Chapter 1

Crystal Structure of Solids

This slide was prepared by Dr. Tan Sin Tee (Department of Physics, Faculty Science, UPM); Updated on 25 September 2023; Tel: +6010-4281371.

Si

TAN SinTee
+6010-4281 371
tansintee@ upm.edu.my
 Learning Objectives

Student able :
1. To discuss the classification of solids and unit cell.
2. To solve the crystal analysis in Cubic System.
3. To describe the diamond crystal structure.
4. To state the growth method of single crystal semiconductor
materials.
 Semiconductor Materials
“Semiconductor materials having the conductivity between the metals and insulator. “

Electrical properties

Chemical Composition Atomic Arrangement in Solid

Electrical Properties of Semiconductor Materials

Classification Resistivity Conductivity Electrical

(W-cm) (W-cm)-1 Resistivity Range
Insulators 1012 10-12 1011 - 1019
(Glass @ RT) (Glass @ RT)

Semiconductors 2.5x105 4.0 x 10-6 10-6 - 106

(Si-intrinsic @ RT) (Si-intrinsic @ RT)

Metals 1.68 x 10-8 5.95 x 107 10-2 - 10-8

(Cu @ RT) (Cu @ RT)

Source: Modified, Telford W.M-1990

 Semiconductor Materials
The conductivity of the semiconductor can be modified:-

1 Impurity / Type of Dopant in the Materials

External Perturbation System

- Electrical (Applied Voltage)
2 - Thermal (Heat)
- Optical (Light illumination)
Classification of Semiconductor Materials
2 Compound (Binary) Group Group
V VI

Group Group
III IV

Group
II

1 Elemental

2 Si 1
GaAs Compound (Binary)
 Classification of Semiconductor Materials

Elemental Semiconductor Semiconductor with single species of atom.

Si Silicon Common semiconductor used in IC.

2 Ge Germanium
Compound Semiconductor Semiconductor with two elemental compound.
GaAs Gallium Arsenide Good optical properties and used in high speed devices.
InP Indium Posphide

Complex Semiconductor Flexible in material selection

AlxGa1-xAs based on the required properties.
 Potential Usage of Semiconductor

Light

Light

GaN Photodetector
 Type of Solids
Atomic Arrangement in Solid
Grain Boundry
Grain

Amorphous
3 Polycrystalline
Single Crystal
Ordered Region = The spatial volume where atom or molecule have a regular geometric arrangement
• Single crystalline material posses a higher electrical conductivity than the non-single crystal sample.
• Grain boundary tends to degrade the electrical characteristic via carrier recombination.
 Space Lattices

Single Crystalline Solid

A group of atoms is repeated
at a regular intervals in three
dimensional space lattice.
 Lattice
A B

Periodic arrangements
of atoms in a crystal.
Note:
The atomic arrangement of the atoms
determine the macro symmetry and
properties of the crystal. The example of
macro properties is conductivity or viscosity.
Silicon Solid: Electrical Conductivity

Ordered Region Ordered Region

Carrier Transport Carrier Transport
 Impact of Lattice in Semiconductor Device
Amorphous Si Polycrystalline Si Single crystal Si
1. Low Cost 1. Moderate electrical 1. Excellent electrical
2. Good Optical transparency properties properties
3. Feasible surface 2. Application: Gate in 2. Application: Active region
modification via doping MOSFET in MOSFET
process.
4. Application: Transistor,
switching devices in LCD,
Solar calculator
 Primitive and Unit Cell

Lattice point: A periodic atomic arrays points

2 dimensional lattice

Unit Cell= Small volume of the crystal that can used to reproduce the entire crystal

3 dimensional lattice (A group of periodic arranged atom)

3 Dimensional Lattice
Lattice translation vector :
r = pa + qb + sc

Example:

A
C

z Consider the lattice constant = a1

y xz plane: A = a𝑥ො + a𝑧Ƹ
xy plane: C = -a𝑥ො + a𝑦ො
xyz plane: B = a𝑥ො + a𝑦ො - a𝑧Ƹ
x
 Basic Crystal Structure
Simple Cubic System

