Chapter 2

Fundamental Solid State Chemistry

Almost all materials are solids. Solid state chemistry
helps us understand the structures and properties of
materials, allowing us to do rational design on materials.

1
 What is Solid State Chemistry?
Solid-state chemistry is the study of solid materials, which
may be molecular. Solid-state chemistry studies both the
synthesis, the structure, and the physical properties of
solids. It therefore has a strong overlap with solid-state
physics, mineralogy, crystallography, ceramics,
metallurgy, thermodynamics, materials science and
electronics with a focus on the synthesis of novel materials
and their characterization

2
solid state materials can be divided into
two categories
AMORPHOUS vs. CRYSTALLINE solids
The crystalline state is more thermodynamically favorable than
the disordered state, the formation of amorphous materials is
favored in kinetically bound processes.

single crystal vs. polycrystalline solid

metastable

quench

3
Crystalline Solids
A crystal is a solid in which the constituent atoms, molecules, or
ions are packed in a regularly ordered, repeating pattern
extending in all three spatial dimensions. (quasicrystal??)
Amorphous Solids (Glass)
An amorphous solid is a solid in which there is no long-range
order (1–10 nm) of the positions of the atoms.

Powder could be either polycrystalline or amorphous.

4
TYPES OF BONDING IN SOLIDS

Ionic Solids

Metallic Solids

Covalent Network Solids

Molecular Solids

hexagonal boron nitride (BN)x

5
 THE CRYSTALLINE STATE
Single crystals comprise an infinite array of ions, atoms, or
molecules, known as a crystal lattice.

6
The overall shape or form of a crystal is known as
the morphology.
Often, there is more than one crystalline form of
the same substance. Each form is known as a
polymorph, differing in both the arrangement of
constituents as well as unit cell dimensions (solid
state phases, 𝛂−, 𝛃− …..etc)

Figure 2.5. Differential scanning calorimetry (DSC) crystal morphology of ice

curves of two polymorphs of picryltoluidine. 7
Crystal Growth Techniques
Crystal growth is very important in making high-quality materials.

Ruby: Cr-a-Al2O3

8
Advanced Crystal Growth Techniques

Czochralski Process KDP (KH2PO4)

of Silicon Wafers Crystal Growth
NLO material

Second Harmonic Generation (倍頻)

9
 CRYSTAL LATTICE
• LATTICE
An infinite array of lattice points in space, in which each point
has identical surroundings to all others.

• CRYSTAL STRUCTURE
The periodic arrangement of atoms in the crystal.
• It can be described by associating with each lattice point a group
of atoms called the MOTIF ( or BASIS)
10
11
Unit Cell Selection
There can be many choices in selecting unit cell, right or wrong, appropriate or
inappropriate. Smallest? Symmetrical?

o 𝑎

12
More than one ways to define unit cells for a lattice

A-centered tetragonal
Primitive tetragonal

13
Crystal Systems
The structures of all crystals can be classified according to the
symmetry of the unit cells.
or Trigonal

Trigonal Cell
Triclinic, Monoclinic P, Monoclinic C, Trigonal (Rhombohedral), Hexagonal
Orthorhombic P, Orthorhombic F, Orthorhombic I, Orthorhombic C
Tetragonal P, Tetragonal I, Cubic P, Cubic F, Cubic I
14
 Crystal system
There are 14 Bravais lattices including centered cells.

primitive unit cell and centered unit cell

15
Representation of Crystal Planes

16
 Lattice planes and Miller indices
• Miller indices (h k l) are a notation system in
crystallography for planes and directions in crystal lattices.
• They are written and denote planes orthogonal to a direction
in the basis of the reciprocal lattice vectors. Reciprocal
lattice is closely related to crystal’s diffraction pattern.

17
Assignment of Miller indices to a set of planes

1. Identify that plane which is adjacent to the one that passes

through the origin.

2. Find the interception of this plane on the three axes of the

cell and write these intersections as fractions of the cell edges.

