Chapter 1 The Crystal

Structure of Solids

W.K. Chen Electrophysics, NCTU 1

Outline

Semiconductor material
Type of solids
Space lattices
Atomic bonding
Imperfections & impurities in solids
Growth of semiconductor materials

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 1.1 Semiconductor Materials

Elemental semiconductors: (C, Si, Ge)

- composed of single species of atoms
Compound semiconductors: (binary, ternary, quarternary)
III-V, II-VI, IV-IV
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1.2 Types of Solids

Amorphous: degree of order only within a few atomic or
molecular dimensions
Polycrystalline: degree of order over many atomic or molecular
dimensions.
- The ordered regions vary in size and orientation with respect to one
another
- The single crystal regions are called grains
Single crystal: regular geometric periodicity throughout the entire
volume of material

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1.3 Space lattices
- The periodic arrangement of atoms in the crystal is called
lattice

lattice
Lattice point
Unit cell
Primitive cell

r r r r
T = n1a + n2b + n3c r r r
unit cell volume V = (a b ) c

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Lattice point

Lattice: the periodic arrangement of atoms in crystal

Lattice point: a dot used to present a particular atomic array
Unit cell: a small volume of the crystal that can be used to
reproduce the entire crystal
A unit cell is not a unique entity
Unit cell A, B, C and D all can be used to construct the entire
lattice by appropriate translation

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 Primitive cell: the smallest unit cell

Every equivalent lattice point in primitive

cell for 3-dim crystal can be found using
the vector
r r r r
r = pa + qb + sc

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1.3.2 Basic crystal structure in semiconductors
Orthorhombic () abc ===90o
Tetragonal () a=bc ===90o
Cubic () a=b=c ===90o
Hexagonal () a=bc ==90o, =90o

a, b are primitive vectors lie on the base plane

r r
: b , c
r r
: c , a
r r
: a , b

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1.3.2 Basic crystal structure

Three basic (cubic) crystal structures
Simple cubic (sc):
- has an atom located at each corner
Body-centered cubic (bcc):
- has an additional atom at the center of cubic
Face-centered cubic (fcc):
- has additional atoms on each center of face plane

Simple cubic Body-centered cubic Face-centered cubic

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The Fourteen Bravais Lattices
The ways in which we can specify the lattice points in space and keep translational symmetry is
limited. In 1848, Auguste Bravais demonstrated that there are in fact only fourteen possible point
lattices and no more. For his efforts, the term Bravais lattice is often used in place of point
lattice. 3D models of the possible lattices can be found here.

Table 1. Seven crystal systems make up fourteen Bravais lattice types in three dimensions
Number of Lattice Symbol Restriction on crystal cell angle
System Lattices
Cubic 3 P or sc, I or bcc,F or a=b=c
fcc = ==90
Tetragonal 2 P, I a=bc = ==90
Orthorhombic 4 P, C, I, F ab c = ==90
Monoclinic 2 F, C ab c ==90
Triclinic 1 P ab c
Trigonal 1 R a=b=c= = <120
,90
Hexagonal 1 P a=bc = =90 =120

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Example 1.1 Volume density

bcc structure
o
a1 = 5 A

How many atoms in one unit cell?

1
1+ 8 ( ) = 2
8

2 atoms
Volume density =
(a1 ) 2
2
= 8 2
= 1.6 1022 atoms/cm3
(5 10 )

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 1.3.3 Crystal plane & Miller indices
How to describe the crystal plane?

The crystal plane intercepts x,y and z axes at pa, qb and sc

Assume g is the plane vector, which is perpendicular to any vector on the plane

plane vector r
r r r r g
g = ha + kb + lc = [h k l ] r r r
l 2 = pa sc
r r r r r r
let l1 = pa qb l 2 = pa sc r r
r
l1 = pa qb
r r r r
g l1 and g l 2

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r r r r r r r r r
g l1 g l1 = 0 (ha + kb + lc ) ( pa qb ) = 0

hp kq = 0 =
k p
h q
r r r r r r r r r
g l2 g l2 = 0 (ha + kb + lc ) ( pa sc ) = 0
l p r
hp ls = 0 = r r
l 2 = pa sc
h s
p p 1 1 1
(h k l) = (h h h) = ( ) r r r
q s p q s l1 = p a q b

1 1 1
Miller indices ( h k l) = ( )
p q s
The integers are referred as the Miller indices.
We will refer to a general plane as (h k l) plane (h k l) plane
And the associated plane vector g is denoted by [hkl] [h k l] vector
[h k l ] vector (h k l)plane
For any plane that parallel to each other, they bear the same miller indices

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Example 1.2 Miller indices

Intercepts of plane
p = 3, q = 2 and s = 1
1 11
( hkl ) = ( ) = ( 2 3 6)
3 21

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Lattice Planes: Miller indeces

1 1 1
Miller index (h k l) = ( )
p q s

p = 1, q = and s = p = 1, q = 1 and s = p = 1, q = 1 and s = 1

(h k l) = (100)plane (h k l) = (110)plane (h k l) = (111)plane

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Example 1.3 surface density
bcc structure

o
a1 = 5 A
2 a1 a1

2 atoms
Surface density at (110) plane =
( a1 )( a1 2 )
2
= 8 2
= 5.66 1014 atoms/cm 2
(5 10 ) 2

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1.3.4 Diamond structure

Diamond structure is the most common structure in elemental semiconductors,
such as Si, Ge

Diamond structure is
basically consisted of body-
centered cubics with four of
the corner atoms missing
Each atom in the
tetrahedral structure (
) has four nearest
neighbors and it is this
structure which is the basic
building block of diamond
lattice
Tetrahedral structure a=bc ===90o

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W.K. Chen Electrophysics, NCTU 19

