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Metals, Semiconductors, and Insulators
Metals, Semiconductors, and Insulators
Metals, Semiconductors, and Insulators
Metals have free electrons and partially filled valence bands, therefore they are highly
conductive (a).
Semimetals have their highest band filled. This filled band, however, overlaps with the next
higher band, therefore they are conductive but with slightly higher resistivity than normal
metals (b). Examples: arsenic, bismuth, and antimony.
Insulators have filled valence bands and empty conduction bands, separated by a large
band gap Eg(typically >4eV), they have high resistivity (c ).
Semiconductors have similar band structure as insulators but with a much smaller band
gap. Some electrons can jump to the empty conduction band by thermal or optical excitation
(d). Eg=1.1 eV for Si, 0.67 eV for Ge and 1.43 eV for GaAs
Conduction in Terms of Band
Metals
An energy band is a range of allowed electron energies.
The energy band in a metal is only partially filled with electrons.
Metals have overlapping valence and conduction bands
Drude Model of Electrical Conduction in Metals
“Freedom”
Electron Energy
Empty States
Energy Band
States Filled with Electrons
Distance
Band Diagram: Metal
T>0
EC
Fermi “filling” Energy band to
function EF be “filled”
Conduction band
(Partially Filled)
E=0
At T = 0, all levels in conduction band below the Fermi energy EF are filled
with electrons, while all levels above EF are empty.
Electrons are free to move into “empty” states of conduction band with
only a small electric field E, leading to high electrical conductivity!
At T > 0, electrons have a probability to be thermally “excited” from below
the Fermi energy to above it.
Resistivity (ρ) in Metals
Resistivity typically increases linearly with temperature:
ρt = ρo + αT
Phonons scatter electrons. Where ρo and α are constants for an
specific material
Impurities tend to increase resistivity: Impurities scatter electrons in
metals
Plastic Deformation tends to raise resistivity dislocations scatter
electrons
1
σ= = nqμ
ρ
The electrical conductivity is controlled by controlling the number of
charge carriers in the material (n) and the mobility or “ease of
movement” of the charge carriers (μ)
Temperature Dependence, Metals
There are three contributions to ρ:
ρt due to phonons (thermal)
ρi due to impurities
ρd due to deformation
ρ = ρt + ρi+ ρd
The number of electrons in the
conduction band does not vary
with temperature.
All the observed temperature
dependence of σ in metals arise
from changes in μ
Scattering by Impurities and Phonons
ρ t = ρ o + aT
Impurity or Composition scattering
Independent of temperature
Proportional to impurity concentration
“Conduction Band”
Empty
Electron
Energy
“Forbidden” Energy
Gap
“Valence Band”
Filled with Electrons
Distance
Band Diagram: Insulator
Conduction band
T>0 (Empty)
EC
Egap
EF
Valence band
EV
(Filled)
Example:
σ = n.Z.q.μ
Suppose that the electrical conductivity of MgO is determined primarily by the
diffusion of Mg2+ ions. Estimate the mobility of Mg2+ ions and calculate the
electrical conductivity of MgO at 1800oC.
Data: Diffusion Constant of Mg in MgO = 0.0249cm2/s ; lattice parameter of
MgO a=0.396x10-7cm ; Activation Energy for the Diffusion of Mg2+ in MgO =
79,000cal/mol ; kB=1.987cal/K=k-mol; For MgO Z=2/ion; q=1.6x10-19C;
kB=1.38x10-23J/K-mol
First, we need to calculate the diffusion coefficient D
⎛ − QD ⎞ cm 2 ⎛ − 79000cal / mol ⎞
D = Do exp⎜ ⎟ = 0. 0239 exp⎜
⎜ ⎟⎟
⎝ kT ⎠ s ⎝ 1.987cal / mol − Kx (1800 + 273)K ⎠
D=1.119x10-10cm2/s
(0.396 ×10 −7 cm )3
Solution:
We can calculate the drift mobility (μ) of the Na+ ions from the conductivity
expression
σ = ni × q × μ i
Where ni is the concentration of Na+ ions in the structure.
