Quantization Concept

plank constant

2.3 Energy band theory

Core electrons

Valence electrons

Quantization Concept

Energy Band Formation (I) Band theory of solids

Two atoms brought together to form molecule splitting of energy levels for outer electron shells

The Shell Model

L shell with two sub shells Nucleus

1s K L 2s 2p

1s22s22p2 or [He]2s22p2
The shell model of the atom in which the electrons are confined to live within certain shells and in sub shells within shells.

Energy Band Formation (I)

Energy Band Formation

Broadening of allowed energy levels into allowed energy bands separated by forbidden-energy gaps as more atoms influence each electron in a solid.

Allowed energy levels of an electron acted on by the Coulomb potential of an atomic nucleus.

Splitting of energy states into allowed bands separated by a forbidden energy gap as the atomic spacing decreases.
The electrical properties of a crystalline material correspond to specific allowed and forbidden energies associated with an atomic separation related to the lattice constant of the crystal.

One-dimensional representation

Two-dimensional diagram in which energy is plotted versus distance.

Energy Band Formation (III)

Conceptual development of the energy band model.
N isolated Si-atoms
Electron energy Electron energy

Energy Band Formation (II) Energy Bandgap

where no states exist
Electron energy

Pauli Exclusion Principle

Crystalline Si N -atoms 4N allowed-states (Conduction Band)

No states

Mostly empty

Etop Ec Ev Ebottom
Only 2 electrons, of spin 1/2, can occupy the same energy state at the same point in space. As atoms are brought closer towards one another and begin to bond together, their energy levels must split into bands of discrete levels so closely spaced in energy, they can be considered a continuum of allowed energy.

p s n=3

Eg
Mostly filled

6N p-states total 2N s-states total (4N electrons total)

4N allowed-states (Valance Band)

Electron energy

p s

4N empty states

2N+2N filled states

isolated Si atoms

Decreasing atom spacing

Si lattice spacing

Strongly bonded materials: small interatomic distances. Thus, the strongly bonded materials can have larger energy bandgaps than do weakly bonded materials.

Energy Band Formation (Si)

Energy levels in Si as a function of inter-atomic spacing
The 2N electrons in the 3s sub-shell and the 2N electrons in the 3p sub-shell undergo sp3 hybridization.

Energy Band Formation

Energy levels in Si as a function of inter-atomic spacing

conduction band (empty)

valence band (filled)

The core levels (n=1,2) in Si are completely filled with electrons.

Energy Band Formation

Energy band diagrams.

N electrons filling half of the 2N allowed states, as can occur in a Metal.

A completely empty band separated by an energy gap Eg from a band whose 2N states are completely filled by 2N electrons, representative of an Insulator.

Metals, Semiconductors, and Insulators

Typical band structures of Metal
Electron Energy,
Vacuum level

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Metals, Semiconductors, and Insulators

Typical band structures of Semiconductor

Covalent bond Si ion core (+4e)

Free electron 3s Band 2 p Band

Electron energy, E
Ec+ Ec Band gap = Eg Ev
Valence Band (VB) Full of electrons at 0 K. ConductionBand(CB) Empty of electrons at 0 K.

E =0
Overlapping energy bands

3p 3s 2p 2s 2 s Band

Electrons

1s ATOM

1s
SOLID

In a metal the various energy bands overlap to give a single band of energies that is only partially full of electrons. There are states with energies up to the vacuum level where the electron is free.

A simplified two dimensional view of a region of the Si crystal showing covalent bonds.

The energy band diagram of electrons in the Si crystal at absolute zero of temperature.

Chap. 2 Carrier Modeling

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Carrier Modeling

Electron Motion in Energy Band

Atomic Bonding in Solids

Ionic bonding Metallic bonding Covalent bonding Van der Waals bonding Mixed bonding

Current flowing

Energy Band Formation Metals, Semiconductors, and Insulators Electron Motion in Energy Band Energy Band Diagram Direct and Indirect Energy bandgap Electrons and Holes Effective Mass Impurity Doping (p-, n-type Semiconductors) Electron motion in an allowed band is analogous to fluid motion in a glass tube with sealed ends; the fluid can move in a half-filled tube just as electrons can move in a metal.

