Basic assumptions of Drude model
* A“ gas of conduction electrons of mass m, which move against a background of heavy
immobile ions
Electron density =0.6022x10™ 7a
0.602210 Avogadro's number
Pn Mass density n gm?
A ‘Atomic mass in g/mole
Z Number of election each alom conrbute
qT Radius ofa sphore whose volume is equa othe volume per conduction electron
‘Tho density is typically 10° times greater than those of a classical gas at normal T and P. v
Electrical conductivity
Drude model: the simplest treatment of the electrical conductivity.
Four major assumption:
. Electrons are treated as classical particles within a free-electron approximation:
neglect the interactions with other electrons and ions;
no extemal electromagnetic fields - move uniformly in a straight line. In the
presence of fields - move according to Newton's laws
Electrons move free only between collisions with scattering centers. Collisions, are
instantaneous - abruptly alter the electron velocity.
A particular type of scattering centers does not matter in the Drude model. Simply
assume that there is some scattering mechanism.
Electron experiences a collision with a probability per unit time 1/ t. The time t —
an average time between the two consecutive scattering events - known as. the
collision time (relaxation time). The relaxation time t is taken to be independent of
electron's position and velocity.
Electrons achieve thermal equilibrium with their surroundings only through
collisions. These collisions are assumed to occur in a simple way: immediately
after each collision an electron emerges with a velocity that is not related to its
velocity before the collision, but randomly directed and with a speed corresponding
to the temperature at the place where the collision occurred. Application of the Drude model for reac conductivity ina a
2 1
Ohm's law: j= cE a
o—conductivity; p=1/o - resistivity ° L .
Jj =WA; V,-V, = EL, R=W/oA = pl/A > I= (V2-Vi/R
n electrons per unit volume all move with velocity v => j || v
inatime dt n(vdf)A electrons will cross an area 4 perpendicular to
the direction of flow => charge crossing A in dt will be -nevAdt >
j=-nev vis the average electronic velocity or drift velocity
Let t - time elapsed since electron's last collision.
Its velocity willbe — vp—eEt/m (vo is velocity immediately after
the last collision — random — no contribution to drift velocity)
average of tis the ya Et > j= neEr oe ner
relaxation time t om m m t=—_; T ~~ 10" 10 10" sec at RT
pne
123,
Moan freopath / =VoT aime = kel
Vp ~ 10? cm/sec. [-1-10AatAT
Estimate of vpis an order of magnitude too small
Actual !~ 10° A at low temperature, a thousand times the spacing between ions
+ Use Drude model without any precise understanding of the cause of collisions.
+ 7 independent quantities yield more reliable information
m
+ 7 calculated using 7=——> is accurate
pne’
+ Be cautious about quantities such as average electron velocity v, and electron specific heat c, The Drude model description of the thermal conductivity of meta
The most important success of Drude’s model was its explanation of the
experimental Wiedemann-Franz law. The WF law states that the ratio
between the thermal (ic) and electrical (a) conductivities is proportional to
the temperature with an almost identical coefficient of proportionality for
many metals.
The ratio * is called Lorenz number.
The basic assumption of Drude is:
> The conduction electrons (the electron gas) are the main heat conductors
(the heat conductivity of the ions may be neglected).
> This assumption is justified by the fact that metals are better heat
conductors than insulators. The Drude model description of the thermal conductivity of metals
Consider the rod illustrated above:
If T;, > Tp the thermal energy will flow from the left to the right until the bar
has a uniform temperature (thermal energy). If the ends are connected to
thermal baths with different temperatures a steady state flow of thermal
energy will be achieved (from hot to cold).
The thermal current density, 7%, is defined to be a vector parallel to the direction
of the thermal energy flow, whose magnitude is equal to the amount of thermal
energy per unit area per unit time crossing a plane perpendicular to the direction
of the flow.
For small temperature gradients Fourier’s law states that:
jl =-KVT
Note the similarity to the charge current density. Electronic thermal conductivity
Heat current density, jg. i.e. the amount of thermal energy crossing a
unit area per unit time is proportional to the temperature gradient:
io =—K — where K is the thermal conductivity
Ee
Already know that in insulators, heat is carried entirely by phonons,
but in metals heat may be transported by both electrons and phonons.
The thermal conductivity Kis therefore = K = K, + Ky,
In most metals, K, >> K,,,, because of high concentration of electrons.
