Lecture 12: Free Electrons

Lecture 12: Free electrons
Quantum mechanics Free electrons in a box Fermi gas Fermi-Dirac distribution function Covers Verdeyen ch. 11 Please ask questions!
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##11 Lecture 12, Slide
Free electron theory of solids

Each atom in the solid gives up one electron Each electron is free to move where-ever it wants, with no scattering Completely the opposite of atom lasers, where each electron is bound to each atom Amazingly, this simple idea makes predictions that are true! Not for semiconductors, but metals Still need to understand this for semiconductors
Electrons are waves, too.
ECE 275B P.J. Burke, Winter 2003
Last modified 1/2/2003 2:27 AM
Lecture 12, Slide ##33 Lecture 12, Slide
r 2 ( r , t )
Quantum mechanics of free particles:

is probability of finding an electron at point r at time t. is complex, and both real and imaginary parts are physical. For a free particle:
= E /h
r ( r , t ) ~ e
Momentum:
rr i ( k r t )
Energy:
r r p = hk
p 2 ( hk ) 2 E= = 2m 2m
Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##44 Lecture 12, Slide
Schrodinger equation:
h2 2 ih ( x, t ) = ( x, t ) 2 t 2m x
Let Then (1 dimension) (Time dependent)
( x, t ) = A e
i ( kx t )
A is a (complex) constant.
r ih ( r , t ) = ih A ei ( kx t ) = ih( i ) A ei ( kx t ) t t
= E A ei ( kx t ) = E ( x, t )
h2 2 h2 2 h2 2 (A ei ( kxt ) ) = 2m (ik ) (A ei ( kxt ) ) ( x, t ) = 2m x 2 2m x 2
h 2k 2 p2 (A ei ( kxt ) ) = 2m ( x, t ) = 2m
Schrodinger equation:
Let Then But:
(3 dimensions)
r 2 h2 r 2 r h2 2 2 r 2 + 2 + 2 ( r , t ) (r , t ) = ih ( r , t ) = t 2m 2m x y z
rr r i (( k x x + k y y + k z z ) t ) i ( k r t ) ( r , t ) = A e = A e
ih
rr h2 2 h2 2 2 2 2 2 r i ( k r t ) 2 + 2 + 2 A e 2 + 2 + 2 ( r , t ) = x 2m 2m x y z y z
r r r ( r , t ) = ih( i ) ( r , t ) = E ( r , t ) t
as before.
rr h 2 (k x 2 + k y 2 + k z 2 ) r h2 2 2 2 ( r , t ) (ik x ) + (ik y ) + (ik z ) A ei ( k r t ) = = 2m 2m
)(
rr r p2 h 2k 2 i ( k r t ) = A e = (r , t ) 2m 2m
Quantum mechanics of free particles:
r ( r , t ) ~ e
n
rr i ( k r t )
Generally,
r i ( k n x n t ) i ( kx t ) ( r , t ) = An e dk A( k )e
is also a possibility.
Time-independent Schrodinger equation rr r i ( k r t )
( r , t ) = A e
i ( k x x + k y y + k z z ) t
= A e
= A e
i ( k x x + k y y + k z z )
it
r h2 r 2 r From: ih ( r , t ) = ( r , t ) 2m t r r it r it r it h2 ih ( r , t ) = ih ( r ) e = ih( i ) ( r ) e = E ( r ) e =
t t
r r it (r , t ) = (r ) e
r2 r h 2 r 2 r it (r , t ) = (r ) e 2m 2m
Call this
r (r )
r h2 r 2 r ( r ) = E ( r ) 2m
Confined particles: A box
L L
Goal: find
r (r )
Similar to electric field inside the box.

Goal: find
r (r )
Everywhere outside the box
x
L
r 2 (r ) = 0
In particular,
r 2 (r ) = 0
on the boundaries.
As before, we will consider all six surfaces:
Lecture 12, Slide ##10 Lecture 12, Slide 10
Boundary conditions:
The plane x=0:
r i ( k x x + k y y + k z z ) (r ) = A e
x
L
Try:
( x = 0, y , z ) = A e
i ( k x x + k y y + k z z )
= A e
i ( k y y + k z z )
Does not solve boundary condition!!!
Boundary conditions: The plane x=L:

r i ( k y y + k z z ) ik x x ik x x (r ) = A e e e
L z
= 2iA sin( k x x ) e
x
L
i ( k y y + k z z )
1 i sin( ) = (e e i ) 2i
i ( k y y + k z z )
( x = L, y , z ) = 2iA sin(k x L) e
If and only if:
= 0?
kn = n / L
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##12 Lecture 12, Slide 12
Boundary conditions: The plane x=L:

