Defects & Impurities

BW, Ch. 5 & YC, Ch 4 + my notes & research papers

Human beings and

semiconductors are
interesting because
of their defects*
*

Peter Y. Yu

U.C.-Berkeley

A primary reason that

Semiconductors are useful for devices:

The electronic (& other) properties can be
significantly altered by incorporating
impurities (& other defects) into the material.
There are good impurities (& defects) & bad ones!

Good Impurities:
Are useful for device operation.

Bad Impurities:
Can make devices useless!

Semiconductors, Dielectrics, Metals

Carrier
Concentration

104 cm

Dielectrics
1012 cm-3

Advantage of Semiconductors:
Their electrical properties can be
easily changed by adding
impurities

DOPANTS

Semiconductors

10 cm
-4

1020 cm-3

Resistivity

Metals

Disadvantage of Semiconductors:
Their electrical properties can be
easily changed by adding impurities

CONTAMINANTS

Example: Impurities in Silicon

Very useful impurities!!
Shallow Impurity
Levels
Benign impurities.
Potentially dangerous
impurities!! Deep

Impurity Levels
Very dangerous for devices!!
Deep Impurity
Levels

p-type dopants: B, Al, Ga, In

n-type dopants: P, As, Sb

Oxygen, Carbon
Slowly diffusing & rare metals

La, Y, Zr, Hf, Ta, ...

Fe, Cu, Ni
Cr, Mn, Au,..

Industrial Data (~ 5 years ago): The integrated circuit

industry consumes ~> 10,000 tons of Si per year!!
Laboratory Data on Si: 10 mg of Fe is sufficient to
contaminate this amount of silicon to the level of 1011 cm-3

~10,000
tons!!
~ 10 mg

A Practical Question: With such possibilities of contamination,

how can a high purity of Si wafers be maintained in the process of
manufacturing of integrated circuits?

Example: Degradation of MOS devices by metal precipitates

Local thinning of the oxide

Trap-assisted tunneling

Effect of Iron (Fe) Contamination on MOS Devices

Threshold Iron Concentration

Note: Fe contamination isnt the only problem! Contamination of Si

(& other materials) by most other metal atoms is also very dangerous!!

There are at least two solutions to the problem of how

to keep metal contamination low in semiconductors

1. Ultra-Clean Technology
Growth Technology

2. Defect Engineering

Physics!!
Metals are dangerous only if they are in the device-active region. If metals
can be removed from the devices, & localized in pre-defined regions of the
wafer, or if they can be passivated, they will not affect the device yield.
However, defects can be engineered only if we know a lot about their

PHYSICS!!

Ultra-Clean
Technology

NOTE!
To alter the electronic properties of a semiconductor only
requires a VERY SMALL absolute impurity concentration:

(NI/NH) ~ 10-6

(NI = # impurity atoms, NH = # host atoms)

Also, impurities & defects CAN produce energy levels in the

fundamental bandgap of the perfect crystal.

Controlling the impurity concentration is

VITAL to device performance!

A first step to controlling them is obtaining a

Theoretical understanding
of their Physics.

Effect of Various
Substitutional
Impurities on the
Resistivity of Si

Some Measured Impurity Levels in Si & GaAs

Some Measured Impurity Levels in Ge

Shallow Donor
Levels

Shallow Acceptor
Levels

Some Measured Impurity Levels in GaAs

This shows that the measured energy for an impurity

may depend on the measurement technique!

Some Measured Shallow Levels in Semiconductors

Some Measured Shallow Donor

Levels in Semiconductors

Some Calculated & Measured Donor Levels in Si

Some Calculated & Measured Acceptor Levels in Si & Ge

Defects & Impurities

From the data, impurity & defect levels in semiconductor
bandgaps are diverse, varied, & complicated, even
for simple substitutional impurities!

In addition to impurity levels, there can also be

bandgap levels due to complex defects.
It is now known that the bandgap levels can be
understood as being signatures of defects & impurities.

NOTE
Whole books have been written on defects &
impurities in semiconductors!
So, we will just discuss the highlights.

Classification of Defects & Impurities

Classification by Level Depth
One obvious way to classify impurities & defects
is by their level depth in the bandgap.

Shallow Impurities
These produce bandgap levels near the conduction

or valence band edges.

These can be accurately calculated by Effective Mass
Theory (Effective Hydrogen Atom Theory). We will
describe this theory in some detail.

Deep Impurities
All others. We will describe a theory of these in detail.

Classification by Spatial Extent

Another way to classify impurities & defects is by the
spatial extent of their potential and their wavefunction.

Point Defects
These are isolated atoms or small groups of atoms
(complexes). This kind is all that well discuss here.
Point defects can be either good or bad for the material,
depending on the individual material and defect.

Line Defects
These are defects in which rows or planes of atoms are
involved (such as dislocations). These are usually bad for
the material. We wont discuss these here.

Types of Point Defects & Impurities

Vacancy: A missing atom at a lattice site.

The symbol is VA for a missing atom of type A.

Interstitial: An atom in between lattice sites.

It is possible to have a self-interstitial.
The symbol is IA for an atom of type A at an interstitial site.

Substitutional Impurity: An impurity atom C

replacing a host atom A.
The symbol is CA for an atom of type C replacing an atom of
type A.

Antisite Defect: In compounds only. A host atom B

occupying a site that should have had a host atom A on it.
The symbol is BA for an atom of type B on an A site.

Types of Point Defects & Impurities

Complexes: Combinations of some point defects.
For example, a vacancy - interstitial pair: VA-IA

Other Classifications
Intrinsic or Native Defects: No matter what the growth
process is, these cannot be completely eliminated.

Examples: Vacancies, Antisite Defects, Self-interstitials.

Extrinsic Defects: Impurities or impurity complexes

of some sort.

Point Defects & Impurities

Our main interest in this discussion will be

Electrically Active Defects

Donors: Contribute electrons to the host material.
Acceptors: Accept electrons from the host.
Or donate Holes to the host.
Isoelectronic Impurities: Are substitutional
impurities from the same column of the periodic
table as the host atom being replaced.

Consider Si (or any column IV atom material)

Some Single Donor Impurities:
These are impurities from column V of the
periodic table (P, As, )

Some Single Acceptor Impurities:

These are impurities from column III of the
periodic table (B, Al, Ga, ..)
There are also Double Donors or Double
Acceptors, etc. which donate or accept two
electrons.