Typically K, ~ 10 Ky.
Heat is transported by electrons having the Fermi energy, because
those well below this energy cancel each other's contributions The Drude model description of the thermal conductivity of metals
Consider the oversimplified picture of a 1D model where the electrons can only
move along the x-axis. In the absence of electric field the average velocity of the
electrons at each location is zero (because it is the thermal velocity).
Ata location x, the electrons coming from the right have a negative velocity and
their average thermal energy is ¢(T(x + vt)) and those coming from the left have
an average thermal energy ¢(T(x — vt)).
Because the motion is thermal half the electrons arrive from the left and half’
from the right such that the average thermal energy current density is:
n
IG) =Zee(te v9) - eM + v0) The Drude model description of the thermal conductivity of metals
as
Assuming that the variation of the temperature over the mean free path is very
small we may write it as
de dT
jU(x) = —nv?2r( ——
IG) = —nv (= +)
When considering the 3D picture the generalization is straightforward, we
replace the derivative with respect to x by the gradient and the velocity along
any direction is just 1/3 of the squared velocity because we assume that the
scattering is isotropic.
Considering also the fact that n = N/V and ==
Cy the heat capacity of the
electron gas we find
1 1
MG) =—gv?tC,0T = —KVT where x =3v7tcy The Drude model description of the thermal conductivity of metals
Problems with the assumptions
The above assumptions lead to the Lorenz number
or ne*t, ne? neeT—2\e.
1 1 1 3
ke 5Ue ty - Zmvec, _gbkelznke 3 (‘*)
w= 1.11- 10-8 watt - ohm/K?
where we used the ideal gas properties c, = skp and pmev? = 3 kT. This
value is about / the typical value but due to Drude’s mistake by a factor of two
he got an answer that is in good agreement with experiments. Electrons in metals: free electron model
* Simplest way to represent the electronic structure of metals
* Although great simplification, works pretty well in many cases, describes
many important properties of metals
* In this model, the valence electrons of free atoms become conduction
electrons in crystal and travel freely
* Neglect the interaction of conduction electrons with ions of the lattice and
the interaction between the conduction electrons — a free electron gas
* Fundamental difference between the free electron gas and ordinary gas of
molecules:
1) electrons are charged particles > to maintain the charge neutrality of
the whole crystal, we need to include positive ions.
This is done within the jelly mode! : the positive charge of ions is smeared
out uniformly throughout the crystal - charge neutrality is maintained,
no field on the electrons exerted
2) Free electron gas must satisfy the Pauli exclusion principle, which
leads to important consequences. Free electron gas in one dimension
Assume an electron of mass m is confined to a length L by infinite barriers
Schrédinger equation for electron wave function y,(x): Hy, (x)= Ew, (a)
E,, - the energy of electron orbital
assume the potential lies at zero => H includes only the kinetic energy >
YC) =E,Y,0)
- this is a one-electron equation —
neglected electron-electron mteractions
General solution: Asin g,x + Bcos g,x
boundary conditions for the wave function:
B= 0:9, san: n=intege, YilO=.(L)=0
(an) — Substitute, obtain _ i? (amy
yx) = Asin| x the eigenvalues: " 2m\ Lb What is Hamiltonian?
+ For particles confined to this box, there is only a kinetic energy term
to the Hamiltonian H
poi dod
H=? = (in y-in
2m on ae ‘e
nr @ Ra
3 AY, =~ an = En
2mde —"wenavewsone Me om aes
_———_ Quantum mechanical operator First three energy levels and wave-functions of a free electron
of mass m confined to a line of length L:
———Energy levels
. { an — Wavefunetions,
y,(x) = Asin ao 2. 2, Wlatve scale
E, --()
2m\L
wie miasens
<>
Feeounene met
Quantem number, n Quantum Theory of the Free Electron Gas
The equation has to be supplemented by boundary conditions. Since
we are interested in the bulk properties the boundaries are expected
to have a negligible effect and we have the freedom to chose the
most convenient boundary conditions.
We will use periodic boundary conditions where we require
wee +L) =p)
In 1D this choice corresponds to a ring of length L.
, , , 2
Acti = Ae) - elk = 1 kL = In k=
Where n € Integers, and k,, can be positive or negative because
the waves can travel in either direction.
p= 2 (200
7 2m.\ L
The energies are: Fermi energy
We need to accommodate N valence electrons in these quantum states.