r i ( k y y + k z z ) ik x x ik x x (r ) = A e e e
L z
= 2iA sin( k x x ) e
x
L
i ( k y y + k z z )
1 i sin( ) = (e e i ) 2i
i ( k y y + k z z )
( x = L, y , z ) = 2iA sin(k x L) e
If and only if:
= 0?
kn = n / L
We can do the same for y, z:

r ( r ) = ( 2i )3 A sin(knx x ) sin(k n y ) sin(knz z )

y
x
L
knx = n x / L kn y = n y / L knz = nz / L
We can do the same for y, z:

r ( r ) = ( 2i )3 A sin(knx x ) sin(k n y ) sin(knz z )

y
x
L
2 2
E=
h 2 (knx + kn y + knz ) 2m
h 2 ( / L) 2 2 2 2 = (nx + n y + nz ) 2m
These are the allowed energy levels, or quantum states

Many electrons:
h 2 ( / L) 2 2 2 2 E= (n x + n y + nz ) 2m
L
x
L
These are the allowed energy levels, or quantum states
Pauli exclusion principle: Each unique combination of nx, ny, nz can only have two electrons (spin up, spin down).
Energy spectrum of free particles:
energy Etc. nx=2, ny=1, nz=1 nx=1, ny=1, nz=1 nx=1, ny=2, nz=1 nx=1, ny=1, nz=2
Density of states:
If L is large, states are very close together. Approximate as a continuum.
energy
E+dE E How many states?
N E dE = ?
Number of states with energy between E and E + dE Number of states with energy between E and E + dE per volume.
( E )dE = ?
Density of states:
Easier first to think of in k-space: Density of states in k-space is uniform: One state per (/L)3:
kz ky kx
Density of states:
Easier first to think of in k-space: Density of states in k-space is uniform: One state per (/L)3:
From Verdeyen
Density of states: Number of states between k, k+dk:
kz
N k dk = ?
ky kx
From Verdeyen
k k +k +k
2 x 2 y
2 z
N k dk = ?
Volume of spherical shell =4k2dk/8 8 is for upper right quadrant
Number of states in volume= Volume x States/volume States/volume = 1 / (/L)3:
1 3 k dk N k dk = (4k dk / 8) ( / L)3 2 = L 2
2 2
N k dk k 2dk k dk = 2 volume
HW you will do calculation for 2 dimensional world.
( E )dE = ?
We use:
k dk = ( E )dE
k dk =
k dk
2
2mE 2m dE h 2k 2 E= k = dk = 2 2m h h2 2 E
2 m 1/ 2 E dE ( E )dE = 2 3 h
1/ 2
3/ 2
Fermi gas:
At zero temperature, as we add electrons to the box, we gradually fill up all the states. (DISCUSS PAULI EXCLUSION PRINCIPLE -IMPORTANT!)
E=EFermi
When we are done filling the box, the energy of the last electron is called the Fermi energy. Gas means we neglect electron-electron interactions.
E=0
P(E)
energy
All these states are filled with electrons.
energy
Fermi energy:
# electrons = N EdE =
0 Ef Ef 0
21 / 2 m 3 / 2 1 / 2 L3 E dE 2 3 h
E=EFermi
21 / 2 m 3 / 2 2 3 / 2 Ef # electrons = L3 2 3 h 3
energy
Ef =
All these states are filled with electrons.
h 3 2m
2 2/3
4/3
# electrons 3 L
2/3
E=0
In a typical metal, L ~ 0.1 nm. Ef ~ 10 eV

Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##25 Lecture 12, Slide 25
Occupation probability:
P(E)
0
energy
E=EFermi
P(E) = probability of occupying a state with energy E What about finite temperature?
Boltzmann:
Recall Boltzmann factor P(): The probability for a physical system to be in a state with energy is proportional to e / k T .
B
This is actually not quite true. It is classical. A quantum calculation shows for electrons:
P( E ) =
1 e
( E E f ) / kT
+1
Called Fermi-Dirac distribution function.

Fermi-Dirac:
P( E ) =
1
1 e
( E E f ) / kT
+1
P(E)
0
energy
E=EFermi
P=1/2 at Ef for all temperatures.

kT
Forget about free electrons for now.

