Crystal Defects, Non-Stiochiometry and Solid Solutions

Imperfect Crystals
Perfect crystal can be obtained, hypothetically, only at absolute zero; at all real temperatures, crystals are imperfect

G = H - TS
Energy changes on introducing defects into a perfect crystal

Types of Defect
stoichiometric defect e.g. Schhottky defect, Frenkel defect non-stoichiometric defect e.g. extrinsic defects point defects Defect line defects plane defects

Defect

Point Defects--Schottky Defect

The Schottky defect is a stoichiometric defect, which consists of a pair of vacant sites, an anion vacancy and a cation vacancy

There must be equal numbers of anion and cation vacancies local electroneutrality

The vacancies tend to associate because they carry effective charge. The dissociation energy of NaCl vacancy pair is ~120 KJ mol-1 Schottky defects are responsible for the optical and electronic properties of NaCl

Schottky Defect
NaNa + ClCl + VNa,S + VCl,S
K=

VNa + VCl + NaNa,S + ClCl,S

[VNa][VCl][NaNa,S][ClCl,S] [NaNa][ClCl][VNa,S][VCl,S]

Since [NaNa,S] = [VNa,S], [ClCl,S] = [VCl,S],

K=

[VNa][VCl] [NaNa][ClCl] [Nv]

2

N and Nv are the total number of sites of each kind and the number of vacancies of each kind For small conc. of defect: N N-Nv

K=

[N-Nv]

Nv N(K)1/2
K = exp(-G/RT) = exp(-H/RT)exp(S/R) = constant exp(-H/RT)

Nv = N constant exp(-H/2RT)

Point Defects--Frenkel Defect

Frenkel defect is a stoichiometric defect involves an atom displaced off its lattice site into an interstitial site that is normally empty.

Some covalent interaction between interstitial Ag+ and Cl-, which stabilize the defect The vacancy and interstitial are oppositely charged and may attract each other to form a pair (electrically neutral)

Frenkel Defect
AgAg + Vi
[Agi][VAg] [AgAg][Vi ]

Agi + VAg

K = exp(-G/RT) = constant exp(-H/RT)

K=

Ni = N()1/2exp(-H/2RT) = constant Nexp(-H/2RT)

Let N be the number of lattice sites in a perfect crystal. Let Ni be the number of occupied interstitial sites

Ni = [VAg] = [Agi] N Ni = [AgAg] [Vi ] = N

K=
2

Ni

(N Ni )(N)

N2

Ni

Ni N(K)1/2

Color Centers
F-center: an electron trapped on an anion vacancy. It can be prepared by heating an alkali halide in vapor of an alkali metal or by irradiation e.g. X-ray Na1+Cl: <<1 electron in a box The color depends on the host crystal but not the source of the electron

H-center

V-center

Extrinsic Defects
Intrinsic defects: Schottky and Frenkel defect (thermally created) Extrinsic defects: doping pure crystals with aliovalent impurities For example: NaCl doped with CaCl2 Na1-2xCaxVNaxCl 2Na+ Ca2+ + VNax K ~ [VNa][VCl] For crystals with dilute defect concentrations, K is a constant that is proportional to the product of [VNa] and [VCl] The addition of Ca2+ will increase the cation vacancy concentration and decrease anion vacancy concentration
(preserve electrically neutral)

Defect Clusters
The interstitial atoms may perturb the host structure in the immediate vicinity of the interstitial atom

The defect involves two atoms, both of which are on distorted interstitial sites split interstitial For ionic crystals, the smallest clusters is either an anion vacancy/ cation vacancy pair or an aliovalent impurity/cation vacancy pair

Interchanged Atoms
In certain crystalline materials, pairs of atoms or ions may swap places order-disordered phenomena For example: -brass vs. -brass (CuZn) Ordered structure: primitive cubic structure (long range order and superstructure) Disordered structure: body centre cubic structure

Spinel structures: good examples of interchanged cations in non-metallic oxide structures