E=0

E0

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Electron Motion in Energy Band

Electron Motion in Energy Band

Fluid analogy for a Semiconductor

E=0

E0

No flow can occur in either the completely filled or completely empty tube.

No fluid motion can occur in a completely filled tube with sealed ends.

Fluid can move in both tubes if some of it is transferred from the filled tube to the empty one, leaving unfilled volume in the lower tube.

Chap. 2 Carrier Modeling

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Carrier Modeling

Metals, Semiconductors, and Insulators

Atomic Bonding in Solids

Ionic bonding Metallic bonding Covalent bonding Van der Waals bonding Mixed bonding

Carrier Flow for Metal

Energy Band Formation Metals, Semiconductors, and Insulators Electron Motion in Energy Band Energy Band Diagram Direct and Indirect Energy bandgap Electrons and Holes Effective Mass Impurity Doping (p-, n-type Semiconductors)

Carrier Flow for Metals.mov

Carrier Flow for Semiconductor

Carrier Flow for Semiconductors.mov

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Metals, Semiconductors, and Insulators

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Material Classification based on Size of Bandgap

Ease of achieving thermal population of conduction band determines whether a material is an insulator, metal, or semiconductor.

Typical band structures at 0 K.

Insulator

Semiconductor

Insulator

Semiconductor

Metal

Metal

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Metals, Semiconductors, and Insulators

Range of conductivities exhibited by various materials.

Problem 2.18 (text book)

Insulators
Many ceramics Alumina Diamond Inorganic Glasses

Semiconductors

Conductors
Superconductors Metals
Degenerately doped Si Alloys Te Graphite NiCrAg

Mica Polypropylene PVDF Soda silica glass Borosilicate Pure SnO2 PET

SiO2
10-18 10-15

Amorphous Intrinsic GaAs As2Se3

10-12 10-9 10-6

Intrinsic Si

10-3

100

103

106

109

1012

Conductivity (m)-1

Energy Band Diagram

E-k diagram, Bloch function.
PE(r) r

Energy Band Diagram

E-k diagram, Bloch function.

PE of the electron around an isolated atom When N atoms are arranged to form the crystal then there is an overlap of individual electron PE functions.

d 2 2m e + 2 [ E V ( x )] = 0 dx 2 h
Schrdinger equation

V ( x ) = V ( x + ma ) m = 1,2,3...
Periodic Potential

V(x) a 0 a

PE of the electron, V(x), inside the crystal is periodic with a period a.

x
x=L

k ( x ) = U k ( x ) e i k x
Periodic Wave function

x=0

2a

3a

Bloch Wavefunction
Moving through Lattice.mov
There are many Bloch wavefunction solutions to the one-dimensional crystal each identified with a particular k value, say kn which act as a kind of quantum number. Each k (x) solution corresponds to a particular kn and represents a state with an energy Ek.

Surface

Crystal

Surface

The electron potential energy [PE, V(x)], inside the crystal is periodic with the same periodicity as that of the crystal, a. Far away outside the crystal, by choice, V = 0 (the electron is free and PE = 0).

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Energy Band Diagram

E-k diagram of a direct bandgap semiconductor
The E-k D iag ram
Ek

Energy Band Diagram

The energy is plotted as a function of the wave number, k, along the main crystallographic directions in the crystal. Si Ge GaAs

The Energy B and D iag ram

CB Conduction B and (CB ) Eg V alence B and (V B ) h+ Ev O ccupied k eEm pty k Ec h e-

Ec Ev
h+ VB

k
/a /a

The E-k curve consists of many discrete points with each point corresponding to a possible state, wavefunction k (x), that is allowed to exist in the crystal. The points are so close that we normally draw the E-k relationship as a continuous curve. In the energy range Ev to Ec there are no points [k (x), solutions].