Back to the hydrogen atom.
Chemical bonds:
n=inf. n=3 n=2 n=inf. n=3 n=2 n=inf. n=3 n=2
+
n=1 n=1
n=1
Chemical bonds:
n=inf. n=3 n=2 n=inf. n=3 n=2 n=inf. n=3 n=2
+
n=1 n=1
=
n=1 Bonding and anti-bonding
Chemical bonds:
n=inf. n=3 n=2 n=inf. n=3 n=2 n=inf. n=3 n=2 n=inf. n=3 n=2
+
n=1
+
n=1 n=1
=
n=1 N atoms give N levels
Band theory of solids:

1 Hydrogen atom: n=inf. n=3 n=2
energy
2 Hydrogen atoms:
antibond bond antibond bond
3 Hydrogen atoms:
N Hydrogen atoms:
N levels
N levels
n=1
antibond bond
N levels
Band theory of solids:

N Hydrogen atoms: N -> infinity
N levels -> band of energy energy
N levels -> band of energy
N levels -> band of energy
Band theory of solids: Filled bands do not conduct electricity! Insulator:
energy
Band theory of solids: Filled bands do not conduct electricity! Insulator: Metal:
energy
Band theory of solids: Filled bands do not conduct electricity! Insulator: Metal: Semiconductor:
Thermally excited electrons
Empty states: holes
energy
Conduction band
Bandgap Thermally excited electrons
Valence band
Empty states: holes
energy
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM
Conduction band
Bandgap Thermally excited electrons
Valence band
Empty states: holes
energy
We usually dont care about lower bands. LASER will be formed by electrons going from conduction to valence band...
Semiconductors: Finite temperature:

Thermally excited electrons Bandgap Empty states: holes energy energy
Zero temperature:
NO thermally excited electrons Bandgap NO Empty states: holes NO CONDUCTION AT ZERO TEMPERATURE. Only at finite temperature. Hence the name, semiconductors.
Group** Period
1 IA 1A
1 2 3 4 5 6 7
1.008
H
3
2 IIA 2A
Silicon: Gap = 1.1 eV

3 IIIB 3B 4 IVB 4B 5 VB 5B 6 VIB 6B
24
VIIIA
18
8A
2
13 IIIA 3A
14 IVA 4A
15 VA 5A
16 VIA 6A
17 VIIA 7A
4.003
He Ne Ar Kr
54 36 18 10
6.941 11
Li
9.012 12
Be
10.81
B
13
12.01 14
14.01 15
N P
33
16.00 16
O S
34
19.00 17
20.18
22.99 19
Na K
37
Mg
24.31 20
7 VIIB 7B
25
10
------- VIII ------------- 8 -------
11 IB 1B
29
12 IIB 2B
26.98 31
Al
28.09 32
Si
30.97
32.07
35.45 35
Cl
39.95
39.10
40.08
Ca Sr
56 38
44.96
Sc Y
57 39
21
47.88
Ti
40
22
50.94
V
41
23
Cr
52.00
Mn
54.94
55.85
Fe
44
26
58.47
Co Rh Ir
77 45
27
58.69
Ni
46
28
Cu
63.55
65.39
Zn
48
30
69.72
Ga In
81 49
72.59
Ge Sn Pb --() 114 82 50
74.92
As
51
78.96
Se Te
84 52
79.90 53 126.9
Br I
83.80
85.47
Rb Cs Fr
87 55
87.62
88.91
91.22
Zr
72
92.91
Nb Ta
105 73
Mo
95.94
42
Tc
(98) 75
43
101.1
