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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##22 Lecture 12, Slide

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
ECE 275B P.J. Burke, Winter 2003

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
Lecture 12, Slide ##55 Lecture 12, Slide

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

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

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:

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.
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##77 Lecture 12, Slide

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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##88 Lecture 12, Slide

Confined particles: A box

L L

Goal: find

r (r )

Similar to electric field inside the box.

ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##99 Lecture 12, Slide

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:

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

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!!!

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:

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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##13 Lecture 12, Slide 13

Boundary conditions:
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

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

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

Boundary conditions:
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
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

ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##15 Lecture 12, Slide 15

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).

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:

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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##17 Lecture 12, Slide 17

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.
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##18 Lecture 12, Slide 18

( 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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##19 Lecture 12, Slide 19

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

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:

kz

N k dk = ?

ky kx

From Verdeyen

k k +k +k
2 x 2 y
ECE 275B P.J. Burke, Winter 2003

2 z

knx = n x / L kn y = n y / L knz = nz / L
Lecture 12, Slide ##21 Lecture 12, Slide 21

Last modified 1/2/2003 2:27 AM

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.
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##22 Lecture 12, Slide 22

 ( 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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##23 Lecture 12, Slide 23

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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##24 Lecture 12, Slide 24

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

ECE 275B P.J. Burke, Winter 2003

Occupation probability:

P(E)
0

energy
E=EFermi

P(E) = probability of occupying a state with energy E What about finite temperature?
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##26 Lecture 12, Slide 26

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.

ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##27 Lecture 12, Slide 27

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.

ECE 275B P.J. Burke, Winter 2003

kT
Lecture 12, Slide ##28 Lecture 12, Slide 28

Last modified 1/2/2003 2:27 AM

Forget about free electrons for now.

Back to the hydrogen atom.

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

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

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

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##30 Lecture 12, Slide 30

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

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##31 Lecture 12, Slide 31

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

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##32 Lecture 12, Slide 32

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

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##33 Lecture 12, Slide 33

Band theory of solids:

N Hydrogen atoms: N -> infinity
N levels -> band of energy energy
ECE 275B P.J. Burke, Winter 2003

N levels -> band of energy

N levels -> band of energy

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##34 Lecture 12, Slide 34

Band theory of solids: Filled bands do not conduct electricity! Insulator:

energy
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##35 Lecture 12, Slide 35

Band theory of solids: Filled bands do not conduct electricity! Insulator: Metal:

energy
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##36 Lecture 12, Slide 36

Band theory of solids: Filled bands do not conduct electricity! Insulator: Metal: Semiconductor:
Thermally excited electrons

Empty states: holes

energy
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##37 Lecture 12, Slide 37

Band theory of solids: Filled bands do not conduct electricity! Insulator: Metal: Semiconductor:
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

Lecture 12, Slide ##38 Lecture 12, Slide 38

Band theory of solids: Filled bands do not conduct electricity! Insulator: Metal: Semiconductor:
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

We usually dont care about lower bands. LASER will be formed by electrons going from conduction to valence band...
Lecture 12, Slide ##39 Lecture 12, Slide 39

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.

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##40 Lecture 12, Slide 40

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)

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##41 Lecture 12, Slide 41

Group** Period
1 IA 1A 18

1 2 3 4 5 6 7

1.008

H
3

2 IIA 2A

Ge:
3 IIIB 3B 4 IVB 4B 5 VB 5B 6 VIB 6B
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

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)

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##42 Lecture 12, Slide 42

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

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)

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##43 Lecture 12, Slide 43

Group** Period
1 IA 1A 18

1 2 3 4 5 6 7

1.008

H
3

2 IIA 2A

InP:
3 IIIB 3B 4 IVB 4B 5 VB 5B 6 VIB 6B
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

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)

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##44 Lecture 12, Slide 44

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:
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##45 Lecture 12, Slide 45

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!
ECE 275B P.J. Burke, Winter 2003

P(E)

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##46 Lecture 12, Slide 46

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)
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##47 Lecture 12, Slide 47

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:

21/ 2 m 3 / 2 electrons ( E )dE = 2 3 / 2 ( E Ec )1/ 2 dE h

Ev

energy
21/ 2 m 3 / 2 holes ( E )dE = 2 3 / 2 ( Ev E )1/ 2 dE h

energy

Ec

(E)
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM

m m ,m
* e
Lecture 12, Slide ##48 Lecture 12, Slide 48

* h

How many electrons in conduction band?

energy

EFermi

energy

Ec Ev

ni = P( E ) ( E )dE
Ec
21/ 2 m 3 / 2 electrons ( E )dE = 2 3 / 2 ( E Ec )1/ 2 dE h

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
ECE 275B P.J. Burke, Winter 2003

( E f Ec ) / kT e
Lecture 12, Slide ##49 Lecture 12, Slide 49

3/ 2

Last modified 1/2/2003 2:27 AM

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

21/ 2 m 3 / 2 electrons ( E )dE = 2 3 / 2 ( E Ec )1/ 2 dE h

P(E)

(E)

P( E ) =

+1

m kT ( Ev E f ) / kT pi = 2 2h 2 e
* h
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##50 Lecture 12, Slide 50

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
ECE 275B P.J. Burke, Winter 2003

3/ 2

(m m )
* e

* 3/ 4 h

E g / 2 kT

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##51 Lecture 12, Slide 51

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:
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##52 Lecture 12, Slide 52

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

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

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)

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##53 Lecture 12, Slide 53

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!

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##54 Lecture 12, Slide 54

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..
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##55 Lecture 12, Slide 55

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
21/ 2 m 3 / 2 electrons ( E )dE = 2 3 / 2 ( E Ec )1/ 2 dE h

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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##56 Lecture 12, Slide 56

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

P(E) Intrinsic Fermi energy

energy

21/ 2 m 3 / 2 electrons ( E )dE = 2 3 / 2 ( E Ec )1/ 2 dE h

(E)

P( E ) =

+1

m kT ( Ev E f ) / kT e pi = 2 2 2h
* h
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##57 Lecture 12, Slide 57

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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##58 Lecture 12, Slide 58

We can do the whole exercise again with HOLES.

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##59 Lecture 12, Slide 59

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

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)

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##60 Lecture 12, Slide 60

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!

ECE 275B P.J. Burke, Winter 2003

Last modified 1/2/2003 2:27 AM

Lecture 12, Slide ##61 Lecture 12, Slide 61

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

Lecture 12, Slide ##62 Lecture 12, Slide 62

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..
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM

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

P(E) Intrinsic Fermi energy

energy

21/ 2 m 3 / 2 electrons ( E )dE = 2 3 / 2 ( E Ec )1/ 2 dE h

(E)

P( E ) =

+1

m kT ( Ev E f ) / kT e pi = 2 2 2h
* h
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##63 Lecture 12, Slide 63

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
21/ 2 m 3 / 2 electrons ( E )dE = 2 3 / 2 ( E Ec )1/ 2 dE h

P(E) Intrinsic Fermi energy

(E)

P( E ) =
3/ 2

1 e
( E E f ) / kT

+1

m kT ( E f Ec ) / kT n = 2 2h 2 e
* e
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##64 Lecture 12, Slide 64

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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##65 Lecture 12, Slide 65

In conclusion: Intrinsic:
energy

EFermi

P(E)

n= p
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##66 Lecture 12, Slide 66

In conclusion: Intrinsic:
energy energy

n-type:

EFermi

EFermi

P(E)

P(E)

n= p
ECE 275B P.J. Burke, Winter 2003

n> p
Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##67 Lecture 12, Slide 67

In conclusion: Intrinsic:
energy energy

n-type:
energy

p-type:

EFermi

EFermi

EFermi

P(E)

P(E)

P(E)

n= p
ECE 275B P.J. Burke, Winter 2003

n> p
Last modified 1/2/2003 2:27 AM

n< p
Lecture 12, Slide ##68 Lecture 12, Slide 68

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
ECE 275B P.J. Burke, Winter 2003 Last modified 1/2/2003 2:27 AM Lecture 12, Slide ##69 Lecture 12, Slide 69