The bottom axis describe different directions of the crystal.

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Energy Band Diagram

E-k diagram

Direct and Indirect Energy Band Diagram

E CB Direct Bandgap Eg VB k GaAs k k Ec Ev Photon

Indirect Bandgap, Eg CB kcb VB kvb Si Ec Ev k k VB Er

CB Ec Phonon Ev k

Si with a recombination center

In GaAs the minimum of the CB is directly above the maximum of the VB. direct bandgap semiconductor.

Recombination of an electron In Si, the minimum of the CB is displaced from the maximum of and a hole in Si involves a recombination center. the VB. indirect bandgap semiconductor

(a) Direct transition with accompanying photon emission. (b) Indirect transition via defect level.

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Energy Band
A simplified energy band diagram with the highest almost-filled band and the lowest almost-empty band.

Metals vs. Semiconductors

Pertinent energy levels

vacuum level

: electron affinity
work function

work function

electron affinity

conduction band edge

valence band edge

Metal
Only the work function is given for the metal.

Semiconductor

Semiconductor is described by the work function qs, the electron affinity qs, and the band gap (Ec Ev).

Chap. 2 Carrier Modeling 2.3 Carrier properties

Electrons and Holes

Generation of Electrons and Holes
Electron energy, E
Ec+

Electrons and Holes

Electrons: Electrons in the conduction band that are free to move throughout the crystal.

Holes:

Missing electrons normally found in the valence band (or empty states in the valence band that would normally be filled).

CB h > Eg
Ec
Free e Eg Hole h+

hole

Ev

VB
0

A photon with an energy greater then Eg can excitation an electron from the VB to the CB.

Each line between Si-Si atoms is a valence electron in a bond. When a photon breaks a Si-Si bond, a free electron and a hole in the Si-Si bond is created.

These particles carry electricity. Thus, we call these carriers

Effective Mass (I)

Carrier Movement Within the Crystal

An electron moving in respond to an applied electric field. E E

Density of States Effective Masses at 300 K

within a Vacuum within a Semiconductor crystal
F = q E = mn

F = q E = m0

dv dt

dv dt
Ge and GaAs have lighter electrons than Si which results in faster devices
( m0 = Electron rest mass, 9.11x10-31 kg )

It allow us to conceive of electron and holes as quasi-classical particles and to employ classical particle relationships in semiconductor crystals or in most device analysis.

Chap. 2 Carrier Modeling 2.2 Semiconductor models

Effective Mass (II)

Electrons are not free but interact with periodic potential of the lattice. Wave-particle motion is not as same as in free space.

Energy Band Diagram

The energy is plotted as a function of the wave number, k, along the main crystallographic directions in the crystal. Si Ge GaAs

p = hk

E = h

Plank-Einstein-De Broglie Relation

Moving through Lattice.mov

The bottom axis describe different directions of the crystal.

Curvature of the band determine m*. m* is positive in CB min., negative in VB max.

Exercise
Indicate where the effective mass of the electron is greatest and least on the band diagram.

Effective Mass Approximation

The motion of electrons in a crystal can be visualized and described in a quasi-classical manner. In most instances The electron can be thought of as a particle. The electronic motion can be modeled using Newtonian mechanics. The effect of crystalline forces and quantum mechanical properties are incorporated into the effective mass factor. m* > 0 : near the bottoms of all bands m* < 0 : near the tops of all bands Carriers in a crystal with energies near the top or bottom of an energy band typically exhibit a constant (energy-independent) effective mass. `

d 2E 2 = constant : near band edge dk

Chap. 2 Carrier Modeling 2.3 Carrier properties

Covalent Bonding

Covalent Bonding

Chap. 2 Carrier Modeling 2.3 Carrier properties

Band Occupation at Low Temperature (0 K)

