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Example Use of Miller Indices

Wafers The at loca=on shows: 1- crystal direc=on 2-p-type or n-type
[1 10]

[011]

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Example Use of Miller Indices

hIp://edocs.soco.agilent.com/display/iccapmhb/Wafer+Prober
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Example Use of Miller Indices

Gallium nitride semiconductor structures including lateral gallium nitride layers

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Lecture 2
Types of Bonding Ionic bonding Covalent bonding Metallic bonding

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Crystal Bonding

Crystal Bonding
Model Classical electrosta=c aIrac=ve and repulsive forces can mostly explain bonding in these crystals

Ionic bonding Van der Waals Metallic bonding Covalent bonding

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Quantum mechanical treatment is needed to explain the bonding in these crystals

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Crystal Bonding

A]er C. KiIel

(a) Van der Waals

(b) ionic

(c) metallic

(d) covalent

a) Neutral atoms with closed electron shells are bound together weakly by Van der Walls forces associated with the uctua=ons in charge distribu=ons b) Electrons are transferred from one atom to another. The resul=ng ions are held together by aIrac=ve electrosta=c forces between posi=ve and nega=ve ions. c) The valence electrons are taken away from each atom to form a communal sea of electrons in which the posi=ve ions are dispersed d) The neutral atoms are bound together by the overlapping parts of their electron distribu=ons
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Interatomic forces
An NaCl crystal is more stable than an isolated collec=on of free Na and Cl atoms Similarly, a Ge crystal is more stable than a collec=on of free Ge atoms This implies that the atoms aIract each other when they get close to each other We may conclude that some aIrac=ve interatomic force exists which holds the atoms together. This force is responsible for crystal forma=on

The energy of the crystal is lower than that of the atoms by an amount equal to the energy required to pull the crystal apart into free atoms.

Binding Energy or Cohesive Energy of the crystal

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Cohesive Energy
The poten=al energy (V) represen=ng the interac=on varies greatly with distance between two atoms Above an equilibrium value (R>R0), V increases gradually reaching 0 at R = (a9rac:on) R<R0, V increases very fast reaching at small distance (repulsive) V repulsive
R (interatomic distance)

R0 V0 equilibrium a0rac2on

The two-atom system has the lowest poten=al energy at R0 (most stable point) Then R0 is the equilibrium posi:on and the energy at R0 is the cohesive energy (binding energy). R0 is called the interatomic distance -V0 is the binding energy Typical values of R0 ( in solids) are 10-30
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Energy & Force

R < R0

Interatomic force

F=0
Ro

F =

V R

R R > R0 distance

Force is a9rac:ve for R > R0 Force is repulsive for R < R0

Figure from Surface Science Reports 66, Issue 1, 2011, 127

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Ionic bond
In an ionic bond (e.g. NaCl), each Na atom loses one valence electron to a neighboring Cl atom, resul=ng in an ionic crystal containing both posi=ve and nega=ve ions
Na Cl Na+ Cl-

An electrosta:c coulomb a9rac:ve force exists between the two oppositely charged ions 2

F(R) pair =
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Ionic bonds are created mostly between dierent electronega=vity elements

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q 4 0 R 2

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Ionic bonding in solids

AIrac=ve energy of isolated ion pair:
Na Cl

3s

3s 3p

V (R) pair =

q2 4 0 R

Closed K and L shells

becomes larger ClFA

Closed K and L shells (a)

ClNa+

becomes smaller Na+

FA

3s

3p

R r

ro Ro (c)

(b)

The formation of an ionic bond between Na and Cl atoms in NaCl. The attraction is due to coulombic forces.
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Repulsive Forces in ionic bonds

As two oppositely charged ions are brought together, the atoms repel each other, why? the orbits of the electrons begin to overlap Results in: 1. Repulsive classical electrosta=c forces 2. Pauli exclusion principle :no two electrons can have all their quantum numbers equal These two factors cause a fast rise in energy, prevenAng the two atoms from geBng closer to each other.

Electron charge distribu=ons overlap as atoms approach.

