Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

Chapter 4

Metals: Free Electron Model

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

Contents
1. Introduction
2. Energy level and Fermi-Dirac distribution
3. Free electron gas and density of states
4. Electrical properties
5. Thermal properties

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

4.2 Energy level and Fermi-Dirac distribution

4.2.1 Energy levels
- Energy levels
- Fermi energy

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

Energy levels of free electrons

Particles in a Box (one-dimension)
V(x) V(x) = 0 inside box
V(x) = ∞ outside box

Y(x) = 0 when x=0, or x=L

0 L
x
n2h2
2 2 2 2 n
n h h æ np ö 8mL2
en = = ç ÷
8mL2 2m è L ø 22 h 2
n = 1, 2, 3, …. (E: quantized) 8mL2 2
h2 1
8mL2

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

h2 d 2
The Schrödinger eq. - 2 2
Y = EY (1.14)
8p m dx
Y = eax , e -ax , sin(ax), cos(ax), etc
Y (0) = 0, Þ Y = sin(ax ) (1.15)

Y (a ) = 0, Þ aa = np (n = 1,2,3....)
np (1.16)
\a =
a
h2 d 2 æ npx ö æ npx ö V(x)
- 2 2
sin ç ÷ = E sin ç ÷
8p m dx è a ø è a ø
h 2 æ n 2p 2 ö æ npx ö æ npx ö
Þ - 2 çç - 2 ÷÷ sin ç ÷ = E sin ç ÷
8p m è a ø è a ø è a ø0 a
n2h2
ÞE= 2
(1.17)
8ma n = 1, 2, 3, …. (E: quantized)
CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je
Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

For N free electrons, e

n2h2
2nF = N en =
8mL2
2 2
h2 æ nF p ö h2 æ Np ö e n µ n2
eF = ç ÷ = ç ÷
2me è L ø 2me è 2L ø
Fermi energy ~ 5 eV in metals n
(
e = n + 1 2 hv ) n2h2
n
8mL2 nF
nF: the top most filled
energy level 22 h 2
8mL2 2
Pauli exclusion principle h2 1
8mL2

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

 Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

4.2 Energy level and Fermi-Dirac distribution

Distribution function, f(e):
f(e)

1 T=0ºK

T>0ºK
0 eF e

f(e) at T ¹ 0ºK
1
f (e ) =
exp[(e - e F ) / k BT ] + 1

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

4.3 Free electron gas in 3-D and density of states

2
h2 æ np ö
en = ç ÷
2me è L ø
2
ny
2
h æp ö 2
en = 2
(2
ç ÷ nx + n y + nz
2me è L ø
) for 3-D

3
14 3 pn
(volume) = pnmax = max nmax
83 6
1 cube of unit volume « 1 state
3
N pnmax
=
2 6 nx
1
3
æ 3N ö
nmax =ç ÷ nz
è p ø

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

1
3
æ 3N ö
nmax =ç ÷
è p ø
2
h2 æp ö
( 2
nmax = n + n + n 2 2
1
) 2 en =
2me
2
(
2 2
ç ÷ nx + n y + nz )
x y z
èLø
2 2 2 2
2 2 2 2 3
h æp ö 2 h æ p ö æ 3N ö h 3 æ 3p N ö
eF = ç ÷ nmax= ç ÷ ç ÷ = çç ÷÷
2me èLø 2me èLø è p ø 2me è V ø
N
eF « 2 2
V h æ Np ö
eF = ç ÷ for 1 - D
2me è 2 L ø
Velocity of Fermi electron, vF?
1
2 3
1
e F = me vF2 ® vF = ç h ÷
æ ö æ 3p N ö
çm ÷ çç ÷÷
2 è eø è V ø

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

 Fundamentals 2 Science
for 2Materials Chapter 4 Metals: Free Electron Model 1
2 3 2 3
h æ 3p N ö æ h ö æ 3p N ö
eF = çç ÷÷ vF = çç ÷÷ çç ÷÷
2me è V ø è me ø è V ø
Element N (m-3) eF (eV) vF(m/s)
Li 4.6x1028 4.7 1.3x106
Na 2.5 3.1 1.1
K 1.3 2.1 0.85
Rb 1.1 1.8 0.80
Cs 0.85 1.5 0.75
Cu 8.45 7.0 1.6
Ag 5.85 5.5 1.4
Au 5.90 5.5 1.4
Zn 13.10 9.4 1.82
CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je
 Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model
2
Density of states, g(e): h 2
æ 3p N ö2 3

eF e = çç ÷÷
N = ò g (e )de 2me è V ø
0
3 3
dN V æ 2me ö 2 12 V æ 2me ö 2 3 2
g (e ) = = 2 ç 2 ÷
e N= 2ç 2 ÷ e
de 2p è h ø 3p è h ø
Total # of electrons in energy ≤ e
g(e)
3
V æ 2me ö 2 12
g (e F ) = 2 ç 2 ÷
eF
N at 2p è h ø
0ºK
eF e 2
2 2 3
h æ 3p N ö
eF = çç ÷÷
2me è V ø
CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je
 Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model
f(e)
1 density of occupied states

T>0ºK
0 eF e
g(e)

N at
0ºK
eF e
)e(g)T,e(f

g(e)

eF e
CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je
Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