3. Take reciprocals of these fractions. (213)

normal
Miller index is the normal vector of
𝟏
the parallel planes. The length of it is .
𝒅𝒉𝒌𝒍
𝑑ℎ𝑘𝑙 is interlayered spacing.

intercept the x-axis at a/2, the y-axis at b and the z-axis at c/3;
take the reciprocals of (1/2, 1, 1/3); then Miller index is ( 2 1 3 )
18
Miller index of hexagonal unit cell

(112)

Examples of planes (in parentheses) and directions [in

brackets] of a hexagonal unit cell. Planes are designated by
the (h k i l) designation, where i = -h-k.
19
The Miller index is usually used to denote a set of
equally spaced parallel planes, including one
through the origin.

20
2D Miller Indices
Exercise:

Draw parallel planes

denoted by Miller
indices (h k):

(1 2), (1 2), (3 2)

HRTEM
high resolution
transmission electron microscope
21
Lattice, Miller Indices and Diffraction Patterns

Real and Reciprocal Lattice

Diffraction Lattice
22
Ewald Sphere: relating the geometry of X-ray, detector,
crystal lattice, reciprocal lattice and diffraction pattern

All the reciprocal lattice

points (hkl) on the
reciprocal lattice surface of Ewald sphere
satisfy Bragg’s law and
can be observed.
𝟏
d* =
𝒅𝒉𝒌𝒍
crystal lattice

constructive interference

𝟏
𝒅𝒉𝒌𝒍 = 𝐬𝐢𝐧 𝜽
𝟐
∴ 2d sin θ = λ
𝝀
23
 Structures of Solids
It is important to understand the structures of solid in order
to fine-tune the their structures to obtain specific properties.

Many important solids, minerals, can be described and

understood by close-packing models. (e.q. ccp, hcp)

Au, Ag, Cu, Ni, Pd, Pt etc

ZnS, ZnO, CdS, CdSe, CdTe, GaN etc

semiconductors
Zinc Blende
MgAl2O4, LixCo2O4 cathode of Li-Battery
Fe3O4 (FeFe2O4) magnetite
Spinel AB2O4 24
Cubic and Hexagonal Close Packing Models of Spheres
(ccp and hcp)

hcp ccp

25
Octahedral and Tetrahedral Interstices of Close Packing
holes

n(P) : n(Oh) : n(Td) = 1:1:2

Ionic compounds:
Large anions do close-packing
Small cations put in Oh or Td interstices
26
How to make descriptions of solids based
on close-packing notions?
Exercises: NaCl ZnS, zinc blende

wurtzite?

MgAl2O4

O-anions do cubic close-packing,

while Mg2+ ions occupied 1/8 Td
sites, and Al3+ ions occupied 1/2
Oh sites.

n(P) : n(Oh) : n(Td) = 1:1:2

27
Radius Ratio Rule

28
 Polytypism (疊形) The existence of multiple forms differing
in only one of the dimensions of the unit cell.

Polytypes of graphite

There are over 200 known polytypes of SiC; the most common
include 3C, 2H, 4H, 6H, 8H, 9R, 10H, 14H, 15R, 19R, 20H, 21H,
and 24R.
29
 Symmetry
• “A body is said to be symmetrical when it can be divided into
parts that are related to each other in certain ways. The operation
of transferring one part to the position of a symmetrically related
part is termed a symmetry operation, the result of which is to
leave the final state of the body indistinguishable from its original
state. In general, successive application of the symmetry operation
must ultimately bring the body actually into its original state again.”

30
Symmetry Operations: mirror

m or s

The symbol for the mirror is a solid line.

31
Symmetry Operations: rotations

Cn

32
Examples of symmetry group elements and
molecular point group assignments

C3v

Oh

http://www.staff.ncl.ac.uk/j.p.goss/symmetry/ 33
A little tricky one to assign point group
CH3 Si

O Si O

H3C Si
H3
C
O
Si
CH3

CH3
D3h Si
Si

C Si
O H3 O
Si CH3 Si
O

CH3 Si

34
35
Space group
= point group + translation

P21/c, C2/c etc

36
41 43

Symmetry Operations:
screw axes
rotation + translation

21(//a), 21(//b), 41(//c), 42(//c), 31(//c) etc

37
Symmetry Operations: glides

c-glide (┴ b), n-glide,

d-glide etc

38
 Andy Wahol
• Pop artist of postmodernism

39
Diffraction from Crystalline Solids
X-ray, electron, neutron diffractions

ED

XRD
40
Real Lattice ↔ Reciprocal Lattice
Diffraction pattern is the reciprocal lattice (Fourier
transformation) from the real lattice of the crystal.