Zincblende (sphalerite) structure

For GaAs, each Ga atom
has four nearest As
neighbors and each Ga has
four nearest As atoms

Zincblende structure differs

from diamond structure only
in that there are two
different types of atoms in
the lattice

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Zincblende Lattice()
1
1

per unit cell

2
4 6 Ga = 4
5 1 1
As = 4 ( ) + 6 ( ) = 4
4 2
4
corner Face center

3 3

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1.4 Atomic bonding

The interaction of atoms in crystal is determined largely by the outmost, i.e.,
valence electrons of an atom

Ionic bond:
Covalent bond:
Metallic bond
Van der Waals bond

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 Covalent bond:
electrons being shared between bond atoms so that the valence
energy shell of each atom is fully occupied (8 eletrons) by
electrons (II-VI, III-V, IV-IV)

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Metallic bonding
such as solid sodium (Na).
Solid sodium has a body-
centered cubic structure, each
sodium has one valence
electron, so each atoms has
eight nearest neighbors with
each atom sharing many
valence electrons Body-centered cubic
Van der Waals bond
Interaction between dipoles
HF
(most in gaseous form, solid
HF
form exhibits a relatively HF
melting temperature

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1.5 Imperfections & impurities in solids
Perfect crystal for most of time is less useful,
In a real crystal, the lattice is not perfect, but contains imperfections or defects.
Such imperfections tend to alter the electrical properties of a material, in some
cases, electrical parameters can be dominated by these defects or impurities

Native defects (Imperfections)

vacancy
interstitial
line dislocation
anti-site
Impurities
substitutional impurity
interstitial impurity

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Native defects (Imperfections)

vacancy:
missing of atom at a particular lattice site
interstitial
atoms located between lattice sites

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 Native defects (Imperfections)
Frenkel defect
vacancy-interstitial defect
line dislocation
entire row of atoms is missing from its normal lattice
sites

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Impurities
substitutional impurity
Anti-site
interstitial impurity
anti-site

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 Point defect
- The point defects involve single atoms or single-atom
locations. That is one atom is missing or misplaced in the
crystal lattice

vacancy
interstitial
substitial
anti-site

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1.6 Growth of semiconductor materials

Ingot growth
Epitaxial growth

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 Silicon Crystal Pulling Apparatus

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Liquid Encapsulated Czochralski (LEC)

Encapsulation by thin (8-17

mm) molten B2O3 layer
High inert gas pressure (up
to 100 bar) to suppress
volatility of group V
50 mm round-shaped
GaAs, 200-400 cm-2

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 3300m
1Semiconductor Thin Film Deposition
Liquid Phase Epitaxy (LPE)
Metalorganic Chemical Vapor Deposition
(MOCVD)
Molecular Beam Epitaxy (MBE)
Chemical Beam Epitaxy (CBE, MOMBE)

Trichloride Vapor Phase Epitaxy (ClVPE)

Hydride Vapor Phase Epitaxy (HVPE)

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Liquid Phase Epitaxy

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Metal-Organic Chemical Vapor Deposition

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MOCVD Growth Mechanism

V
III

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 Molecular Beam Epitaxy

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Chemical Beam Epitaxy

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 Trichloride Vapor Phase Epitaxy

Hot wall reactor

Etch & grow
Pure AsCl3 and PCl3 attainable
Low-background doping epilayer
Low cost
Not possible to grow AlGaAs
(TAlAs=1100oC>>TGaAs=750oC)
Difficult in composition control ( use
both group III & V clorides)
Poor reproducibilty

Ga(l)+HCl GaCl+1/2H2
4AsCl3+6H2As4+12HCl
4GaCl+As4+2H24GaAs+4HCl

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Hydride Vapor Phase Epitaxy

Etch & growth

Indept. Control of III & V
species
Multi-wafer feature
All GaInAsP alloy
Highly toxic
Complicated reaction
hydride Memory effect
Poor hydride purity
Use corrosive HCl gas
Difficult to grow Al and Sb
Ga(l)+HCl GaCl+1/2H2 compound
AsH31/2As2+3/2H2
2GaCl+1/2As4 2GaAs+2HCl

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 Figure 2. Schematic diagram of MBE machine.

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n Deflection (RHEED) measurement system. Electrons are scattered more when a new mono-layer of atoms are being form. The intensity of the RHEED signal oscillates a

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Table 1. Common etchants for various semiconductor materials and etch rates.

Approx. etch rate m

Etchant and ratio of mixture Material Etched
per min at 20 C

HCl (conc.) InP 5-15

HCl (conc.) Surface oxide on GaAs Fast
HCl (conc.) InGaAs <0.02
HCl:H 2 0 (2:1) InP 8
HCl:H 2 O (1:1) InP 0.7
HCl:H 2 O (1:2) InP 0.09
H 3 PO 4 :HCl (1:1) InP 2.5
H 3 PO 4 :HCl (1:2) InP 4.8
H 3 PO 4 :HCl (1:3) InP 6.6
H 3 PO 4 :HCl (3:1) InP 0.75
H 3 PO 4 :H 2 O 2 :H2O (3:4:3) GaAs 6
H 2 O:NH 4 OH:H 2 O 2 (20:2:1) GaAs 0.5
HBr:CH 3 COOH:K 2 Cr 2 O 7 (1:1:1) Most III-V compounds 2-5
H 2 O 2 :NH 4 OH:H 2 O (0.7:2:100) GaAs 0.1
H 2 SO 4 :H 2 O 2 :H 2 0 (1:8:80) InGaAs 0.5
Br:CH 3 OH (1:100) Most III-Vs 1-10

W.K. Chen HCl:H 2 O 2 :H 2 O (1:4:80) GaAs

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