Pauli principle: no two electrons can have identical quantum numbers.
Electronic state in a 1D solid is characterized by quantum numbers n
and m,, where n describes the orbital y,(x), and m, - the projection of
the spin: m, =+%.
=> each orbital labeled by the quantum number n can accommodate
two electrons, one with spin up and one with spin down orientation.
Let n; - the highest filled energy level. Start filling the levels from the
bottom ( = 1) and continue until all N electrons are accommodated.
Condition 2n; = N determines ne
The energy of the highest occupied level is called the Fermi energy Er
he ( aN }
For the one-dimensional system of N electrons Ee= on OD
2m\ 2 Finite temperature: the Fermi - Dirac distribution
The ground state of the N electron system
at zero temperature: all the electronic
levels are filled up to the Fermi energy.
All the levels above are empty.
®p
What happens if the temperature is increased?
The kinetic energy of the electron gas increases with temperature
=> some energy levels become occupied which were vacant at 0 K:
some levels become vacant which were occupied at 0 K.
The distribution of electrons among the levels is described by the
distribution function, f(E) - the probability that the level E is occupied
Dyan dietriby 1
Fermi - Dirac distribution: S(@)= [ent | l AE) at T=0Kand T> 0K
S(E) = ent | SE)
ft — the chemical potential.
It can be determined in a way that
the total number of electrons in the
system is equal to N.
AtT=0K y=E;
AtanyT if fE)=1/2 whenE =u
High energy tail of E), whenE-p>>kgT: f (E) =e 2st
called Maxwell — Boltzmann distribution Effect of temperature on Fermi-Dirac distribution
1
exp[(e — 1) /kT] +1
/ \
fle)=
/
Probab chemical potential
!
Poverty ator (~ amountoof energy needed to add an
‘electron to the oyster)
~ Fermi energy
‘fk (inunits of 10K) Free electron gas in three dimensions
The a — in the three dimensions:
> |yir) = Eyer)
If the electrons are confined to a cube of edge L, the solution is
i
vir)= Asin{ sin) My }sin( Sts
introduce periodic boundary conditions, as we did for lattice vibrations
—assume that our crystal is infinite and disregard the influence of the
outer boundaries of the crystal on the solution
—require that our wave function is periodic in x, y, and z directions with
period, sothat wv 7, y,2)=y(x,y,2)
and similarly for the y and 2 coordinates. The solution of the Schrédinger equation satisfying these boundary
conditions has the form of the traveling plane wave:
yar) = de®?
provided that the component of the wave vector k satisfy
24, 2mn, 2an, F
£3 k,=—; = where n,, 7, and 7, - integers
k=, =
x 7 y
substitute this to the Schrédinger equation. obtain the energy of the
orbital with the wavevector k: a ie
= —(k2 +h +12)
Im 2m
Wave functions y,,— the eigenfunctions of the momentum operator
p=-ihV — The eigenvalue of the momentum is hk.
The velocity of the electron is defined by v = p/m = hk/m Back to k-space
+ Each value of k occupies a volume of (2Tr/L) in k-space
t SEER, How many k states (orbitals)
4 Ky \ are in a sphere of radius k,?
mes Total no. of states Unit of k-space
Yk i ) (N/2)= (Volume of sphere)/(2T1/L)
(N/2)= (417k 3/3)/(2r/L)S
(each dot is separated by 2m/L,
and represents a wave with wavevectors (K,, K,, K,)) We can also define a Fermi temperature to be Ty= E,/k;
(Boltzmann's constant)
Meaning of the Fermi Temperature
+ The Fermi temperature is not the temperature of the
electron gas!
+ Itis a measure of where the Fermi energy is at (typically
on the order of ~ 10000 K)
+ So, for most metals say at room temperature, not many
electrons are excited above the Fermi energy. Fermi energy and Fermi momentum
In the ground state a system of N electrons occupies states with lowest
possible energies = all the occupied states lie inside the sphere of
radius ky.
The energy at the surface of this sphere is the Fermi energy Ep.
The magnitude of the Fermi wave vector ky Ik,
and the Fermi energy are related by the equation: r=
2m
The Fermi energy and the Fermi momentum are determined by
the number of valence electrons in the system N.
We need to count the total number of energy orbitals in a sphere
of radius k, which should be equal to N.