41
 History of Diffractions
Interference of waves structures of materials

42
 Discovery of X-ray
WILHELM CONRAD RÖ NTGEN (1845-1923)
• 1901 Nobel Laureate in Physics
in recognition of the extraordinary services he
has rendered by the discovery of the
remarkable rays subsequently named after
him.

http://www.resonancepub.com/wroentgen.htm43
Generation of X-ray
What is Ka and K ?
Ka : 2p 1s
K : 3p 1s

44
 MAX VON LAUE
(1879-1960)
• 1914 Nobel Laureate in Physics
His best known work, however, for
which he received the Nobel Prize for
Physics for 1914, was his discovery
of the diffraction of X-rays on
crystals.

45
http://nobelprize.org/physics/laureates/1914/laue-bio.html
 SIR WILLIAM HENRY BRAGG (1862-1942)
SIR WILLIAM LAWRENCE BRAGG (1890-1971)

• 1915 Nobel Laureate in Physics

for their services in the analysis of crystal structure
by means of X-rays.

http://nobelprize.org/physics/laureates/1915/wh-bragg-bio.html 46
 Bragg’s Law
• There are many sets of parallel planes, whose normal vectors are
represented by Miller indices (hkl). When the incident beam, the
diffracted beam and the normal are in plane and obey Bragg’s
law, all the photons in the diffracted beam are in phase, or
constructively interfered.

47
Electron densities can be obtained by Fourier
Transformation of structure factors, Fhkl

diffraction (I, (hkl)) electron density

48
 Powder Diffractions
probably the most often used technique by material scientists
• Conventionally, structure determination is done by single
crystal X-ray diffraction.
• In many cases, good single crystals cannot be obtained. In
these cases, powder diffractions can be performed to
obtain structural information.

49
In XRPD many (hkl) spots form
many rings, each of which has only
one variable, 2q

50
 FRANCIS HARRY COMPTON CRICK (1916~2004)
JAMES DEWEY WATSON (1928~)
MAURICE HUGH FREDERICK WILKINS (1916~2004)

• 1962 Nobel Laureate in Medicine

for their discoveries concerning the molecular
structure of nuclear acids and its significance
for information transfer in living material.

James Watson
Maurice Wilkins Rosalind Franklin (1920–1958)
and Francis Crick
http://www.chemheritage.org/classroom/chemach/pharmaceuticals/watson-crick.html 51
 In Photograph 51 Nicole
Kidman plays scientist
Rosalind Franklin, the
focused, demure woman
who took the X-ray
photograph that prompted
the discovery of the
double-helix structure of
DNA.

In this hostile, masculine, sexist world, Dr Rosalind Franklin, whom they persist in
addressing as ‘Miss’, took the clearest X-ray diffraction photo of DNA crystal. Her
doctoral assistant, Ray Gosling, ‘shares’ the photo with rival scientists Maurice Wilkins,
Francis Crick and James Watson, and they build the model of the double-helix structure.

They were awarded the Nobel Prize; Franklin was little more than a footnote in
Wilkins’s paper. But by then, the cancer caused by fatal X-ray beams had killed her. 52
 CLINTON JOSEPH DAVISSON
(1881-1958)
SIR GEORGE PAGET THOMSON (1892-1975)
son of J. J. Thomson

• 1937 Nobel Laureate in Physics

for their experimental discovery of
electron diffraction by crystals.

http://nobelprize.org/physics/laureates/1937/davisson-bio.html 53
http://nobelprize.org/physics/laureates/1937/thomson-bio.html
 CLIFFORD G. SHULL
(1915~2001)
• 1994 Nobel Laureate in Physics
for the development of the neutron
diffraction technique.

54
http://nobelprize.org/physics/laureates/1994/shull-autobio.html
Neutron diffraction
• Crystal structure determination
especially for light atoms like H
• Magnetic structure analysis
to find magnetic lattice

55
The paradox of quasicrystals
Quasicrystal is a structure that is
ordered but not periodic.
Ho-Mg-Zn alloy quasicrystal
Dan Shechtman was awarded the
Nobel Prize in Chemistry in 2011.

