*

Crystalline and Solid State

* Crystal Structures
* Metallic crystal structure
* Ionic lattice (NaCl and CsCl)
* Giant molecule crystal structures
* Crystal Defects
* Stoichiometric defect
* Non-stoichiometric defect
* Semiconductor
* Metallic Bonding
* Electron Sea Model
* Band Theory of Metals

*
 * LEARNING OUTCOMES

1)Explain the crystal structures.

2)Explain the type of defect in crystal structure.

3)Explain semiconductor.

4)Explain Electron Sea Model & Band Theory.

 * SOLID

Atoms, molecules or ions in solid are arranged closely

together & regularly in a complete order.

Can only vibrate & rotate about fixed position.

Rigid arrangement.

Cannot move freely without disrupting the whole

structure.

The shape is independent of its container.

 Solid can be divide into

Amorphous: poorly defined shape

Crystalline: well defined
Their particles lack long range ordering
shape,
- Short range order
Their particles
(atoms,molecules,ions) in
orderly arrangement
- Long range order
 *
Atoms (and later ions) will be viewed as hard
spheres. In the case of pure metals, the packing
pattern often provides the greatest spatial efficiency
(closest packing).

Ionic crystals can often be viewed as a close-

packed arrangement of the larger ion, with the smaller
ion placed in the “holes” of the structure.
 *
* Crystals consist of repeating asymmetric units which may
be atoms, ions or molecules.
* The space lattice is the pattern formed by the points
that represent these repeating structural units.
* Usually the smallest unit cell which exhibits the greatest
symmetry is chosen.
* If repeated (translated) in 3 dimensions, the entire
crystal is recreated.
* Points or corner where atoms, ions or molecules are
placed.
* In many case lattice point does not actually contain such a
particle- may be several atoms, ions or molecules identical
arrange
* For simplicity, assume each lattice point occupied by an
atom

*
 * Coordination number

The number of atoms or ions surrounding an

atom or ions in a crystal lattice.
The value is a measurement of how tightly the
spheres are packed together.
The larger the value, the closers the spheres are
to each other.
* BASIC CRYSTAL SYSTEM
* LATTICE
* Since metal atoms and ions lack directional bonding,
they will often pack with greatest efficiency.
* In close or closest packing, each metal atom has 12
nearest neighbors.
* The number of nearest neighbors is called the
coordination number.
* Six atoms surround an atom in the same plane, and the
central atom is then “capped” by 3 atoms on top, and
3 atoms below it.

*
*

There are two types of holes

created by a close-packed
arrangement.

Octahedral holes lie within

two staggered triangular
planes of atoms.
*

The coordination number of

an atom occupying an
octahedral hole is 6.

For n atoms in a close-

packed structure, there are
n octahedral holes.
 *
Tetrahedral holes are formed by a planar triangle of atoms,
with a 4th atom covering the indentation in the center. The
resulting hole has a coordination number of 4.
*
The orange spheres show atoms
in a cubic close-packed
arrangement.

The small white spheres behind

each corner indicate the
location of the tetrahedral
holes.
*
For atoms in a cubic unit
cell:
Atoms in corners are ⅛
within the cell
*
For atoms in a cubic unit
cell:

Atoms on faces are ½

within the cell
*
A face-centered cubic unit
cell contains a total of 4
atoms: 1 from the corners,
and 3 from the faces.
 For atoms in a cubic unit cell:

 Atoms in corners are ⅛

within the cell
 Atoms on faces are ½ within
the cell
 Atoms on edges are ¼ within
the cell

*
 * COUNTING THE NUMBER OF PARTICLES IN A
UNIT CELL

*Particlesin a unit cell can be seen at the lattice point but

may not contribute the whole entities to the unit.
*Particles located on edges, faces & corner are actually
shared by neighboring unit cell.
* COUNTING THE NUMBER OF PARTICLES IN A
UNIT CELL

Particles at the corner

Shared by 8 unit cell.

Contributes only 1/8 towards its own unit cell.

Particles at the edge

Shared by 4 unit cell.

Contributes only ¼ towards its own unit cell.
* COUNTING THE NUMBER OF PARTICLES IN A
UNIT CELL

Particles at the face

Shared by 2 unit cell.

Contributes only ½ towards its own unit cell.

Particles at the centre

Belongs only to one cell.

 *
*SIMPLE CUBIC
-the centres of 8 identical particles define
the corners of cube
-Attraction pull particles together, so they
touch along cube’s edges
-They do not touch diagonally along cube’s
faces or centre.
-Coordination num= 6, 4 its own layer,
1 in the layer above, 1 in the layer below
Eg: Oxygen molecule
*BODY- CENTRED CUBIC UNIT
- identical particles lie at each corners
- those at corners do not touch each other but
they all touch the one in centre
-Each particle surrounded by 8 nearest neighbor:
4 above, 4 below so coordination num = 8
- Eg: Na, Fe
*FACE-CENTRED CUBIC
-Identical particles lie at each corner and in the
centre of each face but not in the centre of the
cube
-Those at corner touch those in the face but not
each other.
-Coordination num=12
-Eg: Cu, Au
 *
* The simplest structure – every lattice point in a crystal occupied
by an atom of the same metal.
* Generally body-centered cubic, face-centered cubic or hexagonal
close pack
 * METALLIC CRYSTAL STRUCTURE

STRUCTURE

Body Centered Face Centered Hexagonal

Cubic Cubic Closed Packed
(BCC) (FCC) (HCP
Cr, Fe Cu, Al, Ag, Au Cd, Mg, Zn, Ti
* Usually very dense
* Bonding- bonding electron are delocalised over the entire
crystal
* The great cohesive force resulting from delocalisation is
responsible for metal strength
* The mobility makes the metal good conductor of heat and
electricity
* Have wide range of melting points and hardnesses- depend
on packing efficiency of the crystal structure and the
number of valence electron available for bonding
* Eg. Group 2A are harder and higher melting point than Group 1A
because 2A have closest pack structure and twice as many
delocalised valence electron

*
 * METALLIC CRYSTAL STRUCTURE
(BCC)

*Coordination number of 8.
*The bcc unit cell consists of a net total of 2 atoms; one in
the center and eight eighths from corners.
*The bcc arrangement does not allow the atoms to pack
together as closely as the fcc or hcp arrangements.
 * METALLIC CRYSTAL STRUCTURE
(FCC)

*coordination number of 12.

*The fcc unit cell consists of a net total of four atoms;
eight from corners atoms and six of the face atoms.
*the atoms can pack closer together than they can in the
bcc structure.
*The atoms from one layer nest themselves in the empty
space between the atoms of the adjacent layer.
 * METALLIC CRYSTAL STRUCTURE
(HCP)

* coordination number is 12 . Six nearest neighbors in the same close

packed layer, three in the layer above and three in the layer below.

* there are six atoms in the hcp unit cell. 12 atoms in the corners of the top
and bottom layers contribute 1/6 atom to the unit cell, the two atoms in
the center of the hexagon of both the top and bottom layers each
contribute ½ atom and each of the three atom in the middle layer
contribute 1 atom.
 * METALLIC CRYSTAL STRUCTURE
(HCP)

*The atoms from one layer nest themselves in the empty

space between the atoms of the adjacent layer just like in
the fcc structure.

*has three layers of atoms. In each the top and bottom

layer, there are six atoms that arrange themselves in the
shape of a hexagon and a seventh atom that sits in the
middle of the hexagon.
* In most ionic compounds, the anions are much larger
than the cations, and it is the anions which form the
crystal array. The smaller cations reside in the holes
between the anions.
* Lattice points occupied by cations and anions, example
NaCl, CsCl, MgSO4
* Held together by electrostatic attraction
* Hard, brittle, high melting point
* Poor conductor of heat and electricity

*
* Ionic solids are made up of positively and negatively
* charged ions called cations and anions.
* As a general rule, a cation is always smaller than an
anion
* The sizes of these ions are represented by their radii.
* In the subsequent discussion we will take r+ as the radius
of the cation and r– as the radius of the anion.

*
*
1. The Rock Salt (NaCl) structure-

A face-centered cubic array of the

cations with anions in all of the
octahedral holes.
The coordination number is 6 for
both ions.
Num of atom (unit cell) for cl-
[(8x1/8)+(6x1/2)] =4
Num of atom (unit cell) for Na+
[(12x1/4)+1=4
 * IONIC CRSYTAL (NaCl)
*Calculate how many Na+ & Cl- in a unit cell.
8 Na  ions at the corner  1 Na  ions
1
: 8
8

6 Na  ions at the face  3 Na  ions

1
: 6
2

Total of Na  ions : 4 Na  ions

12 Cl ions at the edge  3 Cl ions

1
: 12 
4

1 Cl ions at the centre : 1 1  1 Cl ions

Total of Cl ions : 4 Cl ions

**4 sodium ions & 4 chlorides ion

contained within the unit cell.
*
2. The CsCl structure-

Chloride ions occupy the corners of a

cube, with a cesium ion in the center
(called a cubic hole) or vice versa.

Both ions have a coordination number of

8, with the two ions fairly similar in
size.

Num of atom(unit cell) for cl-

[(8x1/8)]=1

Num of atom (unit cell) for Cs

1
 * IONIC CRSYTAL (CsCl)

*Calculate how many Cs+ & Cl- in a unit cell.

1 Cs  ions at the centre : 1 1  1 Cs  ions

Total of Cs  ions : 1 Cs  ions

8 Cl ions at the corner  1 Cl ions

1
: 8
8

Total of Cl ions : 1 Cl ions

**1 caesium ions & 1 chlorides ion contained within

Cs+ the unit cell.

Cl-
* Direct consequence of the fixed ion positions and very strong
interionic forces which create high lattice energy
* Thus ionic solid have high melting point and low electrical
conductivities
* When large amount heat supply, ion gained energy to break
free – the solid melts and the mobile ion conduct current
* It is hard because only strong external force can change the
relative position – if enough force apply to move them, ion of
like charge are brought near each other and their repulsion
crack the crystal

*
 *
*The giant covalent structure of diamond
-Carbon has an electronic arrangement of 2:4. In diamond,
each carbon shares electrons with four other carbon atoms -
forming four single bonds.

-This is a giant covalent structure - it continues on and on in

three dimensions. It is not a molecule, because the number of
atoms joined up in a real diamond is completely variable -
depending on the size of the crystal.
Diamond

* has a very high melting point (almost 4000°C). Very strong

carbon-carbon covalent bonds have to be broken throughout
the structure before melting occurs.

* is very hard. This is again due to the need to break very strong
covalent bonds operating in 3-dimensions.

* doesn't conduct electricity. All the electrons are held tightly

between the atoms, and aren't free to move.

* is insoluble in water and organic solvents. There are no possible

attractions which could occur between solvent molecules and
carbon atoms which could outweigh the attractions between
the covalently bound carbon atoms .

*
 * GIANT MOLECULE CRYSTAL STRUCTURE
(GRAPHITE)

*Each C is connected with 3 other C by covalent bond.

C use only 3 of its 4 valence electron, so it has one
unused electron .
The electron are able to move freely thus conduct
electricity.
Graphite is an electric conductor.
has a high melting point, similar to that of diamond.
In order to melt graphite, it isn't enough to loosen
one sheet from another.
have to break the covalent bonding throughout the
whole structure.
6-member rings form flat layer which are held loosely
by weak VDW forces.
The layers are able to slide past each other, resulting
in softness of graphite.
Used as lead in pencil & lubricant.

*
* Ideal crystal does not exit; all contain large no. of defects or
imperfections - based on theoretical and experimental results

Point Defects: Irregularities or deviation from ideal arrangement

of constituent particles around the point or atom in a crystalline
solid is known as point defects.
Intrinsic defects
-Occur in pure substances
-do not involve changes in the
overall composition

Extrinsic defects
-Due to impurities
-involve changes in the
overall composition

Line Defects: Irregularities or deviation from ideal arrangement of

constituent particles in entire row of lattice is known as line
defects.

*
 *
* Point Defects: Point Defects are divided into
three types:

(i) Stoichiometric Defects

(ii) Impurities Defects

(iii) Non-stoichiometric Defects

* It is a type of point defects which does not
disturb the stoichiometry of solid. This is also
known as Intrinsic or Thermodynamic Defects.

* They have 4 types:

Vacancy Defects
Interstitial defects
Frenkel Defects
Schottky Defects.

*
*Vacancy defects and Interstitial defects are found in
non-ionic compounds
a) Vacancy defects:
- When some lattice sites left vacant while the formation
of crystal, the defect is called Vacancy Defects.
-In vacancy defects, an atom is missing from its regular
atomic site. Because of missing of atom the density of
substance decreases, i.e. because of vacancy defects.
-The vacancy defect develops on heating of substance –
increase vibrational motion and expand a crystal
b) Interstitial defects:
-Sometime in the formation of lattice structure some of the
atoms occupy interstitial site, the defect arising because of
this is called Interstitial Defects.
-In interstitial defect, some atoms occupy sites at which;
generally there is no atom in the crystal structure. Because of
the interstitial defects, the number of atoms becomes larger
than the number of lattice sites.
-Increase in number of atoms increases the density of
substance, i.e. interstitial defects increase the density of
substance
 * found in ionic compounds are known as Frenkel Defects and Schottky Defects.
a) Frenkel defects:
- It is a type of vacancy defect. In ionic compounds, some of the
ions (usually smaller in size) get dislocated from their original
site and create defect.
- This defect is known as Frenkel Defects. Since this defect arises
because of dislocation of ions, thus it is also known as
Dislocation Defects.
- As there are a number of cations and anions (which remain equal
even because of defect); the density of the substance does not
increase or decrease.

Ionic compounds; having large difference in the

size between their cations and anions; show
Frenkel Defects, such as ZnS, AgCl, AgBr, AgI, etc.
These compounds have smaller size of cations
compared to anions
b) Schottky defects:
- Schottky Defect is type of simple vacancy defect and shown by
ionic solids having cations and anions; almost similar in size, such
as NaCl, KCl, CsCl, etc. AgBr shows both types of defects, i.e.
Schottky and Frenkel Defects.

-When cations and anions both are missing from regular sites, the
defect is called Schottky Defect. In Schottky Defects, the number
of missing cations is equal to the number of missing anions in order
to maintain the electrical neutrality of the ionic compound.

-Since, Schottky Defects arises because of mission of constituent

particles, thus it decreases the density of ionic compound.
* There are large numbers of inorganic solids found which contain
the constituent particles in non-stoichiometric ratio because of
defects in their crystal structure.
* Thus, defects because of presence of constituent particles in
non-stoichiometric ratio in the crystal structure are called Non-
stoichiometric Defects.

* They have two types

Metal Excess Defects
Metal Deficiency Defects.

*
* Metal Excess Defects: Metal excess defects are of two types:
(a) Metal excess defects due to anionic vacancies:

* These type of defects seen because of missing of anions from

regular site leaving a hole which is occupied by electron to maintain
the neutrality of the compound. Hole occupied by electron is called
F-centre and responsible for showing colour by the compound.

* This defect is common in NaCl, KCl, LiCl, etc. Sodium atoms get
deposited on the surface of crystal when sodium chloride is heated
in an atmosphere of sodium vapour. In this process, the chloride ions
get diffused with sodium ion to form sodium chloride. In this
process, sodium atom releases electron to form sodium ion. This
released electron gets diffused and occupies the anionic sites in the
crystal of sodium chloride; creating anionic vacancies and resulting
in the excess of sodium metal.
* The anionic site occupied by unpaired electron is called F-
centre. When visible light falls over the crystal of NaCl, the
unpaired electron present gets excited because of absorption
of energy and impart yellow colour.

* Because of similar defect if present, crystal of LiCl imparts

pink colour and KCl imparts violet.
(b) Metal excess defect due to presence of extra cations at
interstitial sites:

* Zinc oxide loses oxygen on heating resulting the number of

cations (zinc ion) become more than anions present in zinc
oxide.

* The excess cations (Zn++ions) move to interstitial site and

electrons move to neighbouring interstitial sites. Because of
this zinc oxide imparts yellow colour when heated. Such
defects are called metal excess defects.
* Metal Deficiency Defects:

-Many solids show metal deficiency defects as they have less

metals compare to ideal stoichiometric proportion. The less
proportion of metal is compensated by same metals having higher
valency.

-Arise due to cationic vacancies. It occurs when positive ions are

missing from its crystal lattice.

-To maintain electrical neutrality, one of the nearest metal ion

acquires two positive charge.

- Such defects are shown generally by transition elements. Thus,

when metal present less than ideal stoichiometric proportion in a
solid, it is called metal deficiency defect.
Example – FeO is generally found in composion
of Fe0.95O. In the crystal of FeO, missing Fe++
ions are compensated with Fe+++ ions in order
to maintain neutrality.
*Has intermediate conductivity between a conductor &
insulator.
*Can resist & allow flow of electron depending on the
energy applied.
*Commonly used in electronics as transistor or diodes.
*Silicon is the most commonly used semiconductor
material

*
 * SEMICONDUCTOR

*Element that normally are not conductor but will conduct

electricity at elevated temperatures or when combined
with a small amount of certain other element.

*The electrons are held in place so they cannot move or

change their energy. Electrons in a bond are not
considered "free" and cannot participate in current flow,
absorption or other physical processes of interest.
 * SEMICONDUCTOR

* Atelevated temperatures, the electron can gain enough

energy to escape from its bond, the electron is free to move
about the crystal lattice and participate in conduction.

* At room temperature, a semiconductor has enough free

electrons to allow it to conduct current, while at, or close to
absolute temperatures, a semiconductor behaves like an
insulator.

* Dopingis a process wherein impurities are added to the

semiconductor to improve conductivity.
Semiconductors: Chemical Structure
* Start with a silicon substrate (block of silicon).
* Silicon has 4 valence electrons, and therefore a “lattice”
structure:
Each atom bonds with 4 neighbors.

No free electrons (poor conductor) unless

you heat it up (semi conductor).

* Other Group IV elements can be used for substrate, but they

* are harder to come by (carbon lattice for instance…)

*
 * The addition of a small percentage of foreign
atoms in the regular crystal lattice of silicon or
germanium produces dramatic changes in their
electrical properties, producing n-type and p-
type semiconductors.

Pentavalent impurities Trivalent impurities

Impurity atoms with 5 valence Impurity atoms with 3 valence
electrons produce n-type electrons produce p-type
semiconductors by contributing semiconductors by producing a "hole"
extra electrons. or electron deficiency.

*
* The addition of pentavalent impurities such as antimony,
arsenic or phosphorous contributes free electrons, greatly
increasing the conductivity of the intrinsic semiconductor.
Phosphorous may be added by diffusion of phosphine gas (PH3).

*
* The addition of trivalent impurities such as boron, aluminum or
gallium to an intrinsic semiconductor creates deficiencies of
valence electrons,called "holes". It is typical to use B2H6
diborane gas to diffuse boron into the silicon material.

*
* The application of band theory to n-type and p-type
semiconductors shows that extra levels have been added by
the impurities.
* In n-type material there are electron energy levels near
the top of the band gap so that they can be easily excited
into the conduction band.
* In p-type material, extra holes in the band gap allow
excitation of valence band electrons, leaving mobile holes
in the valence band.

*
There are two broad categories of semiconductor:
- Intrinsic Semiconductors
• Naturally have a moderate band gap. A small
fraction of the electrons in the valence band can
be excited into the conduction band. They can
carry current.
• The “holes” these electrons leave in the valence
band can also carry current as other electrons in
the valence band can be excited into them.
– Extrinsic Semiconductors
• Have had impurities added in order to increase the
amount of current they can conduct. (impurities
called dopants; process called doping)
• The dopants can *either* provide extra electrons
*or* provide extra holes:
– A semiconductor doped to have extra electrons is an
n-type semiconductor (‘n’ is for ‘negative’)
– A semiconductor doped to have extra holes is a
p-type semiconductor (‘p’ is for ‘positive’)
* The properties of metals suggest that their atoms possess strong
bonds, yet the ease of conduction of heat and electricity
suggest that electrons can move freely in all directions in a
metal.
* The general observations give rise to a picture of "positive ions
in a sea of electrons" to describe metallic bonding.
* Metals are not ionic but share several properties with ionic
compounds.
* Metals also form lattices in the solid state, where 8 to 12 other
atoms closely surround each metal atom.
* Within the crowded lattice, the outer energy levels of metal
atoms overlap.