Characteristic of
Cubic System
Crystal Analysis

Volume Density
Surface Density
 Crystal Analysis

#𝒂𝒕𝒐𝒎 𝒊𝒏 𝒂 𝒔𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒑𝒍𝒂𝒏𝒆

Surface Density =
𝑨𝒓𝒆𝒂 𝒐𝒇 𝒔𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒑𝒍𝒂𝒏𝒆

#𝒂𝒕𝒐𝒎 𝒊𝒏 𝒂 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍

Volume Density =
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍

# Practice 1:
**Calculate the
(i) Surface density at (100) plane and (Ans= 11.89 atom/nm2 )
(ii) volume density of simple cubic system. (Ans= 41.00 atom/nm3 )

Given a = 0.29 nm
 Crystal Plane
• Semiconductor devices is fabricated from the near surface.
• Surface properties of a crystal may influence the device characteristic
• The surface and the intercept plane in the crystal can be denoted from (h k l ) Miller Indices.

1 2 Check the intercept

Determine 3 Join the intercept point

the origin
4 Draw the plane
# Practice 2:

Sketch the
(i) (101) plane and
(ii) [111] direction in the Simple Cubic system.
Diamond Structure in Elemental Semiconductor
1 Element
• Lattice constant, a = 5.431 Å Unit cell: a/2
• Coordinate number = 8 Tetrahedral
• Atom inside the cells = 4 structure
• Atom on the plane = 6
• Atom at the edge = 8

• Total # atom in unit cell= 4+3 +1 =8

• Cell volume, a3 = 160.2 Å3
• #Practice 3: Calculate the volume density of Si atom.
(Ans= 5x 1022 atomcm-3 )
• #Practice 4: Determine the density of Si crystal. Given the atomic
weight is 28.1.
(Ans= 2.33 g cm-3 ) a3 = (nM / NAρ)
 Crystal Plane in Silicon Wafer

The crystal plane in Silicon wafer is very important in cleaving Si wafer.

 Properties of Silicon Semiconductor
1. Outstanding native oxide (silicon dioxide SiO2) which is essential for
fabrication of transistors.
2. Low recombination rate - Si/SiO2 interface.
3. High hole mobility that enables fabrication of high-speed P-channel
field-effect transistors necessary for complementary metal oxide
semiconductor logic (basis of microprocessors).
4. Mechanically stable and strong. It showed an excellent performance
in MEMS sensors.
5. Low defect density
 Application of Silicon Semiconductor
Solar Concentrator

Silicon chips Solar Panel

Piezoelectric Detector

AMDL UPM-UTAR Chemical Sensor

Zinc Blend Structure in Compound Semiconductor
Unit cell:
2 Element Tetrahedral
• Lattice constant, a = 5.653 Å structure
• Coordinate number = 8
• Atom Ga inside the cells = 4
• Atom As on the plane = 6
• Atom As at the edge = 8
• Total # atom in unit cell= 4+3 +1 =8
• #Practice 5: Calculate the volume density of GaAs atom.
• #Practice 6: Determine the density of GaAs crystal. Given the
atomic weight of Ga and As is 69.72 and 74.92,
respectively.

a3 = (nM / NAρ)
 Properties of Semiconductor GaAs
1.High electron mobility and saturated drift velocity, which
enables high frequency transistors operating above 250 GHz.
2.Direct bandgap which leads to efficient emission of light in LED
application.
3.Wide bandgap (1.42 eV as compared to 1.12 eV for Si) makes
GaAs more radiation hard and less susceptible to thermal effects.
4.Low parasitic capacitance and inductance.
 Application of Semiconductor GaAs

Source: MACOM technology

HCP Structure in Compound Semiconductor
2 Element
• Unit Cell= Wurtzite structure
• Coordinate number = 4
• Atom Ga = 2
• Atom N = 2
• Total # atom in unit cell= 2+2 = 4
 Properties of Semiconductor GaN

1.High saturated drift velocity - high frequency and power

electronic device in communication applications
2.Direct bandgap - *visible light emission (red to blue) if
incorporated with InN
3.Wide bandgap (3.4 eV) – High electron mobility
4. Less susceptible to thermal effects.
5.High power density
6.Miniature device
 Application of Semiconductor GaN
IC
Transistor