Ru Os Hs
108 76
102.9
106.4
Pd Pt
110 () 78
107.9
Ag Au --() 111 79
47
112.4
Cd Hg --() 112 80
114.8
118.7
121.8
Sb Bi
83
127.6
131.3
Xe
86
132.9
137.3
Ba
88
La*
138.9 89
178.5
Hf Rf
104
180.9
183.9
W
106
74
186.2
Re Bh
107
190.2
190.2
195.1
197.0
200.5
204.4
Tl
207.2
209.0
(210)
Po --() 116
(210)
At
85
Rn
(222)
(223)
Ra
(226)
Ac~
(227)
(257)
Db
(260)
(263)
Sg
(262)
(265)
(266)
Mt
109
---
--()
118
Lanthanide Series*
140.1 90
Ce Th
58
140.9 91
Pr
59
144.2 92
Nd U
60
(147)
P m
93
61
Sm
150.4 94
62
152.0 95
Eu
63
157.3 96
Gd
64
158.9 97
Tb Bk
65
162.5 98
Dy Cf
66
164.9 99
Ho Es
67
From http://pearl1.lanl.gov/periodic/default.htm
167.3 100
Er
68
Tm
168.9 101
69
173.0 102
Yb
70
175.0 103 (257)
Lu Lr
71
Actinide Series~
232.0
(231)
Pa
(238)
Np
(237)
(242)
Pu
Am
(243)
Cm
(247)
(247)
(249)
(254)
Fm
(253)
Md
(256)
No
(254)
Group** Period
1 IA 1A 18
1 2 3 4 5 6 7
1.008
H
3
2 IIA 2A
Ge:
24
VIIIA
8A
2
13 IIIA 3A
14 IVA 4A
15 VA 5A
16 VIA 6A
17 VIIA 7A
4.003
He Ne Ar Kr
54 36 18 10
6.941 11
Li
9.012 12
Be
10.81
B
13
12.01 14
14.01 15
N P
33
16.00 16
O S
34
19.00 17
20.18
22.99 19
Na K
37
Mg
24.31 20
7 VIIB 7B
25
10
------- VIII ------------- 8 -------
11 IB 1B
29
12 IIB 2B
26.98 31
Al
28.09 32
Si
30.97
32.07
35.45 35
Cl
39.95
39.10
40.08
Ca Sr
56 38
44.96
Sc Y
57 39
21
47.88
Ti
40
22
50.94
V
41
23
Cr
52.00
Mn
54.94
55.85
Fe
44
26
58.47
Co Rh Ir
77 45
27
58.69
Ni
46
28
Cu
63.55
65.39
Zn
48
30
69.72
Ga In
81 49
72.59
Ge Sn Pb --() 114 82 50
74.92
As
51
78.96
Se Te
84 52
79.90 53 126.9
Br I
83.80
85.47
Rb Cs Fr
87 55
87.62
88.91
91.22
Zr
72
92.91
Nb Ta
105 73
Mo
95.94
42
Tc
(98) 75
43
101.1
Ru Os Hs
108 76
102.9
106.4
Pd Pt
110 () 78
107.9
Ag Au --() 111 79
47
112.4
Cd Hg --() 112 80
114.8
118.7
121.8
Sb Bi
83
127.6
131.3
Xe
86
132.9
137.3
Ba
88
La*
138.9 89
178.5
Hf Rf
104
180.9
183.9
W
106
74
186.2
Re Bh
107
190.2
190.2
195.1
197.0
200.5
204.4
Tl
207.2
209.0
(210)
Po --() 116
(210)
At
85
Rn
(222)
(223)
Ra
(226)
Ac~
(227)
(257)
Db
(260)
(263)
Sg
(262)
(265)
(266)
Mt
109
---
--()
118
Lanthanide Series*
140.1 90
Ce Th
58
140.9 91
Pr
59
144.2 92
Nd U
60
(147)
P m
93
61
Sm
150.4 94
62
152.0 95
Eu
63
157.3 96
Gd
64
158.9 97
Tb Bk
65
162.5 98
Dy Cf
66
164.9 99
Ho Es
67
167.3 100
Er
68
Tm
168.9 101
69
173.0 102
Yb
70
175.0 103 (257)
Lu Lr
71
Actinide Series~
232.0
(231)
Pa
(238)
Np
(237)
(242)
Pu
Am
(243)
Cm
(247)
(247)
(249)
(254)
Fm
(253)
Md
(256)
No
(254)
Group** Period
1 IA 1A
1 2 3 4 5 6 7
1.008
H
3
2 IIA 2A
GaAs: Gap = 1.4 eV