56
 Shechtman and Pauling Debate
Quasicrystal Theory

Linus Carl Pauling (1901 –1994)

video video 57
Bonding in Crystalline Solids:
Introduction to Band Theory

58
Illustration of d-orbital overlap between
adjacent metal atoms in an extended metallic
network

Molecular orbital (MO)

diagram for the homonuclear
diatomic molecule Ti2
59
The band diagram for a metallic solid, illustrating the
continuum between valence and conduction bands (no
band gap) for increasingly larger numbers of atoms

60
The splitting of 3s and 3p atomic
orbitals of Six into bands

61
The band diagram for Mg metal, showing the formation of
valence/conduction bands and zero band gap through
overlap of 3s/3p atomic orbitals on neighboring Mg atoms

62
Schematic of the density of states (DOS) – the number of
available energy states per unit volume in an energy interval

63
P-N Junction

64
Introduction to Magnetism

65
Magnetization and Magnetic Susceptibility

• If a body is placed in a homogeneous magnetic field Ho,

the magnetic field with the body varies from free-space
value.
• That is,
• B = Ho + 4p M
• B : magnetic induction (the field within the body)
• M : intensity of magnetization
• B/Ho = 1 + 4p (M/Ho) = 1 + 4p c
• M/Ho : dimensionless
c : magnetic susceptibility

66
Macroscopic Point of View
• Magnetic moment, M, can be related to the rate the
energy change of a body in the magnetic field, Ho.

-E B/Ho = 1 + 4p (M/Ho) = 1 + 4p c

M=
Ho 10 Tesla = 105 Guass
The sign of the induced magnetic moment, M, defines
two types of magnetic behaviors:
Paramagnetism (+), Diamagnetism (-)

video video 67
 Ferromagnetism, Antiferromagnetism and
Ferrimagnetism (亞鐵磁性)
• Ferromagnetism, antiferromagnetism and ferrimagnetism
can be considered as special forms of paramagnetism.

68
Derivation of M and cm
microscopic point of view

For S = 1/2 system (Spin only, no orbital contribution)

 = -gS
 : magnetic moment
: spin angular momentum
S
ge : electron g-factor (ge = 2.0037 for free e-)
 ( or B) : Bohr magneton of the electron

 = 9.3 x 10-21 erg/Gauss

69
 Interaction energy between magnetic
moment and applied field (Zeeman effect)
• The Hamiltonian (𝐇) describing
the interaction energy of magnetic
moment () with the applied
magnetic field, H, is:

H = -.H = gS.H
energy

 = -gS

Zeeman effect
70
 The energy states for S = ½ system
The energies (eigen values) for S = ½ (ms = +½ , −½ ) system are:
E = msgHo E1/2 = (½ )gHo and E-1/2 = −(½ )gHo
𝒈𝜷
−
𝟐
Energy ms=1/2
E½ = +(½ )gHo
Ho
ms=1/2
Zeeman effect E=gH
m o
s=-1/2 𝒈𝜷
𝟐

E-½ = −(½ )gHo

ms=-1/2
Ho
71
Relative populations of ½ and –½ states
When Ho = 25 kG E ~ 2.3 cm-1
At 300 K, kT ~ 200 cm-1 m
Energy s=1/2

Boltzmann distribution ms=1/2

E=gHo
ms=-1/2
P1/2 = e-E/kT ~ 1
P-1/2 ms=-1/2
Ho
The populations of ms = 1/2 and –1/2 states are almost equal with only a
very slight excess in the –1/2 state.

That means that even under very large applied field, the net magnetic
moment is still very small.

72
To obtain M ( or cm), we need to consider all the
energy states that are populated. Energy ms=1/2

ms=1/2
E=gHo
ms=-1/2

∵ H = -.H = gS.H ms=-1/2

Ho

∴ The magnetic moment, n with the direction // Ho, of an

electron in a quantum state n can be obtained by:
n = -(∂En)/(∂H) = −msg
So we consider:
(1) The magnetic moment of each energy state.
(2) The population of each energy state.