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Repulsive Forces in ionic bonds

as orbital overlap occurs, some electrons try to occupy orbits already occupied by other electrons, but they cannot violate the Pauli exclusion principle AIrac=ve and repulsive forces balance out at R0
V
R (interatomic distance)

R0 V0

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Eect of Pauli Exclusion Principle

Total energy -79 eV

Total energy -59 eV

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Example: ionic bond of NaCl

The ionic bond is relaAvely strong with cohesive energy around 5-10 eV Mel=ng temperatures of ionic crystal are high NaCl Na 801C 97.8C (metallic)

Ro

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Covalent Bonding
Sharing the outer electrons the bond is composed of two electron Due to coulomb aIrac=on between e- and nucleus. For example: C, Si and Ge.
shared Si Si

Si

Si

electron
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Which materials with covalent bonding?

Chemical bonds within small molecules are almost always covalent (NH3, H2O, H2, ect). But we are interested in crystals. It is safe to sat that most atoms in with coordinaAon number (CN) of 4 or less, are bonded covalently For example, elements of group IV, group III-V compounds, and group II-VI compounds have the diamond, sphalerite, and wurtzite structures, respec=vely. All atoms in these structures are tetrahedrally coordinated. All silicate compounds (Si,O) have high degree of covalent bonding because Si is always 4-fold coordinated (CN=4) and oxygen has lower coordina=on number.
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Periodic table

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Example: Silicon
Si14: 1s2 2s2 2p6 3s2 3p2
Core electrons (bound =ghtly with small radius) Valence electrons (bound loosely with big radius)

4 electrons in the outer electrons (Valence electrons) Tetrahedral structure 4 bonds per atom each atom is bonded to 4 nearest neighbours)

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Silicon

Broken bond hole electron

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Bonding and an=bonding

Symmetric bonding aIrac=on lled states An= symmetric repulsion empty states

Hybrid states: Molecular states

A specic molecule can be formed bonding two or more atoms together. The individual atomic orbitals are mixed together to form molecular hybrid state. These hybrid states are atom-like localized with geometry of molecule. create molecular states.

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Both sp3 and sp2 bonding are common in semiconductors. sp3 bonding is common in diamond and zincblende structure. sp2 bonding is common in hexagonal wurtzite structure.

Molecular states in semiconductors

Molecular states: example

Example: Water molecular The bond angle between the two hydrogen atoms is 108 why? because: Three 2p + one 2s = four 2sp3 hybrid orbitals of Oxygen. 2sp3 orbital poin=ng to the ver=ces of a tetrahedron separated by 108. Only two 2sp3states are par=ally lled which are lled by two electrons from two Hydrogen atoms.

hIp://www.wiredchemist.com

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SP3 hybridiza=on
(a) (b) (c) (d)
CONDUCTION BAND

hyb

A
3p Energy gap, Eg 3s
Si ATOM

VALENCE BAND

hyb

Si CRYSTAL

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SP2 hybridiza=on

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Mixed bonding
In some crystals, the bonds are not pure but mix of ionic and covalent bonding.

These types of mixed bonds are exists in semiconductors (such as divalent, trivalent semiconductors) due to the dierent size of atoms (dierent electronega=vity) .

Example GaAs: has 0.46 of electron transfer (ionic) although the bonds are covalent

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Metallic bonds
How can assembly of atoms, say Na, brought together to form a crystal aIract each other to form a solid ? Should we not expect the electrons to repel each other ? Should we not expect the ion cores to repel each other ? Can we expect an ionic bond between two Na atoms? Can we expect a covalent bond between Na toms?

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Metallic Bonding in Solids

As we shall see the correct explana=on for the metallic bonding in Na (as example) is that each Na atom, which has 1s electron loosely bound to the Na atom, detaches that electron making it essen=ally free to move throughout the crystal This is dras=cally dierent from ionic or covalent bonds where electrons are localized. The energy of the crystal is lesser than free Na atoms, why?

Electron gas

(nucleus and core electrons

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Screening eect of electrons

The free electron gas in the metal crystal actually screens the ion cores from each other (screening coulomb interac=on) , resul=ng in eec=vely neutralized, non-interac=ng ions, much as is the case of free metal atoms.

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Metallic bonds
From quantum mechanics we know that when a par=cle is restricted to move in a small volume, the Kine=c energy of its electron increases. The energy is propor=onal to V-2/3, where V is the volume of connement In an isolated atom, the electrons are conned to a very small volume, giving them very high kine=c energy In a metal crystal, the electrons are moving in a much larger volume, resul=ng in substan=al reduc=on in their kine=c energy. (lesser than the free ions) This signicant reduc=on in the energy of the system favors the metallic bond (crystal forma=on)

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Bonding in solids

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Bonding in Solids

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