13 IIIA 3A
10.81
VIIIA
18
8A
2
14 IVA 4A
15 VA 5A
16 VIA 6A
17 VIIA 7A
4.003
He Ne Ar Kr
54 36 18 10
6.941 11
Li
9.012 12
Be
B
13
12.01 14
14.01 15
N P
33
16.00 16
O S
34
19.00 17
20.18
22.99 19
Na K
37
Mg
24.31 20
3 IIIB 3B
4 IVB 4B
5 VB 5B
6 VIB 6B
24
7 VIIB 7B
25
10
------- VIII ------------- 8 -------
11 IB 1B
29
12 IIB 2B
26.98 31
Al
28.09 32
Si
30.97
32.07
35.45 35
Cl
39.95
39.10
40.08
Ca Sr
56 38
44.96
Sc Y
57 39
21
47.88
Ti
40
22
50.94
V
41
23
Cr
52.00
Mn
54.94
55.85
Fe
44
26
58.47
Co Rh Ir
77 45
27
58.69
Ni
46
28
Cu
63.55
65.39
Zn
48
30
69.72
Ga In
81 49
72.59
Ge Sn Pb --() 114 82 50
74.92
As
51
78.96
Se Te
84 52
79.90 53 126.9
Br I
83.80
85.47
Rb Cs Fr
87 55
87.62
88.91
91.22
Zr
72
92.91
Nb Ta
105 73
Mo
95.94
42
Tc
(98) 75
43
101.1
Ru Os Hs
108 76
102.9
106.4
Pd Pt
110 () 78
107.9
Ag Au --() 111 79
47
112.4
Cd Hg --() 112 80
114.8
118.7
121.8
Sb Bi
83
127.6
131.3
Xe
86
132.9
137.3
Ba
88
La*
138.9 89
178.5
Hf Rf
104
180.9
183.9
W
106
74
186.2
Re Bh
107
190.2
190.2
195.1
197.0
200.5
204.4
Tl
207.2
209.0
(210)
Po --() 116
(210)
At
85
Rn
(222)
(223)
Ra
(226)
Ac~
(227)
(257)
Db
(260)
(263)
Sg
(262)
(265)
(266)
Mt
109
---
--()
118
Lanthanide Series*
140.1 90
Ce Th
58
140.9 91
Pr
59
144.2 92
Nd U
60
(147)
P m
93
61
Sm
150.4 94
62
152.0 95
Eu
63
157.3 96
Gd
64
158.9 97
Tb Bk
65
162.5 98
Dy Cf
66
164.9 99
Ho Es
67
167.3 100
Er
68
Tm
168.9 101
69
173.0 102
Yb
70
175.0 103 (257)
Lu Lr
71
Actinide Series~
232.0
(231)
Pa
(238)
Np
(237)
(242)
Pu
Am
(243)
Cm
(247)
(247)
(249)
(254)
Fm
(253)
Md
(256)
No
(254)
Group** Period
1 IA 1A 18
1 2 3 4 5 6 7
1.008
H
3
2 IIA 2A
InP:
24
VIIIA
8A
2
13 IIIA 3A
14 IVA 4A
15 VA 5A
16 VIA 6A
17 VIIA 7A
4.003
He Ne Ar Kr
54 36 18 10
6.941 11
Li
9.012 12
Be
10.81
B
13
12.01 14
14.01 15
N P
33
16.00 16
O S
34
19.00 17
20.18
22.99 19
Na K
37
Mg
24.31 20
7 VIIB 7B
25
10
------- VIII ------------- 8 -------
11 IB 1B
29
12 IIB 2B
26.98 31
Al
28.09 32
Si
30.97
32.07
35.45 35
Cl
39.95
39.10
40.08
Ca Sr
56 38
44.96
Sc Y
57 39
21
47.88
Ti
40
22
50.94
V
41
23
Cr
52.00
Mn
54.94
55.85
Fe
44
26
58.47
Co Rh Ir
77 45
27
58.69
Ni
46
28
Cu
63.55
65.39
Zn
48
30
69.72
Ga In
81 49
72.59
Ge Sn Pb --() 114 82 50
74.92
As
51
78.96
Se Te
84 52
79.90 53 126.9
Br I
83.80
85.47
Rb Cs Fr
87 55
87.62
88.91
91.22
Zr
72
92.91
Nb Ta
105 73
Mo
95.94
42
Tc
(98) 75
43
101.1
Ru Os Hs
108 76
102.9
106.4
Pd Pt
110 () 78
107.9
Ag Au --() 111 79
47
112.4
Cd Hg --() 112 80
114.8
118.7
121.8
Sb Bi
83
127.6
131.3
Xe
86
132.9
137.3
Ba
88
La*
138.9 89
178.5
Hf Rf
104
180.9
183.9
W
106
74
186.2
Re Bh
107
190.2
190.2
195.1
197.0
200.5
204.4
Tl
207.2
209.0
(210)
Po --() 116
(210)
At
85
Rn
(222)
(223)
Ra
(226)
Ac~
(227)
(257)
Db
(260)
(263)
Sg
(262)
(265)
(266)
Mt
109
---
--()
118
Lanthanide Series*
140.1 90
Ce Th
58
140.9 91
Pr
59
144.2 92
Nd U
60
(147)
P m
93
61
Sm
150.4 94
62
152.0 95
Eu
63
157.3 96
Gd
64
158.9 97
Tb Bk
65
162.5 98
Dy Cf
66
164.9 99
Ho Es
67
167.3 100
Er
68
Tm
168.9 101
69
173.0 102
Yb
70
175.0 103 (257)
Lu Lr
71
Actinide Series~
232.0
(231)
Pa
(238)
Np
(237)
(242)
Pu
Am
(243)
Cm
(247)
(247)
(249)
(254)
Fm
(253)
Md
(256)
No
(254)
Remember free electrons now.