That is, M = NSn.Pn

N : Avogadro’s number Pn : probability in state n.
73
Energy ms=1/2 magnetic moment
ms=1/2
E=gH
n = −(∂En)/(∂H) = −msg
m o
s=-1/2

H = -.H = gS.H
ms=-1/2
Ho

Magnetization M = NSn.Pn

Boltzmann distribution function

-En/kT
Pn = Nn
= e Nn: population of state n
Se
NT -E /kT n
NT: population of all the states

74
 energy magnetic moment

En n
m s= 1 /2
E nergy 1 /2 g  H -1 /2 g 

m s= 1 /2
E = gH o
m s= -1 /2

-1 /2 g  H 1 /2 g 
m s= -1 /2
H o

E = msgHo n = -(∂En)/(∂H) = -msg

-En/kT
M= NSn.Pn Pn = Nn
= e
Se
NT -E /kT n

75
 En n
m s= 1 /2
E nergy 1 /2 g  H -1 /2 g 

m s= 1 /2
E = gH o

NS
-En/kT

m s= -1 /2
ne
M= ms
m s= -1 /2
-1 /2 g  H 1 /2 g 

Se
H
-En/kT o

ms Since gH<<kT when Ho ~ 5kG

g/2kT -g/2kT
N[ e
g/2 -g/2e ] e±x
~ 1± x
= -g/2kT
approximation

[e g/2kT
+e ] when x << 1

N g [ 1 + g/2kT (1 g/2kT) ]
= 2 1 + g/2kT + (1 g/2kT)
N g2
= 4kT = M 76
Curie Law of paramagnetic materials

cm = M
= N g2  
 4kT

Curie Law: cm = C/T

c
m
s
l
op
e=
C
∴ C= N g2
4k
Curie constant

1
/
T
77


c Curie-Weiss Law

q
q
T
m

(K)

1
dashed lines:
extrapolation
cm = C/(T-q)
θ is called Weiss constant.
If q > 0, the magnets interact
ferromagnetically.

If q < 0, the magnets interact

antiferromagnetically.

There are two different ways of coupling among magnetic moments,

parallel alignment (ferromagnetic) or antiparallel alignment
(antiferromagnetic). At high temperature, they exhibit paramagnetic-like
behavior and follow Curie-Weiss law, because these couplings are less
significant comparing to thermal influences.
78
For general S values (not only S = 1/2)

En = msgbH ms = -S, -S+1, …. , S-1, S

S (-m g)e
S
-msgH/kT
N s N g2H S(S+1)
M= ms=-S
=
Se
-m gH/kT s
3kT
ms

cm = M
= N g2 S(S+1)
spin only
 3kT

79
 Definition of eff
cm = N g2 S(S+1)
3kT

) ( cmT ) ~ 2.828( cmT )

1/2 1/2 1/2
3k
eff = ( N

eff = g[S(S+1)]1/2 (BM, Bohr Magneton)

or eff = [n(n+2)]1/2 where n= number of unpaired e-

80
 Interactions of micromagnets

Paramagnetic materials
Interactions ignored p
ara
m a
g n
etic
among magnets
c
m

These magnets are

oriented randomly
under zero applied
magnetic field. T

If interactions are significant among these micromagnets, these

materials are ferromagnetic, antiferromagnetic or ferrimagnetic.

81
Interactions significant among micromagnets

Ferromagnetic, Antiferromagnetic and Ferrimagnetic

cm
Curie-Weiss Law

f e r r o m a g n e t ic

+ C u r ie t e m p e r a t u r e

T
p a r a m a g n e t ic
cm


c m

q
q
T

1

' temperature
Neel
+
paramagnetic

antiferromagnetic

T 82
B–H magnetization hysteresis curve for a
ferromagnetic material
When a ferromagnetic material is magnetized in one
direction, it will not relax back to zero magnetization
when the imposed magnetizing field is removed. It
must be driven back to zero by a field in the opposite
direction.

R: remanent 剩餘的
Domain size C: coercive 強制的
Increases. 83
 Magnetic behaviors of nanoparticles of
Fe, Co, Ni
Nanoparticle
Superparamagnetism is a form of magnetism, which appears in
small ferromagnetic (or ferrimagnetic) nanoparticles. In sufficiently
small nanoparticles, magnetization can randomly flip direction under
the influence of temperature.

each small domain can be viewed as a unpaired electron Hysteresis loop

Magnetization can randomly flip direction
under the influence of temperature. The
typical time between two flips is called the
Néel relaxation time.

84