20%Na2O-80%SiO2 can be written as M At = 0.2 × ( 2( 23) + 1(16)) + 0.8 × (1( 281.1) + 2(16))
(Na2O)0.2-(SiO2)0.8 . Its mass can be
M At = 60.48g .mol −1
calculated as:
The number of (Na2O)0.2-(SiO2)0.8 units per unit volume can be found from the
density
ρ × NA ( 2.4g .cm −3 ) × (6.023x10 23 mol −1 )
n= =
M At 60.48g .mol −1
n = 2.39 ×10 22 (Na 2O ) 0.2 (SiO 2 ) 0.8 units − cm −3
The concentration of Na+ ions (ni) can be obtained from the concentration of
(Na2O)0.2-(SiO2)0.8 units
⎡ 0.2 × 2 ⎤ −3
ni = ⎢ ⎥ × 2. 39 × 10 22
= 3 . 18 × 10 21
cm
⎣ 0 . 2 × ( 2 + 1) + 0 . 8 × (1 + 2 ) ⎦
σ (8.25 × 10 −6 Ω −1m −1 )
And μi μi = =
q × ni (1.60 ×10 −19 C ) × (3.186 × 10 21 × 106 m −3 )
μ i = 1.62 ×10 −14 m 2V −1s −1
T>0
Conduction band
(Partially Filled)
EC
EF
EV
Valence band
(Partially Empty)
Si Si Si Si Si Si Si
free
electron
Si Si Si Si Si Si Si
free
hole
Si Si Si Si Si Si Si
Semiconductors in Group IV
Carbon
Silicon
Germanium
Tin
Each has 4 valence Electrons.
Covalent bond
Generation of Free Electrons and Holes
In an intrinsic semiconductor, the number of free electrons equals the
number of holes.
Thermal : The concentration of free electrons and holes increases with
increasing temperature.
Thermal : At a fixed temperature, an intrinsic semiconductor with a large
energy gap has smaller free electron and hole concentrations than a
semiconductor with a small energy gap.
Optical: Light can also generate free electrons and holes in a
semiconductor.
Optical: The energy of the photons (hν) must equal or exceed the energy
gap of the semiconductor (Eg) . If hν > Eg , a photon can be absorbed,
creating a free electron and a free hole.
This absorption process underlies the operation of photoconductive light
detectors, photodiodes, photovoltaic (solar) cells, and solid state camera
“chips”.
UV 100-400 nm 12.4-3.10 eV
Violet 400-425 nm 3.10-2.92 eV
Blue 425-492 nm 2.92-2.52 eV
Green 492-575 nm 2.52-2.15 eV
Yellow 575-585 nm 2.15-2.12 eV
Orange 585-647 nm 2.12-1.92 eV
Red 647-700 nm 1.92-1.77 eV
Near IR 10,000-700 nm 1.77-0.12 eV
Red Violet
Orange Blue
Yellow Green
Photoconductivity
Conductivity is dependent on
the intensity of the incident
Eg hων ≥EEgg electromagnetic radiation
As T ↑ then ni ↑
As Eg ↑ then ni ↓
What is the detailed form of these dependencies?
We will use analogies to chemical reactions. The electron-hole formation can be
though of as a chemical reaction…….. bond ⇔ e − + h +
Similar to the chemical reaction……… H 2O ⇔ H + + (OH ) −
The Law-of-Mass-Action relates concentration of
reactants and reaction products. For water…… [H + ][OH − ] ⎛ E ⎞
K= ≈ exp⎜ − ⎟
Where E is the energy released or consumed [H 2O ]
during the reaction………….
⎝ kT ⎠
This is a thermally activated process, where the rate of the reaction is limited by the
need to overcome an energy barrier (activation energy).
By analogy, for electron-hole formation: [ no ][ po ] ⎛ Eg ⎞
K= ≈ exp⎜⎜ − ⎟⎟
Where [bonds] is the concentration of unbroken bonds [ bonds ] ⎝ kT ⎠
and Eg is the activation energy
[bonds] >> no ,po
In general, relative few bonds are broken to form an
electron-hole and therefore the number of bonds are [bonds] = cons tan t
approximately constant.