4.4 Electrical properties

4.4.1 Electrical conductivity and Ohm’s law

r
r At t, E
At t = 0, E = 0 ky Fermi surface ky
r
Fermi sphere F

kx kx
r
dk

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model
r
r At t, E
r dk r ky
F =h = -eE
dt r
r F
r r eEt
k (t ) - k (0) = -
h
r
r eEt r
kx
dk = - dk
h

Ohm’s law
r r Why resistance? Collisions!
j = sE
t: collision time r
conductivity r dv r r eEt
Current F = m = - eE ®v =-
flux charge, -e dt m
r
r r æ eEt ö e 2
t r Incremental velocity
j = nqv = n( -e)ç ÷
ç- m ÷= n m E
è ø e 2t
\s = n
Electron concentration (Ohm’s law) m
CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je
Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

e 2t 1 m
s =n ® r º =
m s ne 2t
Electrical resistivity
r r r 1 r
j = sE or j = E (Ohm’s law)
r
r 1 r
Cf I = V
R
Mean free path, l?
l = v Ft
Ex) for pure Cu, t ~ 2x10-9 s at 4ºK, t ~ 2.7x10-14s at 300ºK
l(300ºK) ~ 3x10-6 cm; l(4ºK) ~ 0.3 cm
Collision with lattice phonons Collision with impurities or
lattice defects
1 1 1
= + ® r = r L + ri
t tL ti

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

Resistivity of metals
x10-3 x10-2
5 21
)Kº092(r/)T(r

)Kº092(r/)T(r
4
14
3
2
7
1

0 6 10 14 18 22 0 20 40 60 80 100
T, ºK T, ºK

m
r= ® r = r L + ri
ne 2t

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

4.4.2 Hall effect r

What happens for electrons under B
E?
y
x r
z Bz
+ + + + + + r +- + +
r vx
EH - jx
- - - - - - - - -
Hall field
r r r
FL = ev x B
Lorentz force = - FH (Hall force) in steady state
r r r r r r r r
- eE H = -ev x B ® E H = v x B j = - nev
r 1 r
EH = - jx B 1
ne Hall constant, RH = -
ne

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

Hall constants (volt m3/amp weber at RT)

Li Na Cu Ag Au Zn Cd Al

-1.7x10-10 -2.50 -0.55 -0.84 -0.72 +0.3 +0.6 -0.30

Q: jx « Bz? x r
z Bz
+ + + + + + r +- + +
r vx
EH - jx
- - - - - - - - -

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

4.5. Thermal properties

4.5.1 Heat capacity of the electron gas
æ ¶U ö
CV = ç ÷
è ¶T øV

For phonon U = ò e (v ) g (v )dv For electrons

setats deipucco fo ytisneD

k BT
U = ò eg (e ) f (e )de
0
g(e) ~ T/TF

f(e,T)g(e)

eF e

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

¥
U = ò eg (e ) f (e )de
0

¶U ¥ ¶f minus
Cel = = ò eg (e ) de
¶T 0 ¶T
¥ ¥
N = ò g (e ) f (e ) de ® e F N = e F ò g (e ) f (e ) de
0 0

¶N ¥ ¶f
® eF = 0 = e F ò g (e ) de
¶T 0 ¶T
¥ ¶f
® Cel = ò (e - e F ) g (e ) de
0 ¶T
¥ ¶f
Cel @ g (e F ) ò (e - e F ) de
0 ¶T
1 2 (homework)
Cel = p g (e F )k B2T
3
CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je
Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

1 2
Cel = p g (e F )k B2T
3
3 2
2 2 3
V æ 2me ö 1 2
h æ 3p N ö
g (e F ) = 2 ç 2 ÷
e F2 eF = çç ÷÷
2p è h ø 2me è V ø
3N
® g (e F ) =
2e F
1 2 k T 1 T
Cel = p Nk B B = p 2 R TF k B = e F
2 eF 2 TF

Heat capacity of metals at low T

C = gT + AT 3 = Ce + C ph

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

4.5.2 Thermal conductivity in metals

dT 1
jv = - K K = Cvl
dx 3
1 1 æ p 2 Nk B2T ö
K el = Cv v F l F = ç ç ÷
÷ vF l
3 3è 2e F ø
p 2 Nk B2T l e = 1 mv 2
= F 2 F
3m vF
2 2 l = v Ft
p Nk BTt
\ K el =
3m

K = K el + K ph
Pure metals: Kel >> Kph Impure metals: Kel ~ Kph

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

K K p 2 Nk B2Tt 1
=? =
s s 3m ne 2t / m
p 2 k B2 1
= 2
T
3 e
K
Lº
sT
Lorentz number
2
1 æ pk B ö
L= ç ÷ = 5.8 x10 -9 cal - ohm / s° K
3è e ø

Element Na Cu Ag Au Al Cd Ni Fe

K, cal/mºK·s 33 94 100 71 50 24 14 16
L, cal·ohm/s·ºK 5.2x10-9 5.4 5.6 5.9 4.7 6.3 3.7 5.5

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

4.5.3 Thermionic emission

BaO

CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je

Fundamentals for Materials Science Chapter 4 Metals: Free Electron Model

- Vacuum
- -
- f, work function
- -

ygrenE
- 1.5 ~ 5 eV
- -
eF

f(e)
T=0ºK
1 T1 <T2 <T3

0 eF e
CRI – X-ray Imaging Center (XIC)--POSTECH Prof. Jung Ho Je