Chapter 1

Introduction to Semiconductors

• Electronic properties of solid state materials

• Semiconductors in equilibrium: band diagram and
statistics
• Semiconductors under perturbation: carrier transport,
generation, and recombination
(Many concepts have been covered in 207 and 733, and
therefore this chapter will go through quickly).

Chapter 1 EE 620, IIT Bombay 1

 Three Most Important Topics (MIT) Today
• Bandgap viewpoints on solid state materials (and
why Si is “close to” perfect in this perspective)
• Equilibrium carrier statistics (and the fermi level)
in intrinsic semiconductors
• Equilibrium carrier statistics (and the fermi level)
in extrinsic semiconductors (degenerate and
nondegenerate)

(Reading Assignments: Chap 1, Sec. 2.1, Appendix A.3 and

A.4 of Taur and Ning)

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 Introduction to Semiconductors
• Semiconductor is the class of material where the
conductivity of the material can be controlled to vary a
large orders of magnitude.
– Elemental semiconductor: Si, Ge
– Compound semiconductor (fixed composition): SiC, GaAs,
GaN
– Alloy: Si1-xGex, Al1-xGaxAs, Hg1-xCdxTe, etc.
• Purity: VLSI devices are made of semiconductors with
ultra purity: unintentional doping < 10-9 in composition,
i.e., 0.001 ppm in solids (how to maintain the periodical
potential, instead of governing by traps).
– To increase range of control in conductivity
– To increase mobility (faster and more powerful devices)
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 Structure of Solids
• Amorphous (no short/long-range order, “glass” phase included?)
• Poly-crystalline (short-range order, typically, 1nm - 50μm
range)
• Crystalline (long-range order, irregularity treated as defects,
faults, stacked faults or line faults)
• There is also another class of quasi-crystals, and other types of
long-range orders such as those in oligomers and polymers.
• To achieve nanoscale devices, usually we need crystalline, fine-
grain poly-crystalline, or amorphous.
• Crystals can be described by the unit cell, which can be repeated
to form the entire crystal. Lattice + base = crystal.
grains

crystalline poly-crystalline
grain boundary
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 Atomic Structures
Grain
Grain/domain boundary

Amorphous Polycrystalline Crystal

Diamond lattice cell Zincblende lattice cell

(C, Si, Ge, etc.) (GaAs, AlAs, GaP, ZnS, etc.)

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 Crystal Orientation of Cubic Materials
• Planes are represented by the
normal vector
• Face-center-cubic (FCC) has offset by d/4
8 corner and 6 face atoms in
the Cartesian lattice
• Diamond (covalent, Si, Ge,
C, etc.) and Zinc-blend
(ionic, GaAs, InP, etc.) face atom in FCC
consist of 2 interleaved FCC corner atom in FCC
with 1/4 diagonal offset
• Tetrahedral bonding sp3

(110) (111)

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Zinc Blende

Simple cubic body center cubic face center cubic

Can you see the interpenetrating FCC ?

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 Use of Crystal Orientation
• Electrical anisotropy: (100) has
the highest mobility, also
scattering rates are slightly
different
• Mechanical anisotropy: different
surface has different modulus
components (later)
• Chemical anisotropy: e.x., KOH
will not etch (111) Newer wafers (8” and 12”) now
use a groove to mark the
• Angles: (100) vs. (110): 45, 90  orientation, instead of a cut to
; (100) vs. (111): 54.74; (110) save some area for test structures
vs. (111): 35.26, 90  or 144.74
• Important for strain engineering

Chapter 1 EE 620, IIT Bombay 8

 Semiconductor Carriers in Equilibrium
• Equilibrium implies detailed balance: carriers relaxed to
steady state for both spatial, momentum and energy states
• Frame of reference before perturbation (driving forces)
• Not QM-exact description, but to build a model usable for
rapid device analysis. More QM in EE 723. Also, since
much material has been gone through in 207 and 733, I
will emphasize more on the physical concepts.
• Atom can be approximated with “the core” and “the
valence electrons” (similar to the “pseudo-potential”
approximation: The core is the filled states of all electrons
with the same major quantum number (not so true for the
d orbit), such as 1S2, 2S2, 2P6, etc...