*
* The general properties of metals include malleability and
ductility and most are strong and durable.
* They are good conductors of heat and electricity. Their
strength indicates that the atoms are difficult to separate,
but malleability and ductility suggest that the atoms are
relatively easy to move in various directions.
* The electrical conductivity suggests that it is easy to move
electrons in any direction in these materials. The thermal
conductivity also involves the motion of electrons

*
* Metals are malleable because they can be hammered into
sheets.
* Metals are ductile because they can be drawn into wires.
* In metallic bonds, the valence electrons from
the s and p orbitals of the interacting metal
atoms delocalize.
* That is to say, instead of orbiting their
respective metal atoms, they form a "sea" of
electrons that surrounds the positively charged
atomic nuclei of the interacting metal ions
* The electron-sea is acting as glue holding the
positive ions.

*
* Lustrousness (shininess) also results from the delocalization of electrons. Metals
are shiny because the delocalized electrons absorb energy easy, which causes
them to vibrate. This vibrational energy is then reemitted as visible light
* Metals are soluble in non-polar solvents, but not water, because metals are non-
polar substances. Remember, "like dissolves like".
• Malleable solid
• High melting point and boiling point
• Insoluble in water
• Insoluble in nonpolar solvents
• Conducts heat and electricity
• Lustrous
• Examples: gold, copper
* Band (Molecular Orbital) Model: Electrons assumed to
travel around metal crystal in MOs formed from valence
atomic orbitals of metal atoms

* Theory : delocalized electrons move freely through bands

formed by overlapping MO.

* Used the concept of orbital & based on the modern MO.

* It explain the metals are good conductor, as they are

capable of conducting electric current.

*
* Band theory is a quantitative model of bonding in solids.
– The wave functions of the valence electrons interact with each other.
– Bonding molecular orbitals result from constructive interference.
– Antibonding molecular orbitals result from destructive interference.

* The number of molecular orbitals formed equals the number of atomic

orbitals involved.
– For every bonding molecular orbital formed, one antibonding molecular
orbital is also formed.
– For odd number of bonding atoms, a nonbonding molecular orbital is
formed.
– The molecular orbitals formed belong to the entire set of atoms

*
* Band Theory
• Extension of MO theory
– Valence orbitals on N
atoms combine to form
N molecular orbitals
– for large N, the energies
of the MO’s are closely
spaced
– Each valence orbital will
generate a band with
different energy range

*
 *BAND THEORY OF METALS

*VALENCE BAND: Band of orbitals that are filled or partially

filled by valance electron.
- lower MOs are occupied by valence e-

*CONDUCTION BAND : Higher energy unoccupied bands in

which electron are free to migrate.
- empty MOs that are higher in energy

*BAND GAP : The energy difference between the valence

and conduction band is the.
*The band model propose that the lower MOs are occupied
by valence e- and make up valence band.The empty MOs
that are higher in energy make up the conduction band.
*In metals, the valence and conduction band are contiguous,
which means electrons can jump from filled valence band
to unfilled conduction band if receive any
energy(delocalised electron-free to move)

*Band Theory and Conductivity

• Electrons fill the lowest energy band first.
• The energy difference between the filled and empty bands
determines the electrical properties of the bulk material.
• The band populated by valence electrons is the valence
band.
• The empty band above the valence band is the conduction
band.
• The energy difference between the valence and conduction
band is the band gap.
• Current flows when electrons move from the valence band to
the conduction band.
– Conductors have small band gaps( no energy gap). A very
small amount of energy is required to move electrons to
the conduction band. When temp rised, greater random
motion hindered e- movement-decrease the conductivity
– Insulators have large band gaps. A large amount of
energy is required to move electrons to the conduction
band.
– Semiconductors have band gap intermediate of
conductors and insulators.thermally excited e- can cross
the gap,allow small current flow-the conductivity
increase when it heated
* The valence e- fill in these MO’s
* Depending on the substance, bands are partially or completely full
* A partial filled band allows conduction
* For a filled band to conduct, e- must be promoted from the highest
occupied MO to the lowest unoccupied MO
* The amount of energy required to promote these will determine
how well the substance conducts