The volume element in the k space an
(volume per single set of k,. k,, and k.) is equal to (+ } nk,
Thus in the sphere of 7, = the total number of states is
4 372 V
2 a = where does the factor 2 come from ?
30° N
y3
- depends only of the electron concentration
2y\8
-2(% ) (~ 10° mvs!) Density of states
Defined as the number of electronic states per unit energy range —
an important characteristic of electronic properties of a solid
To find it, write the total number of orbitals of energy < E.
2 2 yy, ae oe
We had putt (=| =, wE)= 2 |
i
cae wo
~ 2m Vv
So, the density of states D(E) is
?
D(£)=
density of states
&
the integral N= / D(E)dE
°
- total number of electrons in system (at 0K)
At T#0 should take into account
the Fermi distribution: ZU J DE) S (EAE Quantitative expression for the electronic heat capacity
at low temperatures
kg <
dflaT is large only at the energies very close to the Fermi energy >
can ignore the variation of D(E) under the integral
so
C, =D(E, fe- E, a D ag
Also ignore the variation of the chemical potential with temperature
and assume that 4; = £, (good approximation at room T and below).
Then df(E,T)_E-E, OF!"
= a (gSRALGE id
dt [ef =) mip an
es op At (By Vege
Ge DE, {FP =
1 kT’ [erent 1
=DE,) |
Ep iksT Quantitative expression for the electronic heat capacity
at low temperatures
kgI<
dffdT is large only at the energies very close to the Fermi energy >
can ignore the variation of D(E£) under the integral
C, =DE, fe- E, ea
Also ignore the variation of the chemical potential with temperature
and assume that «= £, (good approximation at room T and below).
Then df(E,T) _E-E, efF-Fr) har
dP al” eV] am
<(E-E.y) lbEelitt
Cy = DE, [FY ae =
> AT [res]
= D(E,) [ (sry S
celine BT? (e41) Taking into account that E,>> k,7. we can put the low integration
limit to -c0 and obtain
= ue
7 e \w
Cy = DEp \kgT
ax = DE aT
e*+1)
Fora free electron gasuse D(E)= = for the density of states
Obtain |. yg TI where the Fermi temperature
[,| — is‘defined as T,= E,/kg
Result is similar to what we obtained from qualitative arguments
The heat capacity at terhperatures much below both the Debye
temperature and the Fermi temperature can be represented as:
C=C3+ fy =/T+ pr’ Electronic term dominates at sufficiently low T
yand £ can be by fitting the experimental data. Meaning of the Sommerfeld
Constant
So, the Sommerfeld constant is ~ density of states at the Fermi
energy (y = 1/3 17k? D(e,))
This makes sense — it is only these electron states that can absorb
energy
The Sommerfeld constant is also related to an “effective mass” of
the conduction electrons (which should be ~ mass of an electron)
How? Mass of conduction electron
The Fermi Energy is ¢, = hk2/2m = (h2/2m)(31P2N/V)2?
So, rearranging our terms we have:
And therefore, y ~ m In the above discussion we treated electrons on a classical basis.
How are the results modified when the quantum mechanics is taken
i ”
into account? » ilies
ss
Fermi —*
No electric field - the
Fermi sphere is cantered
at the origin. The total
current of the system is
zero.
Applied field — each electron acquires a drift velocity >
the whole Fermi sphere is displaced
displacement is very small: v << vy, e.g. 0.1 V/cm causes v ~ lenvs
vp ~108 cm/s)
=> the great majority of the electrons still cancel each other
some electrons (shaded area) remain uncompensated - produce current Estimate the current density: the fraction of electrons which remain
uncompensated is = v/v’, = concentration of these electrons is n(“/’p)
Each electron has a velocity=vp => j =-en(v/v,;)v, =—nev
- Same result as before = the same formula for conductivity
Actual picture of conduction is quite different from the classical one:
* In the classical picture. the current is carried equally by all electrons,
each moving with a very small drift velocity v.
* In the quantum-mechanical picture the current is carried only by very
small fraction of electrons, all moving with the Fermi velocity.
* Relaxation time is determined only by electrons at the Fermi surface,
because only these electrons can contribute to the transport properties.
° The latter approach is conceptually more accurate.
Since only electrons at the Fermi surface contribute to conductivity,
we can define the mean free path of electrons as ] = tv,.