Even though electrons in a semiconductor live in bands of energy, we can treat them like free electrons, except for the gap.
The price we pay for treating a complicated system like free electrons: 1) EFermi is in the middle of the gap. 3) Density of states origin is referred to edge of band. 2) Electrons, holes have different effective mass values.
We now discuss these three points:
Semiconductors: 1) EFermi in middle of gap:
EFermi
In board, discuss magnitude of gap, kT smearing. Also high energy appr. to Fermi-Dirac, and low Probability of excitation!
P(E)
energy
energy
Semiconductors: 2) Density of states origin is referred to edge of band :

21/ 2 m 3 / 2 electrons ( E )dE = 2 3 / 2 ( E Ec )1/ 2 dE h
Ev
(E)
energy
21/ 2 m 3 / 2 holes ( E )dE = 2 3 / 2 ( Ev E )1/ 2 dE h
energy
Ec
Semiconductors: 3) Effective mass of electrons, holes:

Ev
energy
21/ 2 m 3 / 2 holes ( E )dE = 2 3 / 2 ( Ev E )1/ 2 dE h
energy
Ec
(E)
m m ,m
* e
* h
How many electrons in conduction band?
energy
EFermi
energy
Ec Ev
ni = P( E ) ( E )dE
Ec
energy
P(E)
(E)
P( E ) =
1 e
( E E f ) / kT
(Discuss high energy appr. on board.)
+1
m kT ni = 2 2h 2
* e
( E f Ec ) / kT e
3/ 2
How many holes in valence band?
energy
EFermi
Ev
energy
Ec
pi =
Ec
[1 P( E )] ( E )dE
1 e
( E E f ) / kT
energy
P(E)
(E)
P( E ) =
+1
m kT ( Ev E f ) / kT pi = 2 2h 2 e
* h
3/ 2
Holes and electrons
m kT ( Ev E f ) / kT pi = 2 2h 2 e
* h
3/ 2
energy
m kT ni = 2 2h 2
* e
( E f Ec ) / kT e
3/ 2
But Ef - Ec = (1/2) Egap and Ev - Ef=(1/2) Egap. With some algebra,
kT ni = pi = 2 2 2h
3/ 2
(m m )
* e
* 3/ 4 h
E g / 2 kT
Doping
If we purposely include some impurities in the crystal, we can add more electrons. This works if the impurity atoms have one more electron per atom than the host semiconductor. Since we increase # of electrons, Fermi energy increases Intrinsic means no doping. Examples discussed for Si on next slide:
Group** Period
1 IA 1A
1 2 3 4 5 6 7
1.008
H
3
2 IIA 2A
6.941 11
Li
9.012 12
Be
Silicon Dopants Donors

24
VIIIA
18
8A
2
13 IIIA 3A
14 IVA 4A
15 VA 5A
16 VIA 6A
17 VIIA 7A
4.003
He Ne Ar Kr
54 36 18 10
10.81
B
13
12.01 14
14.01 15
N P
33
16.00 16
O S
34
19.00 17
20.18
22.99 19
Na K
37
Mg
24.31 20
7 VIIB 7B
25
10
------- VIII ------------- 8 -------
11 IB 1B
29
12 IIB 2B
26.98 31
Al
28.09 32
Si
30.97
32.07
35.45 35
Cl
39.95
39.10
40.08
Ca Sr
56 38
44.96
Sc Y
57 39
21
47.88
Ti
40
22
50.94
V
41
23
Cr
52.00
Mn
54.94
55.85
Fe
44
26
58.47
Co Rh Ir
77 45
27
58.69
Ni
46
28
Cu
63.55
65.39
Zn
48
30
69.72
Ga In
81 49
72.59
Ge Sn Pb --() 114 82 50
74.92
As
51
78.96
Se Te
84 52
79.90 53 126.9
Br I
83.80
85.47
Rb Cs Fr
87 55
87.62
88.91
91.22
Zr
72
92.91
Nb Ta
105 73
Mo
95.94
42
Tc
(98) 75
43
101.1
Ru Os Hs
108 76
102.9
106.4
Pd Pt
110 () 78
107.9
Ag Au --() 111 79
47
112.4
Cd Hg --() 112 80
114.8
118.7
121.8
Sb Bi
83
127.6
131.3
Xe
86
132.9
137.3
Ba
88
La*
138.9 89
178.5
Hf Rf
104
180.9
183.9
W
106
74
186.2
Re Bh
107
190.2
190.2
195.1
197.0
200.5
204.4
Tl
207.2
209.0
(210)
Po --() 116
(210)
At
85
Rn
(222)
(223)
Ra
(226)
Ac~
(227)
(257)
Db
(260)
(263)
Sg
(262)
(265)
(266)
Mt
109
---
--()
118
Lanthanide Series*
140.1 90
Ce Th
58
140.9 91
Pr
59
144.2 92
Nd U
60
(147)
P m
93
61
Sm
150.4 94
62
152.0 95
Eu
63
157.3 96
Gd
64
158.9 97
Tb Bk
65
162.5 98
Dy Cf
66
164.9 99
Ho Es
67
167.3 100
Er
68
Tm
168.9 101
69
173.0 102
Yb
70
175.0 103 (257)
Lu Lr
71
Actinide Series~
232.0
(231)
Pa
(238)
Np
(237)
(242)
Pu
Am
(243)
Cm
(247)
(247)
(249)
(254)
Fm
(253)
Md
(256)
No
(254)
N-type doped semiconductors: Finite temperature:

Doped + thermally excited electrons Bandgap Empty states: holes energy energy
Low temperature:
Doped electrons Bandgap NO Empty states: holes CONDUCTION AT LOW TEMPERATURE!
How many electrons in conduction band?