Band Occupation at Low Temperature (0 K)

Chap. 2 Carrier Modeling 2.3 Carrier properties

Band Occupation at Low Temperature (0 K)

Band Occupation at Low Temperature (0 K)

Chap. 2 Carrier Modeling 2.3 Carrier properties

Chap. 2 Carrier Modeling 2.3 Carrier properties

Impurity Doping

Concept of a Donor Adding extra Electrons

The need for more control over carrier concentration

Without help the total number of carriers (electrons and holes) is limited to 2ni. For most materials, this is not that much, and leads to very high resistance and few useful applications. We need to add carriers by modifying the crystal. This process is known as doping the crystal.

Regarding Doping, ...

Chap. 2 Carrier Modeling 2.3 Carrier properties

Chap. 2 Carrier Modeling 2.3 Carrier properties

Concept of a Donor Adding extra Electrons

Binding Energies of Impurity

Hydrogen Like Impurity Potential (Binding Energies)

Effective mass should be used to account the influence of the periodic potential of crystal. Relative dielectric constant of the semiconductor should be used (instead of the free space permittivity). : Electrons in donor atoms : Holes in acceptor atoms

Binding energies in Si: 0.03 ~ 0.06 eV Binding energies in Ge: ~ 0.01 eV

Chap. 2 Carrier Modeling 2.3 Carrier properties

Chap. 2 Carrier Modeling 2.3 Carrier properties

Impurity Doping

Concept of a Donor Adding extra Electrons

Band diagram equivalent view

Donor

Acceptor

Chap. 2 Carrier Modeling 2.3 Carrier properties

Chap. 2 Carrier Modeling 2.3 Carrier properties

Concept of a Donor Adding extra Electrons

Concept of a Donor Adding extra Electrons

V(x), PE (x) V(x)

n-type Impurity Doping of Si

Electron Energy
Electron Energy

x
PE (x) = eV

Energy Band Diagram in an Applied Field

E CB e As+ Ec ~0.05 eV E d As+ As+ As+ As+

Ec EF Ev E c eV E F eV

Energy band diagram of an n-type semiconductor connected to a voltage supply of V volts. The whole energy diagram tilts because the electron now has an electrostatic potential energy as well. Current flowing

Ev As atom sites every 106 Si atoms

Distance into crystal

A B

E v eV

The four valence electrons of As allow it to bond just like Si but the 5th electron is left orbiting the As site. The energy required to release to free fifth- electron into the CB is very small.

Energy band diagram for an n-type Si doped with 1 ppm As. There are donor energy levels just below Ec around As+ sites.

n-Type Semiconductor

Chap. 2 Carrier Modeling 2.3 Carrier properties

Concept of a Acceptor Adding extra Holes

Hole Movement

All regions of material are neutrally charged

One less bond means the acceptor is electrically satisfied.

One less bond means the neighboring Silicon is left with an empty state.
(Really it is thethe Acceptor leaving behind a positively charged hole. valance electrons jumping from atom to atom that creates the hole motion)

The positively charged hole cantheto the Acceptor the crystal. Another Empty state is located next empty state located next to valence electron can fill move throughout

Chap. 2 Carrier Modeling 2.3 Carrier properties

Chap. 2 Carrier Modeling 2.3 Carrier properties

Hole Movement

Concept of a Acceptor Adding extra Holes

Band diagram equivalent view Region around the acceptor has one extra electron and thus is negatively charged.

Region around the hole has one less electron and thus is positively charged.

The positively charged hole can move throughout the crystal.