⎛ Eg ⎞
no po ≈ exp⎜⎜ − ⎟⎟
Two important results: ⎝ kT ⎠
⎛ Eg ⎞
1)…………………….. ni ≈ exp⎜⎜ − ⎟⎟
⎝ 2kT ⎠
2)………………………………………….…….. nO × pO = ni2
⎛ − ΔE ⎞
n i ≈ exp ⎜⎜ ⎟⎟
⎝ k BT ⎠
For intrinsic semiconductor, the energy is half way across the gap, so that
⎛ − Eg ⎞
n i ≈ exp ⎜⎜ ⎟⎟
⎝ 2 k BT ⎠
⎛ − Eg ⎞
σ = σ O exp ⎜⎜ ⎟⎟
⎝ 2 k BT ⎠
Example
Calculate the number of Si atoms per cubic meter. The density of silicon is 2.33g.cm-3
and its atomic mass is 28.03g.mol-1.
Then, calculate the electrical resistivity of intrinsic silicon at 300K. For Si at 300K
ni=1.5x1016carriers.m-3, q=1.60x10-19C, μe=0.135m2(V.s)-1 and μh=0.048m2.(V.s)-1
Solution
N A × ρSi
nSi = = 5.00 ×10 28 Si − atoms.m −3
ASi
⎛ − Eg ⎞ ⎛ − Eg ⎞ ⎛ − Eg ⎞
σ = C . exp⎜⎜ ⎟⎟ σ 473 = C . exp⎜⎜ ⎟⎟ σ 300 = C . exp⎜⎜ ⎟⎟
⎝ 2k BT ⎠ ⎝ 2k B ( 473) ⎠ ⎝ 2k B (300) ⎠
σ 473 ⎛ − Eg − Eg ⎞
= exp⎜⎜ − ⎟⎟
σ 300 ⎝ 2k B ( 473) 2k B (300) ⎠
⎛ σ 473 ⎞ − Eg Eg Eg ⎛ 1 1 ⎞ 1.1eV ⎛ 1 1 ⎞
ln⎜⎜ ⎟⎟ = + = ⎜ − ⎟= ⎜ − ⎟
⎝ σ 300 ⎠ 2k B ( 473) 2k B (300) 2k B ⎝ 300 473 ⎠ 2(8.62 × 10 ) ⎝ 300 473 ⎠
−5
⎛ σ 473 ⎞
ln⎜⎜ ⎟⎟ = 7.777
⎝ σ 300 ⎠
1
σ 473 = σ 300 ( 2385) = ( 2385) = 1 . 04( Ω.m ) −1
2.3 ×103
Example: For germanium at 25oC estimate
(a) the number of charge carriers,
(b) the fraction of total electrons in the valence band that are excited into the conduction
band and
⎛ − Eg ⎞
(c) the constant A in the expression n = A exp ⎜ ⎟ when E=Eg/2
⎜ 2k T ⎟
⎝ B ⎠
Data: Ge has a diamond cubic structure with 8 atoms per cell and valence of 4 ;
a=0.56575nm ; Eg for Ge = 0.67eV ; μe = 3900cm2/V.s ; μh = 1900cm2/V.s ;
ρ = 43Ω-cm ; kB=8.63x10-5eV/K
(a) Number of carriers
T = 25o C
2k BT = ( 2)(8.63 × 10 −5 eV / K )( 273 + 25) = 0.0514eV
σ 0.023 13 electrons
n= = = 2.5 × 10
q ( μe + μ h ) 1.6 ×10 (3900 + 1900)
−19
cm 3
There are 2.5x1013 electrons/cm3 and 2.5x1013 holes/cm3 helping to conduct a charge
in germanium at room temperature.
b) the fraction of total electrons in the valence band that
are excited into the conduction band
n 2.5 × 1013
A= ⎛ −E g ⎞
= ⎛ − 0.67 ⎞
= 1.14 × 10 −19 carriers / cm 3
⎜⎜ ⎟⎟ ⎜ ⎟
⎝ 0.0514 ⎠
e ⎝ 2 k BT ⎠ e
Direct and Indirect Semiconductors
The real band structure in 3D is calculated with various numerical methods,
plotted as E vs k. k is called wave vector p = k p is momentum
For electron transition, both E and p (k) must be conserved.
A semiconductor is
direct if the maximum
of the conduction band
and the minimum of
the valence band has
the same k value