Doped Fermi energy
energy
energy
Ev
Intrinsic Fermi energy P(E) (E)

* me kT = 2 2h 2
1 0
ntotal = ni + N donors
( EFermi (intrinsic) Ec ) / kT e + N donors
We can determine the new Fermi level by the relationship:
ntotal = ni + N donors
* me kT ( EFermi new Ec ) / kT = 2 2h 2 e
HW will calculate what has to be EFermi new for a given dopant density N for this formula to come out right..
energy
EFermi EFermi
Ec
How many electrons in conduction band? A method to calculate if Efermi is known:

Doped Fermi energy
energy
energy
EFermi
energy
Ec Ev
ni = P( E ) ( E )dE
Ec
P(E) Intrinsic Fermi energy
(E)
P( E ) =
3/ 2
1 e
( E E f ) / kT
+1
m kT ( E f Ec ) / kT ni = 2 2h 2 e
* e
How many holes in valence band? A method to calculate if Efermi is known:

Doped Fermi energy
energy
EFermi
Ev
energy
Ec
pi =
Ec
[1 P( E )] ( E )dE
1 e
( E E f ) / kT
energy
(E)
P( E ) =
+1
m kT ( Ev E f ) / kT e pi = 2 2 2h
* h
3/ 2
Holes and electrons when doped N-type
m kT ( Ev E f ) / kT p = 2 2h 2 e
* h
3/ 2
energy
m kT ( E f Ec ) / kT n = 2 2h 2 e
* e
3/ 2
But Ef - Ec (1/2) Egap and Ev Ef (1/2) Egap!
n> p
We can do the whole exercise again with HOLES.
Group** Period
1 IA 1A
1 2 3 4 5 6 7
1.008
H
3
2 IIA 2A
6.941 11
Li
9.012 12
Be
22.99 19
Na K
37
Mg
24.31 20
3 IIIB 3B
4 IVB 4B
5 VB 5B
6 VIB 6B
24
Silicon p-type (hole) dopants acceptors

7 VIIB 7B
25
VIIIA
18
8A
2
13 IIIA 3A
14 IVA 4A
15 VA 5A
16 VIA 6A
17 VIIA 7A
4.003
He Ne Ar Kr
54 36 18 10
10.81 13
12.01 14
14.01 15
N P
33
16.00 16
O S
34
19.00 17
20.18
10
------- VIII ------------- 8 -------
11 IB 1B
29
12 IIB 2B
30
26.98 31
Al
28.09 32
Si
30.97
32.07
35.45 35
Cl
39.95
39.10
40.08
Ca Sr
56 38
44.96
Sc Y
57 39
21
47.88
Ti
40
22
50.94
V
41
23
Cr
52.00
Mn
54.94
55.85
Fe
44
26
58.47
Co Rh Ir
77 45
27
58.69
Ni
46
28
Cu
63.55
65.39
Zn
48
69.72
Ga In
81 49
72.59
Ge Sn Pb --() 114 82 50
74.92
As
51
78.96
Se Te
84 52
79.90 53 126.9
Br I
83.80
85.47
Rb Cs Fr
87 55
87.62
88.91
91.22
Zr
72
92.91
Nb Ta
105 73
Mo
95.94
42
Tc
(98) 75
43
101.1
Ru Os Hs
108 76
102.9
106.4
Pd Pt
110 () 78
107.9
Ag Au --() 111 79
47
112.4
Cd Hg --() 112 80
114.8
118.7
121.8
Sb Bi
83
127.6
131.3
Xe
86
132.9
137.3
Ba
88
La*
138.9 89
178.5
Hf Rf
104
180.9
183.9
W
106
74
186.2
Re Bh
107
190.2
190.2
195.1
197.0
200.5
204.4
Tl
207.2
209.0
(210)
Po --() 116
(210)
At
85
Rn
(222)
(223)
Ra
(226)
Ac~
(227)
(257)
Db
(260)
(263)
Sg
(262)
(265)
(266)
Mt
109
---
--()
118
Lanthanide Series*
140.1 90
Ce Th
58
140.9 91
Pr
59
144.2 92
Nd U
60
(147)
P m
93
61
Sm
150.4 94
62
152.0 95
Eu
63
157.3 96
Gd
64
158.9 97
Tb Bk
65
162.5 98
Dy Cf
66
164.9 99
Ho Es
67
167.3 100
Er
68
Tm
168.9 101
69
173.0 102
Yb
70
175.0 103 (257)
Lu Lr
71
Actinide Series~
232.0
(231)
Pa
(238)
Np
(237)
(242)
Pu
Am
(243)
Cm
(247)
(247)
(249)
(254)
Fm
(253)
Md
(256)
No
(254)
P-type doped semiconductors: Finite temperature:

Doped + thermally excited electrons Bandgap Empty states: holes energy energy
Low temperature:
no electrons Bandgap Empty states: holes CONDUCTION AT LOW TEMPERATURE!
How many holes in valence band?