(Really it is the valance electrons jumping from atom to atom that creates the hole motion)

Chap. 2 Carrier Modeling 2.3 Carrier properties

Chap. 2 Carrier Modeling 2.3 Carrier properties

Concept of a Acceptor Adding extra Holes

p-type Impurity Doping of Si
Electron energy B atom sites every 106 Si atoms

Intrinsic, n-Type, p-Type Semiconductors

Energy band diagrams

Ec
h+
B

x Distance

CB Ec EFi Ec EFn Ev Ec EFp Ev

into crystal

Ea Ev

B h+

~0.05 eV
VB

Ev VB

Boron doped Si crystal. B has only three valence electrons. When it substitute for a Si atom one of its bond has an electron missing and therefore a hole.

Energy band diagram for a p-type Si crystal doped with 1 ppm B. There are acceptor energy levels just above Ev around B- site. These acceptor levels accept electrons from the VB and therefore create holes in the VB.

Intrinsic semiconductors In all cases,

n-type semiconductors

p-type semiconductors

np=ni2

Note that donor and acceptor energy levels are not shown.

Chap. 2 Carrier Modeling 2.3 Carrier properties

Chap. 2 Carrier Modeling 2.3 Carrier properties

Heavily Doped n-Type, p-Type Semiconductors

Impurity Doping

E CB
Impurities forming a band

EFn Ec Ev

CB
Ec Ev EFp VB
Degenerate p-type semiconductor

g(E)

Degenerate n-type semiconductor. Large number of donors form a band that overlaps the CB.

Chap. 2 Carrier Modeling 2.3 Carrier properties

Impurity Doping

Donor / Acceptor Levels (Band Model)

Donor Level ED Ec
Donor ionization energy

Acceptor Level

Acceptor ionization energy

Valence Band

EA

Ev

Ionization energy of selected donors and acceptors in silicon

Donors
Dopant Ionization energy, E c -E d or E a -E v (meV) Sb 39 P 45 As 54 B 45

Acceptors
Al 67 In 160
Valence Band

Impurity Doping

Position of energy levels within the bandgap of Si for common dopants.

donor: impurity atom that increases n acceptor: impurity atom that increases p n-type material: contains more electrons than holes p-type material: contains more holes than electrons majority carrier: the most abundant carrier minority carrier: the least abundant carrier intrinsic semiconductor: n = p = ni extrinsic semiconductor: doped semiconductor

Terminology

Summary of Important terms and symbols

The band gap energy is the energy required to free an electron from a covalent bond.
EG for Si at 300K = 1.12eV Insulators have large EG; semiconductors have small EG

Summary

Dopants in Si:
Reside on lattice sites (substituting for Si) Group-V elements contribute conduction electrons, and are call ed donors Group-III elements contribute holes, and are called acceptors Very low ionization energies (<50 meV) ionized at room temperature

Dopant concentrations typically range from 1014 cm-3 to 1020 cm3

Bandgap Energy: Energy required to remove a valence electron and allow it to freely conduct. Intrinsic Semiconductor: A native semiconductor with no dopants. Electrons in the conduction band equal holes in the valence band. The concentration of electrons (=holes) is the intrinsic concentration, ni. Extrinsic Semiconductor: A doped semiconductor. Many electrical properties controlled by the dopants, not the intrinsic semiconductor. Donor: An impurity added to a semiconductor that adds an additional electron not found in the native semiconductor. Acceptor: An impurity added to a semiconductor that adds an additional hole not found in the native semiconductor. Dopant: Either an acceptor or donor. N-type material: When electron concentrations (n=number of electrons/cm3) exceed the hole concentration (normally through doping with donors). P-type material: When hole concentrations (p=number of holes/cm3) exceed the electron concentration (normally through doping with acceptors). Majority carrier: The carrier that exists in higher population (i.e. n if n>p, p if p>n) Minority carrier: The carrier that exists in lower population (i.e. n if n<p, p if p<n) Other important terms: Insulator, semiconductor, metal, amorphous, polycrystalline, crystalline (or single crystal), lattice, unit cell, primitive unit cell, zincblende, lattice constant, elemental semiconductor, compound semiconductor, binary, ternary, quaternary, atomic density, Miller indices