Can estimate the mean free path for metal at room temperature: ~100A. On the origin of collision time
We see that between two collisions, the electron travels a distance of more
than 20 times the interatomic distance - much larger than one would expect if
the electron really did collide with the ions
This can be explained only using quantum mechanical concepts of wave
character of electron.
Well known from the theory of wave propagation in periodic structures: wave
passes through a periodic lattice without scattering
Atoms in the lattice is to absorb energy from the wave and radiate it back. +
the wave continues without modification in either direction or intensity. but
the speed of wave changes
Effect of periodic lattice: free electron mass mg . eEr
is replaced by effective mass m*: Drift velocity is then
m*
We see that. if the ions form a perfect lattice. there is no collision at all - that
is./=* >1=~ - infinite conductivity.
Finiteness of o- due to the deviation of the lattice from perfect periodicity:
(1) thermal vibration of the ions (2) the presence of defects or impurities. PAT Y/9(290°K)
Temperature dependence of the electrical conductivity
Characteristic temperature dependence of resistivity of a metal:
normalized resistivity (7)/(290K) versus T for Na
p (290°K) ~ 2nQ.cm
ce At higher temperatures
x10? 7 i
p increases with 7.
slowly at first, but
afterward p increases
linearly with 7.
AAT’ 0(290°K)
4 The linear behavior
continues essentially
o % #% @ 40 10 Until the melting point.
Observed in most
metals, and usually
room temperature falls
into the linear range.
low-temperature region
T~OK: phas
asmall constant value ‘We want to explain this behavior of in terms of the Drude model.
Have 1 m*
e— 2
a ner
Two types of the deviations from a perfect lattice:
a) Lattice vibrations (phonons) of the ions around their equilibrium
position due to thermal excitation of the ions.
b) All static imperfections, such as impurities or crystal defects.
Of this latter group we shall take impurities as an example.
The total probability for an electron to be scattered in a unit time is the sum
of the probabilities of scattering by phonons and by impurities:
1 1,1 m* m*
S=St— PR Pp = t+
TOT Tp,
re T; ne> Ton
residual resistivity lattice resistivity
The scattering by impurities is essentially independent of temperature
The number of phonons increases with temperature
=> the scattering by phonons is temperature dependent Very low T: scattering by phonons is negligible > 7, > ». p,, > 0
=> p =p; = constant - in agreement with experiment
As T increases, scattering by phonons becomes more effective
= Ppi{T) increases = p increases
When T becomes sufficiently large. scattering by phonons dominates
= P* Pp(D)
The statement p=,+,, is known as the Matthiessen rule.
(not always valid)
Now let's derive approximate expressions for 7, and ¢,,, from the
kinetic theory. Consider first the collision of electrons with impurities.
Expect that p, should increase with impurity concentration 7,
Write
where /, is the mean free path for collision with impurities. Electronic thermal conductivity
Heat current density, jp. Le. the amount of thermal energy crossing a
unit area per unit time is proportional to the temperature gradient:
jg =-K < where K is the thermal conductivity
x
Already know that in insulators, heat is carried entirely by phonons.
but in metals heat may be transported by both electrons and phonons.
The thermal conductivity Kis therefore = K = K,+ Kx
In most metals. K,
Typically K, ~ 10? K,,,.
Cn» because of high concentration of electrons.
Heat is transported by electrons having the Fermi energy, because
those well below this energy cancel each other's contributions - il
Evaluate the thermal conductivity K quantitatively, use K = = ‘av pl
here C,; - electronic specific heat per unit volume, v;- Fermi velocity:
/is the mean free path of electrons at the Fermi energy.
Use expression for the heat capacity derived earlier: Gye nr Nik rT
el ge
Then ~ T,
E Jour Note that FE, =
F )
obtain x = x nk3tT - expression for thermal conductivity in terms
3m of the electronic properties of the metal
= ne* T
Recall that electrical conductivity o =-
find that
- Wiedemann-Franz law
L=2.45.10% WQ/K? - Lorentz number -
independent of the particular metal (depends only on kg and e) Summary of free electron model
“ Free electron model — simplest way to describe electronic properties of
metals: the valence electrons of free atoms become conduction electrons in
crystal and move freely throughout the crystal.
‘@ Fermi energy - the energy of the highest occupied electronic level at T = 0
K 2 > 2
"4 #(aeNy? , _(3en)" , _a(aen)"
*
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