LED

Source: MACOM technology Battery

Semiconductor Device: Comparison
GaN vs SiC*

Opamp
High Temperature
Power Electronic
Growth of Semiconductor Materials

Czochralski
2
Epitaxial Growth
Metal Solidification
MBE

MOCVD
Liquid phase epitaxy
 Czochralski Method

Output: Polycrystalline sample

Impurity point defects:
1. substitutional and
2. interstitial
Molecular Beam Epitaxy (MBE)
 Imperfections & Impurities in Solids
• In a real crystal, the lattice is not perfect.
• The defect/ imperfection of crystal is deteriorate the electrical properties of the semiconductor materials.

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

Look in detail in next topic
 Crystalline Defects: Point Defects
• Vacancies:
-missing atom from an atomic site.

Vacancy
distortion
of planes

• Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes
 Crystalline Defects: Self-interstitial
An atom from the
crystal that is
crowded into an
interstitial site

Vacancy and self-

interstitial
introduce strains
in lattice
 Crystalline Defects: Impurities
➢Maximum purity possible is 99.9999%, i.e., a
minimum of 1022 - 1023 impurity atoms in 1m3,
➢Alloys are common: for mechanical properties, e.g.:
• Mild steels: Fe-C alloys
• Stainless steels: Fe-Cr alloys
➢The addition of impurity atoms to a metal:
• No new phase: solid solution, and/or
• a new second phase.
➢Solute: impurity/alloying atoms
 Solid Solutions
➢ A solid solution forms when the solute atoms
are added to the host material, the crystal
structure is maintained, and no new structures
(phases) are formed.
➢ A solid solution is compositionally
homogeneous; the impurity/added atoms are
randomly and uniformly dispersed within the
solid.
➢ Impurity point defects:
• substitutional and
• interstitial.
Substitution and Interstitial Impurity
Substitutional Impurity: an impurity atom
substituting an atom at the normal site

Interstitial
Impurity: : an
impurity atom
present in the
interstitial site
Substitution and Interstitial Impurity
“Bubble Raft” Experiment:

Experimental:
Bubbling air through the soup solution and controlled the bubble size using an air
pump connected to a hollow needle.

Objective:
Identify point defect and line defect that analogous to crystal defect.
Substitution and Interstitial Impurity
“Bubble Raft” Experiment:
 Substitution and Interstitial Impurity
• Two outcomes if impurity (B) added to host (A):

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)

Substitutional impurity: Interstitial impurity:

An impurity atom substituting An impurity atom present in
an atom at the normal site the interstitial site
42
 Dislocations: Line Defects
Dislocations:
Linear defect resulting from misalignment of a plane of atoms

Extra or missing
half plane of atoms
Dislocations: Line Defects

Slip by dislocation glide

Slip by movement of entire

lattice plane
 Dislocation Movement: Deformation

Movement of atomic planes is facilitated by

dislocations
(when present in favourable orientations)
Role of crystal defects in deformation
Arresting/minimizing Dislocation
Movement / Deformation:
• Vacancies, impurities, interstitials create strain
and obstacle for movement of dislocations

• Too many dislocations can also hinder each

other’s movements

• Grain boundaries can stop dislocations

• Precipitates can stop/hinder dislocations

 Defect Identification :XRD
• X-ray Diffractogram

• Bragg Rules:
Crystallinity = kλ / β cos θ
where λ = 0.1542 nm
β =FWHM At specific peaks
k=Boltzmann constant
 Defect Identification (ctnd…)

Bragg RULE:

nλ = 2 d sin θ
d = nλ /2 sin θ

d > ; θ < ; lattice expansion

Crystallinity = kλ / β cos θ

Crystallinity > ; FWHM <

 Defect Identification :HRTEM

Have you ever seen an atom?

 Dislocation Movement: Deformation
▪ This movement is analogous to movement of a
caterpillar.
▪ Dislocations move in steps. The edge dislocation at
P moves to Q in steps as depicted by the red (half-
plane) and blue atoms.
▪ When the half-plane reaches a free surface it
produces a slip step