Doped Fermi energy energy
energy
Ev
Intrinsic Fermi energy P(E) (E)

* mh kT = 2 2h 2
1 0
ptotal = pi + N acceptors
( Ev EFermi (intrinsic) ) / kT e + N acceptors ( Ev EFermi new ) / kT e

We can determine the new Fermi level by the relationship:
ptotal = pi + N acceptors
* mh kT = 2 2h 2
HW will calculate what has to be EFermi new for a given dopant density N for this formula to come out right..
energy
EFermi EFermi
Ec
How many holes in valence band? A method to calculate if Efermi is known:

Doped Fermi energy
energy
EFermi
Ev
energy
Ec
pi =
Ec
[1 P( E )] ( E )dE
1 e
( E E f ) / kT
energy
(E)
P( E ) =
+1
m kT ( Ev E f ) / kT e pi = 2 2 2h
* h
3/ 2
How many electrons in conduction band? A method to calculate if Efermi is known:

Doped Fermi energy
energy
energy
EFermi
energy
Ec Ev
ni = P( E ) ( E )dE
Ec
(E)
P( E ) =
3/ 2
1 e
( E E f ) / kT
+1
m kT ( E f Ec ) / kT n = 2 2h 2 e
* e
Holes and electrons when doped
m kT ( Ev E f ) / kT p = 2 2h 2 e
* h
3/ 2
energy
m kT ( E f Ec ) / kT n = 2 2h 2 e
* e
3/ 2
But Ef - Ec (1/2) Egap and Ev Ef (1/2) Egap!
n< p
In conclusion: Intrinsic:
energy
EFermi
P(E)
n= p
energy energy
n-type:
EFermi
EFermi
P(E)
P(E)
n= p
n> p
Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##67 Lecture 12, Slide 67
energy energy
n-type:
energy
p-type:
EFermi
EFermi
EFermi
P(E)
P(E)
P(E)
n= p
n> p
n< p
What weve done:

Free electron density of states Fermi-Dirac distrubution function Band theory of solids (metal, insulator, semiconductor) Effective mass, density of states in semiconductors Electron, hole carrier concentrations in semiconductors

Lecture 12: Free Electrons

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Lecture 12: Free electrons

Free electron theory of solids

Electrons are waves, too.

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##33 Lecture 12, Slide

Quantum mechanics of free particles:

h2 2 h2 2 h2 2 (A ei ( kxt ) ) = 2m (ik ) (A ei ( kxt ) ) ( x, t ) = 2m x 2 2m x 2

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

rr h 2 (k x 2 + k y 2 + k z 2 ) r h2 2 2 2 ( r , t ) (ik x ) + (ik y ) + (ik z ) A ei ( k r t ) = = 2m 2m

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##66 Lecture 12, Slide

Quantum mechanics of free particles:

Time-independent Schrodinger equation rr r i ( k r t )

Confined particles: A box

Similar to electric field inside the box.

Everywhere outside the box

As before, we will consider all six surfaces:

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##10 Lecture 12, Slide 10

Does not solve boundary condition!!!

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##11 Lecture 12, Slide 11

Boundary conditions: The plane x=L:

Boundary conditions: The plane x=L:

r ( r ) = ( 2i )3 A sin(knx x ) sin(k n y ) sin(knz z )

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##14 Lecture 12, Slide 14

r ( r ) = ( 2i )3 A sin(knx x ) sin(k n y ) sin(knz z )

These are the allowed energy levels, or quantum states

These are the allowed energy levels, or quantum states

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##16 Lecture 12, Slide 16

Energy spectrum of free particles:

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##20 Lecture 12, Slide 20

Density of states: Number of states between k, k+dk:

Last modified 1/2/2003 2:27 AM

All these states are filled with electrons.

In a typical metal, L ~ 0.1 nm. Ef ~ 10 eV

ECE 275B P.J. Burke, Winter 2003

Called Fermi-Dirac distribution function.

P=1/2 at Ef for all temperatures.

Last modified 1/2/2003 2:27 AM

Forget about free electrons for now.

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##29 Lecture 12, Slide 29

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM