Department of Chemistry, Bangalore University, Central College Campus

Bonding in Solids

Ionic bonds: A standard ionic solid consists of atoms held together by ionic bonds, that is, by the
electrostatic attraction of opposite charges (the result of transferring electrons from atoms with lower
electronegativity to atoms with higher electronegativity). Ionic solids are compounds formed by alkali
and alkaline earth metals in combination with halogens, ionic crystals are extremely stable since
considerable energy required to break ionic bonds. Metal bonded to non-metal recognized as ionic
compound because of its ionic bond.

Examples
1) Sodium Chloride: NaCl; an electron transferred from Na to Cl, there by forms a stable
compound through ionic bond.
11 Na = 1S2 2S2 2P6 3S1
17Cl = 1S2 2S2 2P6 3S2 3P5

Ionic solids
Ionic solids Lattice energy (KJ/mol) Melting points (°C)
NaCl -766 801
LiCl -829 613
KCl -686 776
RbCl -670 715
CsCl -649 646

Lattice energy: Many properties are dependent on the lattice energy (melting point, hardness, thermal
expansion coefficient) IONIC BOND
(Lattice energy: Energy released when a mole of ionic solid is formed from its ions in the gas state)

Covalent bonds:

How electrons are filled in order

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A network covalent solid consists of atoms held together by a network of covalent bonds (pairs of
electrons shared between atoms of similar electronegativity), and hence can be regarded as a single,
large molecule. The classic example is diamond; Other examples include silicon, quartz and graphite.

Properties: High strength; High elastic modulus; High melting point; Brittle

Their strength, stiffness, and high melting points are consequences of the strength and stiffness of the
covalent bonds that hold them together. They are also characteristically brittle because the directional
nature of covalent bonds strongly resists the shearing motions associated with plastic flow, and are, in
effect, broken when shear occurs. This property results in brittleness for reasons studied in the field of
fracture mechanics. Network covalent solids vary from insulating to semiconducting in their behavior,
depending on the band gap of the material.
Examples
1) Chlorine
Two chlorine atoms could both achieve stable structures by sharing their single unpaired electron as in
the diagram, The fact that one chlorine has been drawn with electrons marked as crosses and

the other as dots is simply to show where all the electrons come from. In reality there is no
difference between them. The two chlorine atoms are said to be joined by a covalent bond. The
reason that the two chlorine atoms stick together is that the shared pair of electrons is attracted to the
nucleus of both chlorine atoms

2) Hydrogen
Hydrogen atoms only need two electrons in their outer level to reach the noble gas structure of helium.
Once again, the covalent bond holds the two atoms together because the pair of electrons is attracted
to both nuclei.

3) Hydrogen chloride
The hydrogen has a helium structure, and the chlorine an argon structure.

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Covalent bonding at ‘A’ level

Most of the simple molecules you draw do in fact have all their atoms with noble gas structures.
4) Examples

CH4 NH3 H2O

Even with a more complicated molecule like PCl3, there's no problem. In this case, only the outer
electrons are shown for simplicity. Each atom in this structure has inner layers of electrons of 2,8.
Again, everything present has a noble gas structure.

5) Boron trifluoride, BF3

A boron atom only has 3 electrons in its outer level, and there is no possibility of it reaching a noble gas
structure by simple sharing of electrons. The boron has formed the maximum number of bonds that it
can in the circumstances, and this is a perfectly valid structure. Energy is released whenever a covalent
bond is formed. Because energy is being lost from the system, it becomes more stable after every

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covalent bond is made. It follows, therefore, that an atom will tend to make as many covalent bonds as
possible. In the case of boron in BF3, three bonds is the maximum possible because boron only has 3
electrons to share.

Metallic solids

Metal has delocalized valence electrons, metallic bonding is the bond between atoms within metals. It
involves the delocalized sharing of free electrons among a lattice of metal atoms. Metallic bonding is
the principal force holding together atoms of metals, the force that binds together the atoms of metal is
metallic bond.
Positively charged nuclei of metal atoms are held together by valence electrons to form metallic solids.
The electrons are considered to be "delocalized" because they aren't bound to any particular atoms, as
in covalent bonds. Delocalized electrons can move throughout the solid. This is the "electron sea
model" of metallic solids. Positive nuclei float in a sea of negative electrons. Metals are characterized
by high thermal and electrical conductivity and are typically hard, shiny and ductile. Example: almost all
metals and their alloys, such as gold, brass, steel

More than 80 elements in the periodic table are metals. Metals are solids at ordinary temperature and
pressure, with the exception (of mercury and gallium). Metals have characteristic properties such as:
 High thermal and electrical conductivity.
 Luster and high reflectivity. Malleability and ductility.
 They can be beaten or shaped without fracture.
 Variability of mechanical strengths (ranging from soft alkali metals to Tungsten, which is
hard).

Low ionization energies: Metals generally have low ionization energies. This implies that the valence
electrons of metal atoms are not strongly held by the nucleus. Valence electrons can move freely out of
the influence of their kernels (atomic orbit/structure minus valence electrons). Thus, metals have free
mobile electrons.

Large number of empty orbitals: It has been observed that in metals a number of valence orbitals
remain empty as the number of valence electrons in metals is generally less than the number of
valence orbitals.
For example, lithium {(Li, Z = 3) 1s2 2s1} has 2p orbitals vacant;
Sodium {(Na, Z = 11) 1s2 2s2 2p6 3s1} has 3p and 5d orbitals vacant
Magnesium {(Mg, Z = 12) 1s2 2s2 2p6 3s2} has 3p and 3d orbitals vacant.

The important features of electron sea model are:

1. The positively charged kernels of metal atoms are arranged in a regular fashion in a metallic lattice.
2. Loosely held valence electrons, surround each kernel in metallic lattice. Being loosely held to its
kernel, the valence electrons enjoy complete freedom in the metallic lattice and are regarded as mobile
electrons.

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3. In short, the metal may be regarded as 'a sea of electrons (common pool of electrons) in which there
is a three dimensional ordered arrangement of positively charged kernels, surrounded throughout by
mobile valence electrons'. This explanation is also responsible for its name electron sea model.
4. Thus, the simultaneous force of attraction between the mobile electrons and the positive kernels that
binds the metal atoms together is known as metallic bond.

Examples for materials having metallic bonds are most metals such as Cu: Copper; Al: Aluminium; Au:
Gold; Ag: Silver.

In summary, metallic solids are held together by a high density of shared, delocalized electrons,
resulting in metallic bonding. Classic examples are metals such as copper and aluminium, but some
materials are metals in an electronic sense but have negligible metallic bonding in a mechanical or
thermodynamic sense. Metallic solids have, by definition, no band gap at the Fermi level and hence
are conducting. Solids with purely metallic bonding are characteristically ductile and, in their pure
forms, have low strength; Melting points can be very low (e.g., Mercury melts at 234 K (−39 °C).
These properties are consequences of the non-directional and nonpolar nature of metallic bonding,
which allows atoms (and planes of atoms in a crystal lattice) to move past one another without
disrupting their bonding interactions. Metals can be strengthened by introducing crystal defects (for
example, by alloying) that interfere with the motion of dislocations that mediate plastic deformation.
Further, some transition metals exhibit directional bonding in addition to metallic bonding.

Molecular Solids
Covalent molecules are held together by intermolecular forces (Vander Waals) to form molecular solids.
While the intermolecular forces are strong enough to hold the molecules in place, molecular solids
typically have lower melting and boiling points than metallic, ionic, or network atomic solids, which are
held together by stronger bonds.

Examples: Water ice, Solid carbon dioxide, Sucrose (table sugar), hydrocarbons, sulphur, white
phosphorus, yellow arsenic, solid halogens, light chalcogens

Properties of molecular solids: The dipole forces are weaker than ionic or covalent bonds. The
relatively weak intermolecular forces cause molecular solids to have relatively low melting points,
typically less than 300 °C. Molecular solids tend to dissolve in organic solvents. Most of molecular
solids are relatively soft, electrical insulator and have low density.

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Comparison bonding and properties

Bond Type of substance Melting and Mechanical Solubility
boiling points properties
Covalent Molecular Low Soft in solid state Depends on
the polarity of
the molecules
Covalent Atomic, covalent, lattice Very high Very hard brittle Insoluble in all
solvent
Ionic Ionic High Hard and brittle Soluble in
polar solvents
Metallic Metallic High Ductile and workable Insoluble in all
solvent

Molecular Orbital (MO) Theory

In MO theory, molecular orbitals form by the overlap of atomic orbitals. Atomic orbital energy correlates
with electronegativity, as electronegative atoms hold electrons more tightly, lowering their energies. MO
modelling is only valid when the atomic orbitals have comparable energy; when the energies differ
greatly, the bonding mode becomes ionic. A second condition for overlapping atomic orbitals is that
they have identical symmetry. Two atomic orbitals can overlap in two ways, depending on their phase
relationship. An orbital's phase is a direct consequence of electrons' wavelike properties. In graphical
representations of orbitals, the orbital phase is depicted either by a plus or minus sign (with no
relationship to electric charge) or by shading one lobe. The sign of the phase itself does not have
physical meaning except when mixing orbitals to form molecular orbitals. Two same sign orbitals have a
constructive overlap, forming a molecular orbital with the bulk of the electron density located between
the two nuclei. This MO is called the bonding orbital, and its energy is lower than that of the original
atomic orbitals.

Principles of MO theory

Principle Details
Total number of molecular orbitals is equal to the total The molecule H2 is composed of two H atoms. Both
number of atomic orbitals used to make them. H atoms have a 1s orbital, so when bonded together,
there are therefore two molecular orbitals.
Bonding molecular orbitals are lower energy than the Electrons in bonding molecular orbitals help stabilize
atomic orbitals from which they were formed. a system of atoms since less energy is associated
with bonded atoms as opposed to a system of
unbound atoms. Bonding orbitals are formed by in
phase combinations of atomic orbitals and increase
the electron density between the atoms
Anti-bonding molecular orbitals are higher energy Electrons in anti-bonding molecular orbitals cause a
than the atomic orbitals from which they were formed. system to be destabilized since more energy is
associated with bonded atoms than that of a system
of unbound atoms. Anti-bonding orbitals are formed
by out of phase combinations of atomic orbitals and
decrease the electron density between atoms

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Following both the Pauli exclusion principle and Electrons fill orbitals with the lowest energy first. No
Hund's rule, electrons fill in orbitals of increasing
more than 2 electrons can occupy 1 molecular orbital
energy. at a time. Furthermore, all orbitals at an energy level
must be filled with one electron before they can be
paired.
Molecular orbitals are best formed when composed of When Li2 forms the two lowest energy orbitals are the
Atomic orbitals of like energies. pair of bonding and antibonding orbitals formed from
the two possible combinations of the 1s on each
atom. The 2s orbitals combine primarily with each
other to form another pair of bonding and antibonding
orbitals at a higher energy.

Aufbau principle states that orbitals are filled starting with the lowest energy

Pauli Exclusion Principle: The Pauli exclusion principle states that the maximum number of electrons
occupying an orbital is two, with opposite spins.

Hund’s rule: It states that when there are several MO's with equal energy, the electrons occupy the
MO's one at a time before two electrons occupy the same MO

For a stable bond, the bond order must be positive.

Bond order = (No of electrons in bonding MOs)-(No of electrons in anti-bonding MOs) / 2

A linear combination of atomic orbitals or LCAO is a quantum superposition of atomic orbitals and a
technique for calculating molecular orbitals in quantum chemistry. In quantum mechanics, electron
configurations of atoms are described as wave functions. In mathematical sense, these wave functions
are the basis set of functions, the basis functions, which describe the electrons of a given atom. In
chemical reactions, orbital wave functions are modified, i.e. the electron cloud shape is changed,
according to the type of atoms participating in the chemical bond. It was introduced in 1929 by Sir John
Lennard Jones with the description of bonding in the diatomic molecules of the first main row of the
periodic table, but had been used earlier by Linus Pauling for H2.

Bonding and anti-bonding orbitals of “hydrogen” and “helium” as examples

Di-hydrogen (H2): The smallest molecule, hydrogen gas exists as dihydrogen (H-H) with a single
covalent bond between two hydrogen atoms. As each hydrogen atom has a single 1s atomic orbital for
its electron, the bond forms by overlap of these two atomic orbitals. In figure below, the two atomic
orbitals are depicted on the left and on the right. The vertical axis always represents the orbital
energies. Each atomic orbital is singly occupied with an up or down arrow representing an electron.

Hydrogen molecule: Bonding and anti-bonding levels in the hydrogen molecules, the two electrons in
the hydrogen atoms occupy a bonding orbital that is lower than the two separated electrons, making
this an energy-favourable event.

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Helium MO diagram

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Some other diatomic molecules and its MO diagrams

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Extension of band theory to metal, semiconductors and insulators

Every solid has its own characteristic energy band structure. In order for a material to be conductive,
both free electrons and empty states must be available

Metals have free electrons and partially filled valence bands, therefore they are highly conductive.

Semimetals have their highest band filled, this filled band, however, overlaps with the next higher
band, therefore they are conductive but with slightly higher resistivity than normal metals
Examples: arsenic, bismuth, and antimony.

Insulators have filled valence bands and empty conduction bands, separated by a large band gap
Example (typically > 4eV), they have high resistivity.

Semiconductors have similar band structure as insulators but with a much smaller band gap. Some
electrons can jump to the empty conduction band by thermal or optical excitation
Examples=1.1 eV for Si; 0.67 eV for Ge and 1.43 eV for GaAs

Metals

 An energy band is a range of allowed electron energies.

 The energy band in a metal is only partially filled with electrons.
 Metals have overlapping valence and conduction bands
 For an electron to become free to conduct, it must be promoted into an empty available energy
state
 For metals, these empty states are adjacent to the filled states
 Generally, energy supplied by an electric field is enough to stimulate electrons into an empty
state

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 At T = 0, all levels in conduction band below the Fermi energy EF are filled with electrons, while
all levels above EF are empty. Electrons are free to move into “empty”
 Electrons are free to move into “empty” states of conduction band with only a small electric field
E, leading to high electrical conductivity!
 At T > 0, electrons have a probability to be thermally “excited” from below the Fermi energy to
above it.

Temperature Dependence, Metals

There are three contributions to resistivity (ρ)
 ρt due to phonons (thermal)
 ρi due to impurities.
 ρd due to deformation

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Insulator
 The valence band and conduction band are separated by a large (> 4eV) energy gap, which is
a “forbidden” range of energies.
 Electrons must be promoted across the energy gap to conduct, but the energy gap is large.

 T = 0, lower valence band is filled with

electrons and upper conduction band is
empty, leading to zero conductivity.
 Fermi energy EF is at midpoint of large
energy gap (2-10 eV) between conduction
and valence bands.
 At T > 0, electrons are usually NOT
thermally “excited” from valence to
conduction band, leading to zero
conductivity.

Energy bands in Semiconductor

Energy gap (Eg)

 Energy Gap in a Pure Semiconductor.

 The energy gap is < 2 eV.
 Semiconductors have resistivity in between those of metals and insulators.
 Elemental semiconductors (Si, Ge) are perfectly covalent; by symmetry electrons shared
between two atoms are to be found with equal probability in each atom.
 Compound semiconductors (GaAs, CdSe) always have some degree of ionicity. In III-V
compounds, eg. Ga+3As+5, the five-valent As atoms retains slightly more charge than is
necessary to compensate for the positive As+5 charge of the ion core, while the charge of Ga +3

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is not entirely compensated. Sharing of electrons occurs still less fairly between the ions Cd+2
and Se+6 in the II-VI compound CdSe.

 At T = 0, lower valence band is filled with electrons and upper conduction band is empty,
leading to zero conductivity.
 Fermi energy EF is at midpoint of small energy gap (<1 eV) between conduction and valence
bands.
 At T > 0, electrons thermally “excited” from valence to conduction band, leading to measurable
conductivity.

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Intrinsic and Extrinsic p and n type semiconductors

Although currents may be induced in pure, or intrinsic, semiconductor crystal due to the movement of
free charges (the electron-hole pairs), these currents are too small to be of real use. This limitation is
due to the relatively small number of electrons that obtain the required energy to jump the band gap
10 3
(typically on the order of 10 electrons/cm at room temperature for silicon). Now, while this may seem
22 3
to be a very large number, you must keep in mind that silicon has on the order of 5 × 10 atoms/cm ,
so this effect is essentially non-existent. What is important here is that, although the intrinsic
concentration, ni, is a function of band gap, temperature, and physical constants through

Where,
C is a material constant that depends on the effective density of states in the conduction and valence
31 o
bands (C=5.4x10 for silicon); T is temperature in degrees Kelvin ( K); Eg is the band gap (Eg=1.12eV
-5 o
for silicon); k is Boltzmann’s constant (k=8.62x10 eV/ K)

For intrinsic silicon,

10 -3
n=p=ni•1.5x10 cm
at room temperature (300 K). Or, in words… the number of free electrons is equal to the number of free
holes and is also equal to the intrinsic carrier concentration (since the only free carriers in an intrinsic
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material are due to EHP). Note that pn=ni . Finally, although the EHP (Electron Hole Pair) generation is
temperature dependent, free carrier generation through external excitation alone is a recipe for
disaster.

The conductivity of a semiconductor can be modelled in

terms of the band theory of solids. The band model of a
semiconductor suggests that at ordinary temperatures
there is a finite possibility that electrons can reach the
conduction band and contribute to electrical conduction.
The term intrinsic here distinguishes between the
properties of pure "intrinsic" silicon and the dramatically
different properties of doped n-type or p-type
semiconductors.

To create practical, useful semiconductor devices, some

really clever idea generated a method of modifying the intrinsic crystal lattice. This process, called

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doping, involves introducing a specific number of atoms with a different valence number than the host
semiconductor into the crystalline lattice. When the semiconductor crystal is doped such that its intrinsic
nature is modified, it is termed extrinsic. In an extrinsic semiconductor, the equilibrium number of free
electrons and holes are no longer equal since a tool other than EHP generation is used to create free
carriers. Depending on the amount and type of impurity (or impurities) introduced many electrical and
optical properties of the semiconductor material may be modified or controlled to optimize to desired
characteristics.

We’re going to concentrate on silicon here and the creation of the two basic types of extrinsic (or
doped) silicon, n-type and p-type - as illustrated in Figure below, silicon is valence IV (four)

n-type Silicon
When a silicon atom in the crystal lattice is replaced
with a valence V (five) atom (such as phosphorous,
arsenic or antimony) the four valence electrons of
silicon are satisfied and there is an electron “left over.”
The left over electron requires very little thermal
energy to release it from its parent atom and easily
becomes a free carrier. Introducing group five
impurities into the silicon lattice is known as n-type
doping since the concentration of free electrons
(remember the symbol for electrons is n) is greater
than that of the intrinsic material. The elements used
for n-type doping are known as donors since they
“donate” electrons to the silicon host and their
concentration in the host material is designated by ND.
Or
When the donor electrons move from their parent
atoms, they leave behind a positively charged ion.
These ions are fixed in the semiconductor lattice so
they cannot contribute to current

p-type Silicon

The addition of pentavalent impurities such as antimony contributes free electrons, greatly increasing
the conductivity of the intrinsic semiconductor.

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Silicon atom in the host lattice is replaced with a

valence III (three) atom, most commonly boron. For
this case, as illustrated below, there is one too few
electrons in the impurity atom to satisfy the four
valence electrons of silicon. This results in an
unsatisfied covalent bond. Introducing group three
atoms into the silicon lattice is known as p-type
doping since the concentration of free holes
(remember the symbol for holes is p) is greater than
that of the intrinsic material. The elements used for p-
type doping are known as acceptors since they
“accept” any free electrons that are mobile to satisfy
the fourth covalent bond. NA designates the
concentration of acceptors in the host material. When
Or the acceptor atom “picks up its fourth,” it becomes a
negatively charged ion.

The addition of trivalent impurities such as boron, aluminium 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

Carrier Concentrations and Excess Carriers

It is important to note that, even when a semiconductor material is doped with impurities, it remains
electrically neutral. This means that overall (macroscopically), the number of positive charges is equal
to the number of negative charges. Conventional doping levels do not change the chemical or
mechanical properties of a semiconductor. For our purposes, we are going to assume that at room
temperature all impurity atoms are ionized – all donors have contributed a free electron and all
acceptors have contributed a free hole (captured an electron). Remember that, for an intrinsic material,
all free carriers are due to electron-hole pair generation and that the number of free electrons is always
equal to the number of free holes (and is equal to the intrinsic carrier concentration ni). This doesn’t
hold true for extrinsic semiconductors. When one type of impurity has been intentionally introduced into
the host material, it is seen to dominate and we speak of majority carriers and minority carriers.
Specifically,
 for n-type semiconductors: ND>> NA, ND >> ni, electrons (n) are the majority carriers and holes
(p) are the minority carriers.
 for p-type semiconductors: NA >> ND, NA >> ni, holes (p) are the majority carriers and electrons
(n) are the minority carriers.

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