CHM361

CHAPTER 3:

CRYSTALLINE & SOLID STATE

 CONTENTS
 Crystal Structures
 Metallic crystal structure
 Ionic lattice (NaCl and CsCl)
 Giant molecule crystal structures
 Crystal Defects – Point 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 that 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.

Crystal vs amorphous solid
 TERM

 Unit Cell
 Smallest part of a crystal which if repeated in 3D space
would produce the entire cell.
 Basic building block of the crystal.

 Lattice Points
 Points or corner where atoms, ions or molecules are placed.
TERM
 TERM

 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.
CUBIC LATICE SYSTEM (SIMPLE CUBIC)

 Also known as the primitive cubic unit cell.

 Consist of 8 lattice which are placed at each corner of the cube.
 Eg: Oxygen molecule
 CUBIC LATICE SYSTEM (BODY-CENTERED CUBIC)

One lattice point at the centre

 Consist of 8 lattice point at the corners of the cube & 1 lattice point at the
centre of the unit cell.

 Eg: Na, Fe
 CUBIC LATICE SYSTEM (FACE-CENTERED CUBIC)

 Consist of 8 lattice point at the corners of the cube & 1 lattice point at
the centre of each face.
 Eg: Cu, Au
 COUNTING THE NUMBER OF PARTICLES
IN A UNIT CELL
 Particles in 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.

 METALLIC CRYSTAL STRUCTURE

 Simplest crystal structure.

 Tend to be densely packed.
 Every lattice point in a crystal is occupied by an atom of the same
metal.
 Bonding- bonding electron are delocalized over the entire crystal.
 The great cohesive force resulting from delocalization is responsible
for metal strength.
 The mobility makes the metal good conductor of heat and electricity.
METALLIC CRYSTAL STRUCTURE

Cr, Fe Cu, Al, Ag, Au Cd, Mg, Zn, Ti

 METALLIC CRYSTAL STRUCTURE (BCC)

Coordination number of 8.

The bcc unit cell consists of a net total of 2 atoms.

1
8 at the corner : 8  1
8
1 at the centre : 1 1  1

Total of atom : 2 atoms

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.
1
8 at the corner : 8  1
8
1
6 at the faces : 6  3
2

Total of atom : 4 atoms

 METALLIC CRYSTAL STRUCTURE (FCC)

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.
 METALLIC CRYSTAL STRUCTURE (HCP)

 there are 6 atoms in the hcp unit cell. 12 atoms in the corners of the
top and bottom layers, the two atoms in the center of the hexagon of
both the top and bottom layers and each of the three atom in the
middle layer.

1
12 at the corner (top & bottom) : 12   2
6
1
2 at the center (top & bottom) : 2  1
2
3 at the middle : 3 1  3

Total of atom : 6 atoms

 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.
 IONIC CRSYTAL

 The binding between the ions is mostly electrostatic and

rather strong.

 it has no directionality.

 There are no free electrons, ionic crystals are insulators.

 IONIC CRSYTAL (NaCl)

 The unit cell can be drawn with either the

Na+ ions at the corners, or with the Cl- ions
at the corners.

 Na+ & Cl- are arranged alternately.

 Face-centered Cubic (FCC)

  6:6-co-ordinated.

Na+  Only those ions joined by lines are actually

touching each other. The Cl- ion in the
Cl-
centre is being touched by 6 chloride ions.
IONIC CRSYTAL (NaCl)
1
8 Na  ions at the corner : 8  1 Na  ions
8

1
6 Na  ions at the face : 6  3 Na  ions
2

Total of Na  ions : 4 Na  ions

1
12 Cl  ions at the edge : 12   3 Cl  ions
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.
 IONIC CRSYTAL (NaCl)
PHYSICAL PROPERTIES
1) High melting point.
 Strong electrostatic forces between ions of opposite charge.
 Requires more energy to overcome the attraction.

2) Hard but brittle.

 Strong electrostatic force make it hard but, if a strong force is
applied, the ion layers shifts slightly.
 Ions of the same charge are brought side-by-side and so the
crystal repels itself.
 IONIC CRSYTAL (NaCl)
PHYSICAL PROPERTIES

3) Does not conduct electricity in solid but does so in

molten or aqueous solution.
 Ions are not free to move because are held strongly by
electrostatic force in fixed position.
 When the solid melt, ions are free to move thus conducting
electricity.
 IONIC CRSYTAL (CsCl)

 Simple Cubic.

  8:8-co-ordinated.

 Each caesium ion is touched by

eight chloride ions.

Cs+

Cl-
 IONIC CRSYTAL (CsCl)

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

Total of Cs  ions : 1 Cs  ions

1
8 Cl  ions at the corner : 8  1 Cl  ions
8

Total of Cl  ions : 1 Cl  ions

**1 caesium ions & 1 chlorides ion contained within

Cs +
the unit cell.

Cl-
 GIANT MOLECULE CRYSTAL STRUCTURE

 Giant molecule consist of particles held together by

covalent bonds.

 Non-metals.

 Allotropes of carbon.
- pure forms of the same element that differ in structure.
 GIANT MOLECULE CRYSTAL STRUCTURE
(DIAMOND)

 Composed of single element (C) arranged in 3D

network.
 GIANT MOLECULE CRYSTAL STRUCTURE
(DIAMOND)
 Each C atom covalently bonded to 4 other C in tetrahedral arrangement by strong
covalent bonding.
 so no free moving electron to conduct electricity.
 Diamond does not conduct electricity.

 Very strong covalent bond.

 So have high melting point 3550°C.
 Very hard.

 Used in cutting tools & grinding.

 GIANT MOLECULE CRYSTAL STRUCTURE
(GRAPHITE)
Each C is connected with 3 other C by covalent bond forming 6-member
rings that form flat layer which are held loosely by weak VDW forces.

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.
 GIANT MOLECULE CRYSTAL STRUCTURE
(GRAPHITE)
 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.

 CRYSTAL DEFECT
(VACANCY)
 An atom is missing from its regular atomic site.
 When some lattice sites left vacant while the formation of crystal.
 Because of missing the atom, the density of substance decreases.
 The vacancy defect develops on heating of substance.
 When the temperature is sufficiently high, the atoms vibrate around
their regular positions, some acquire enough energy to leave the site
completely.
 CRYSTAL DEFECT
(SCHOTTKY)
 A pair of one cation and one anion missing from regular sites in ionic
crystal.
 Almost similar in size, such as NaCl, KCl, CsCl
 the number of missing cations is equal to the number of missing anions
in order to maintain the electrical neutrality of the ionic compound.
 CRYSTAL DEFECT
(INTERSTITIAL)
 when an atom occupies a definite position in the lattice that is not
normally occupied in the perfect crystal.
 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
 CRYSTAL DEFECT
(FRENKEL)
 an ion displaced from a regular site to an interstitial site in ionic crystal.
 As cations are generally the smaller ones, it is possible for them to get
displaced into the void space.
 Anions do not get displaced as the void space is too small compared to
the size of the anions.
 As there are a number of cations and anions (which remain equal even
because of defect); the density of the substance & the overall electrical
neutrality of the crystal does not change.
 such as ZnS, AgCl, AgBr, AgI
 CRYSTAL DEFECT
(METAL EXCESS DEFECT)
(a) Metal excess defects due to anionic vacancies:
 missing of anions from regular site leaving a hole which is occupied by
electron to maintain the neutrality of the compound.
 The trapped electrons are called F-centers or color centers because
they are responsible for imparting color to the crystal.
 This defect is common in NaCl, KCl, LiCl,.
 CRYSTAL DEFECT
(METAL EXCESS DEFECT)
(b) Metal excess defect due to presence of extra cations at interstitial
sites

 Extra cations occupying interstitial sites while electrons occupy another

interstitial site to maintain electrical neutrality

 Similar to Frenkel defect.

 CRYSTAL DEFECT
(METAL DEFICIENCY DEFECT)
 Solids which have less metals compare to ideal stoichiometric proportion.
 CRYSTAL DEFECT
(METAL DEFICIENCY DEFECT)
 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.
 This type of defect occurs in compounds where the same metal can
exhibit variable valency.
 Transition metal compounds like NiO, FeO, FeS.
 SEMICONDUCTOR

 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

 At elevated 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.

 Doping is a process wherein impurities are added to the

semiconductor to improve conductivity.
 SEMICONDUCTOR (N-TYPE)

 The addition of pentavalent impurities (atoms with 5 Ve-)

such as antimony, arsenic or phosphorous contributes free
electrons.

 This electron can move through the structure & function as a

charge carrier.

 Greatly increasing the conductivity of the intrinsic

semiconductor.
 SEMICONDUCTOR (N-TYPE)

 Known as Donor Impurities.

 N-negative (charge of the extra electron)
 SEMICONDUCTOR (P-TYPE)

 The addition of trivalent impurities (atoms with 3 Ve-) such

as boron, aluminum or gallium creates deficiencies of
valence electrons, called "holes".

 so the charge carrier is effectively a positively charged hole.

 Known as acceptor impurities.

 P-positive (holes)
 METALLIC BONDING

 Attraction between a positive ions and the sea of

delocalized electrons.

 strong bonds.

 The strength of metallic bond is proportional to the number

of ve- & inversely proportional to the size of atom.

 Eg: the metallic bond in Mg is stronger than in Na because

Mg atom has 2 ve- and smaller while Na has only one ve-
and larger.
 PROPERTIES OF METALLIC BONDS

 High melting and boiling points

 Metallic bonds are strong and a lot of energy is needed to
break them.
 Conducting electricity
 Since the valence electron are free to move.
 Metallic luster
 Delocalized valence electron can absorb & reemit
electromagnetic radiation.
 Malleable & ductile
 The layers of cations can easily slide past each other
without breaking the lattice structure.
 ELECTRON SEA MODEL

 Atoms in metallic element are packed closely as possible.

 As a result Ve- of each atom become attracted to the

positively charged nuclei of the neighbor and become free
from the attraction of its own nucleus.

 These free electron are said to be delocalized over the

entire solid embedded in a sea of electron.

 The electron-sea is acting as glue holding the positive

ions.
ELECTRON SEA MODEL
 BAND THEORY OF METALS

 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 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.
 INSULATORS SEMICONDUCTORS CONDUCTORS

Conduction Band
Conduction Band Conduction Band
ENERGY

Band Gap
Band Gap

Valence Band Valence Band

Valence Band

Large band gap Small band gap Overlap between the

between the valence between the valence valence &
& conduction band & conduction band conduction band

 Current flows when electrons move from the valence band to the conduction
band.

 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.
 BAND THEORY OF METALS

 In metal, the valence band & conducting band are adjacent to each
other.

 Means, electron can travel freely through the metal (from the valence
band to the conduction band).

 Current flows when electrons move from the valence band to the
conduction band.

 So, the amount of energy needed to promote a valence electron is

negligible.
 REVISION

TYPE OF CRYSTAL FORCES / BONDING GENERAL PROPERTIES

IONIC

GIANT

METALLIC