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Orbit Model:
Connection to Chemistry
• Valence electrons are:
– outermost electrons in orbital concepts
– easiest to break off from the nucleus
– participate in the chemical reactions
– can break the Coulombic potential (ionization) and contribute to
conduction
– dominant in chemical and semiconductor discussions (why the
periodic table is very important)
• Two descriptions of crystal lattice: the bond (spatial)
model and the band (energy) model

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 The Bond and Band Models
• The bond model
– simplification from the 3D lattice (usually plotted in 2D)
– every core has nearest neighbors described by chemical covalent bond.
Remember that electrons are indistinguishable.
– Electrons breaking free from localization (but still remain in solid) need
energy smaller than, but comparable to, the covalence bond strength, due to
lattice readjustment and harmonic/aharmonic vibration:
• point defect (substitutional vacancy, atomically compressive stress)
• interstitial Si (interstitials, atomically tensile stress)
• bond breaking and electrons shared.

E Lattice spacing
at 0K
X = bond strain

Point-defect Ionization
in the bond model in the bond model
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 Atomic Spacing and Bandgap
The band model: (describe the
energy of carriers)
•remember that the carriers are
usually indistinguishable
•when atoms are brought to close
proximity, the energy associated with
valence electrons change
significantly
Relations between atomic spacing
and energy gap
• In compressive stress: Egap
• In tensile stress: Egap
dE gap 4
• T increases: Egap for Si around 300K: dT  2.7  10 eV / K
• A totally filled (or totally empty) band cannot contribute to electrical
conduction (momentum will cancel for filled bands)
• If somehow a valence electron absorbs Egap energy and enters into the
conduction band, it can contribute to conduction

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 Molecular Orbitals to Bands

2 atoms produce levels 10 atoms produce bands of

levels; each level has a slightly
different energy due to Pauli’s
exclusion
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 Material Characterization by Bandgap
• Insulator (in room temperature) : Egap > 4eV (SiO2: 9.1eV,
Si3N4: ~5eV)
• Conductor: Egap < 3 kT ~ 0.1eV, or even negative bandgap
• Semiconductor: anything in between, depending on what
temperature we are talking about.
• Regular semiconductor in room temperature: Si: Egap= 1.12
eV; Ge: Egap= 0.66eV and GaAs: Egap= 1.42 eV: this is the
system that can be dealt with most easily.
• For wide-bandgap materials (Egap~ 2-3eV), conduction is
usually governed more by the structural imperfection (less
different than crytalline insulator)
• For narrow-bandgap materials (Egap~ 0.25eV), conduction is
usually governed by DOS of available states and Mott
transition.
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 Material Characterization by Bandgap

Metal Semi-metal Semiconductor Insulator

E(k) is replaced by E(x) => adding the potential/Efield

info

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 Carriers in Semiconductors
• Properties of carriers (electrons and holes) in
“regular” semiconductors
– Charge: as classical (n, p, ND+, NA and traps)
– Effective mass: almost as classical. It can be defined
differently such as effective mass of DOS, effective
mass of conduction, etc.
• Equilibrium Carriers statistics (this concerns the
number of carriers, and can be “exponentially”
controlled)
– Similar to [H+][OH] = constant for H+ + OH  H2O

np  n2
i
True in equilibrium regardless of doping

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 Intrinsic Semiconductors
Intrinsic case (electrical properties of “pure” semiconductor)
– All conduction caused by thermal breakup of electron-hole pairs
– n=p=ni, 1.41010 cm-3 for Si, 2106 for GaAs, and 21013 for Ge at 300K
– There are about 5  1022 atoms/cm3, and 2  1023 valence electrons
– Because the energy for generating electron-hole pairs is from the thermal
energy, ni increases exponentially with temperature.

Eg

Bond
breaking

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 Total energy to create free carrier
Energy eigenstate of e in attractive potential
due to hole in Si (same as H atom problem)

Free

Eg Bound to hole
Eg

Step 1: Bond breaking Step2 : Escape from electrostatic

creates e-h pair attraction between electron and hole
(exciton)  requires to be free carriers
energy of Eg
Note: potentials from band diagram and
charge can be superposed
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 Doping in Semiconductors
• Use of doping (impurity) to create conduction carriers more
easily
– The bond model: EB = q4m*/2(4s0)2 EHm*/m0s20.1eV
– N-type material: n  ND, p  0 (in linear scale)
– P-type material: p  NA, n  0 (in linear scale)
– There is solid solubility limit depending on temperature.
Above the limit, the dopants will form segregates.

N-type EB(eV) P-type EB (eV)

Donors Acceptors
P 0.045 B 0.045
As 0.054 Al 0.067
Sb 0.039 Ga 0.072
In 0.16

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 N-type Semiconductors

Charge species: n and ND+ and n  ND+ in bulk N-type

semiconductors for charge neutrality.
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 P-type Semiconductors

Charge species: p and NA and p  NA in bulk N-type

semiconductors for charge neutrality.

