered as a separate state, distinct from the liquid, solid, or
gaseous states. It has a higher degree of order - the entropy is zero.

• 75 years after the first discovery of superconductivity in mercury

(H.K. Onnes, Leiden, Holland, 1911) a new class of
superconductors was found by Bednorz and Müller (IBM Zurich,
Switzerland, 1986) which involved copper oxide-based ceramics.
These materials displayed a transition temperature of 35 K, 12K
above what has been known so far.
• Within a few years, new copper oxide-based compounds were
found that were named 1-2-3 superconductors because of the
characteristic molar ratios between rare earth to alkaline earth to
copper. Eventually, ceramic materials having 𝑇𝑐 above 77 K (liquid
The zero-resistance transition of Hg N temp) were synthesized, which were euphorically called “high-𝑇𝑐
measured in 1911 by Kamerlingh Onnes. superconductors”.
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Superconductors

The Nobel Prize in Physics 1987 was awarded jointly to

J. Georg Bednorz and K. Alexander Müller "for their
important break-through in the discovery of
superconductivity in ceramic materials."

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 Timeline of superconductivity
DOI:10.6084/m9.figshare.2075680.v2

Overview of superconducting critical temperatures for a variety of superconducting

materials since the first discovery in 1911.
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Superconductors
• More recently, a new class of superconductors, which is based on layers of iron and arsenic (among
others) has been discovered. Examples are parent compounds consisting of LaOFeAs, BaFe2As2, FeSe,
and iron phosphide (FeP). In many respects, these so called pnictides (i.e. compounds of the nitrogen
group), also called iron-based superconductors or ferropnictides have some properties similar to the
cuprates (compounds based on copper anions).
• LaOFeAs is not superconducting but becomes superconducting when some of the oxygen is replaced by
up to 11% fluorine (F) with 𝑇𝑐 = 26 K.
• Replacing the lanthanum with cerium, samarium, neodymium and/or praseodymium leads to a 𝑇𝑐 of
about 52 K.
• Doped FeSe has a 𝑇𝑐 of 8 K at normal pressure and a 𝑇𝑐 of 27 K under high pressure. Moreover, the
parent compound is antiferromagnetic. This property is destroyed by increased doping, leading to
superconductivity.

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Superconductors
• Conventional superconductivity results from an effective attractive interaction between the electrons.
This attraction comes about due to phonons - quantized vibrations of the ion lattice. It can be shown that
the most energetically favorable situation for this to occur is when the two electrons have a total spin
of zero.
• These interactions lead to correlations between pairs of electrons of opposite spin (forming a singlet)
and oppositely directed wavevectors, 𝑘 and −𝑘 near the Fermi surface, forming ”Cooper pairs”. Since
the exclusion principle does not apply to particles with integer spin, there is no restriction on the energy
state that the Cooper pair can occupy. In particular, at low temperatures thermal agitation is minimal,
and all of the Cooper pairs can occupy the lowest possible energy state. The Cooper pairs act like
composite bosons and below the critical temperature, 𝑇𝑐 , are described by a single effective ground
state wavefunction. That wavefunction may be treated as the order parameter of the superconducting
state and is complex, consisting of an amplitude and a phase.

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Superconductors
• BCS (John Bardeen, Leon Cooper, and Robert Schrieffer )
theory: The rigorous quantum mechanical explanation shows
that the effect is due to electron–phonon interactions, with the
phonon being the collective motion of the positively-charged
lattice. The energy of the pairing interaction is quite weak, of
the order of 10−3 eV, and thermal energy can easily break the
pairs. So only at low temperatures, in metal and other
substrates, are a significant number of the electrons in
Cooper pairs.
• The electrons in a pair are not necessarily close together;
because the interaction is long range, paired electrons may
still be many hundreds of nanometers apart. This distance is
usually greater than the average inter-electron distance, so
many Cooper pairs can occupy the same space.

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Superconductors

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Superconductors
• Although Cooper pairing is a quantum effect, the
reason for the pairing can be seen from a simplified
classical explanation. An electron in a metal normally
behaves as a free particle. The electron is repelled
from other electrons due to their negative charge, but it
also attracts the positive ions that make up the rigid
lattice of the metal.
• This attraction distorts the ion lattice, moving the ions
slightly toward the electron, increasing the positive
charge density of the lattice in the vicinity. This positive
charge can attract other electrons. At long distances, A visual model of the Cooper pair attraction has a
this attraction between electrons due to the displaced passing electron which attracts the lattice, causing
ions can overcome the electrons' repulsion due to their a slight ripple toward its path. Another electron
negative charge, and cause them to pair up. passing in the opposite direction is attracted to that
displacement (they exchange the phonon).

http://hyperphysics.phy-astr.gsu.edu/hbase/Solids/coop.html#c4

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 Superconductors
• Elimination of the superconducting state does not only occur
by raising the temperature, but also by subjecting the
material to a strong magnetic field. The critical magnetic Hc0
field strength, 𝐻𝑐 , above which superconductivity is
destroyed, depends upon the temperature at which the
material is held. In general, the lower the sample
temperature, the higher the critical field 𝑯𝒄 .
• One finds:
𝑇2
𝐻𝑐 = 𝐻𝑐0 1 −
𝑇𝑐 2 Tco
Where Hc0 is the critical magnetic field strength at 0 K.
Ceramic superconductors usually have a smaller 𝐻𝑐 than Dependence of critical field strength, 𝐻𝑐 , at
metallic superconductors, i.e., they are more vulnerable to which superconductivity is destroyed, in
lose superconductivity by a moderate magnetic field. relation to the temperature of the specimen.

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Superconductivity
Ic
• Moreover, another limiting parameter exists, namely,
the critical current 𝑰𝒄, above which superconductivity Io
disappears.

• All taken, an interrelationship between temperature,

current, and magnetic field strength is observed: an
increase in one of these parameters decreases the To Tc
critical value of the remaining two.
Ho
Hc
• In other words, superconductivity is only present
when temperature, magnetic field strength, and The limits of superconductivity are defined in a
current remain within a “critical space” in a T-H-I- critical T-H-I-diagram.
diagram.

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Materials Physics and Technology for Nanoelectronics

Clement Merckling
clement.merckling@kuleuven.be
imec & KU Leuven (MTM)
Kapeldreef 75, B-3001 Leuven

Francisco Molina-Lopez
francisco.molinalopez@kuleuven.be
MTM Functional Materials
Kasteelpark Arenberg 44, B-3001 Leuven