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 Thermalization of Dopants
– This is because the carrier looks at the ionized impurity through
the sea of other Si atoms and valence band, and the bond
strength needs to be corrected with the dielectric constant
(polarization effect) and the effective mass (periodic potential)
– The binding energy of carriers to impurity atom is much
weaker than the Si valence electron to the Si atom.
Freeze-out extrinsic intrinsic

n/ND

ni

– In room temperature, regular semiconductors are extrinsic.

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 Fermi Distribution (Occupancy of States)
• How many states will be filled in a given carrier
system?
– The carrier distribution will be described by the Fermi
functions (both electrons and holes are Fermions. In
contrast, photons and phonons are Bosons). This
describes the number of carriers in a specific energy
level.
– Given the Fermi energy EF of the system (EF is a
constant in equilibrium), the Fermi distribution function
with respect to carrier energy is:

1
f (E)  ( E  E F ) / k BT Detailed balance in equilibrium!!
1 e

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 The Fermi Function
1
f (E)  ( E  E F ) / k BT
1 e
– if E >> EF , f(E)  exp( (EF - E)/kBT ), which is the
Boltzmann distribution for electrons
– if E << EF , f(E)  1 - exp(- (EF - E)/kBT ) or holes for
exp( -(EF - E)/kBT ), Boltzmann’s distributions
– if E = EF , f(E) = 0.5
Below EF: occupied Above EF: occupied
f(E) T=0 f(E) T>0
0.5 0.5

EF EF

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 Carrier Concentrations and the Band Diagram
Assume some states x
Fermi function Free carrier concentration
=
distributed in energy electrons
Nc f(E)
Ec E
EF
Ei
Ev n
NV holes

– For undoped intrinsic materials: n=p=ni since all

electrons and holes are generated in pairs. If we
assume EF will be deep in the bandgap (later on we
will see this assumption is valid except for materials
with very narrow bandgap), and the Boltzmann
approximation can be used (instead of the Fermi
integral). Cancel EF in n=p= ni:
 E gap / 2 k BT
ni  Nc Nv e

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 Intrinsic Levels in the Band Diagram
Nc
Ec f(E) E
EF=Ei
Ev n
NV

– Cancel Nc and Nv:

( EF  Ei ) / k BT ( Ei  EF ) / k BT
n  ni e p  ni e np  n 2
i

– Cancel ni to obtain EF for intrinsic materials (which

we denote as Ei)
Ec  Ev k BT Nv Ec  Ev 3k BT m*p
Ei   ln( )   ln( * )
2 2 Nc 2 4 mn

For Si at 300K,
Chapter 1 EE 620, IIT Bombay
0.3kBT 26
Fully-ionized Dopant in Nondegnerate Materials
– For extrinsic materials, we still have total charge
neutrality: p - n + ND+ - NA - = 0 and constant EF
in space:
ni2
if N D  N A n  ND p
ND
ni2
if N A  N D p  NA n check N D  1016 p  10 4  ni
NA

– For extrinsic materials we further have

 ND   NA 
EF  Ei  k BT ln   n  type Ei  EF  k BT ln   p  type
 ni   ni 

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 Fermi Level and Dopant Ionization

As temperature increases, intrinsic carriers dominate over

extrinsic carriers
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 Properties of Si and SiO2 at room
temperature
Physical property Si SiO2

Atomic/molecular density (cm-3) 51022 2.31022

Crystal structure Diamond Amorphous
Covalent radius (Å) 1.11 around 1
Egap (eV) 1.12 9.1
Dielectric constant 11.7 below 3.9
Intrinsic density 1.4 1010 -
Carrier mobility (cm2/Vs) Electron: 1440 -
Hole: 470 -
Effective DOS (cm-3) NC: 3.2 1019 -
NV: 1.8 1019 -
Breakdown field (V/cm) 3 105 > 107
Melting point (C) 1410 1600-1700
Thermal conductivity (W/cm C) 1.5 0.014

Chapter 1 EE 620, IIT Bombay 29

 Category of Generation-Recombination
Generation-
Recombination • Photons have large
thermal optical carrier
energy but small
momentum, not
(impact ionization)
effective for indirect
bandgap
band-to-band • Phonons have small
energy (kT/q) but
large momentum, not
effective for 1.1eV
(elec. capture) (elec. capture)
bandgap
band-to-trap
• Trap assisted
generation-
recombination is
(change in location)
most efficient at mid-
trap-to-trap (trap hopping/tunneling)
gap (Au, Cu, Mn, Cr,
(change in energy)
Fe in Si)

Chapter 1 EE 620, IIT Bombay 30