Solid Solutions
As the dopant concentration rises, above ~0.1 to 1 percent, it is common practice to refer to the materials as solid solutions rather than as doped materials

1. Substitutional solid solution The atom or ion that is being introduced directly replaces an atom or ion of the same charge in the parent structure

2. Interstitial solid solution The introduced species occupies a site that is normally empty and no ions or atoms are left out

Substitutional Solid Solutions

Good example: (Al2-xCrx)O3 (ruby gemstone) Al3+ and Cr3+ ions are distributed randomly over the octahedral sites that are occupied by Al3+ in Al2O3 Material properties may be changed on doping or formation of solid solutions Al2O3: white, insulating solid Cr:Al2O3: ruby red color, material for laser Requirements The ions that replace each other must have the same charge and fairly similar in size ( within a difference of 15-20% in the radii) Two materials should be isostructural
Thermodynamic explanation and examples in p.227

http://www.surfacenet.de/html/pict ure_crystals.html

Interstitial Solid Solutions

Many metals form interstitial solid solutions in which small atoms, especially H, C, B, N, enter empty interstitial sites within the host metal structure. For example: Pd is well known for its ability to occlude enormous volumes of H2 gas PdHx H atom occupy interstitial sites with fcc Pd metal For example: C dissolves in fcc -Fe but not in bcc -Fe

The short Fe-C bond distance in bcc -Fe hinder the formation of interstitial solid solution

Aliovalent Substitution
Ionic compensation
In aliovalent solid solution, ions are substituted by other ions of different charge Creation of vacancies or interstitials

1. Cation vacancies e.g. Na1-2xCaxVxCl, Mg1-3xAl2+2xO4 2. Interstitial anions e.g. Ca1-xYxF2+x

(Not common because most structures do not have intersitial sites large enough to accommodate extra anions; fluorite structure)

4. Interstitial cations e.g. Lix(Si1-xAlx)O2

(common solid solution provided that the host structures have suitable-sized intersitial sites to accommodate extra cations; Li+ ion)

5. Double substitution e.g. (Mg2-xFex)(Si1-yGey)O4

3. Anion vacancies e.g. Zr1-xCaxO2-x: 0.1 < x < 0.2

(Ag1-xNax)(Br1-yCly) (Ca1-xNax)(Al2-xSi2+x)O8

Aliovalent Substitution
Electronic compensation 1. Cation vacancies e.g. Li1-xCo1-x3+Cox4+O2
(Deintercatalation of Li+ and removal of e-)

4. Interstitial cations e.g. LixW1-x6+Wx5+O3

(Intercatalation of Li+)

2. Interstitial anions e.g. YBa2Cu3O

Mixed valency cations can be created by heating the materials in air or O2 at elevate temperature. e.g. = 6, Cu has mixed +I and +II valence; = 7, mixed II and III valence

5. Double substitution e.g. Ba-doped La2CuO4 La3+ + Cu2+ = Ba2+ + Cu3+ or e.g. K-doped BaBiO3 2Ba2+ + Bi3+ = 2K+ + Bi5+

3. Anion vacancies e.g. YBa2Cu3O

A number of oxides are susceptible to oxygen loss with creation of anion vacancies (reduction at high temperature)

Experimental Methods for Studying Solid Solution

X-ray powder diffraction Density measurement

ZrO2 + CaO
Fingerprint method to determine crystalline phase Determine the d-spacing and unit cell volume

(Zr1-xCa2x)O2 or (Zr1-xCax)O2-X Density changes as x varies

Crystallographic Shear Structures

For example: WO3-x

Point defect

Plane defect

Stacking Faults

Stacking faults (plane defect) are common in materials with layered structures Normal stacking sequence is interrupted by the presence of wrong layers e.g. ABABABCABABA.

Boundaries
Subgrain boundaries Antiphase boundary

Dislocations
Dislocations are stoichiometric line defects, which is an extremely important class of crystal defect

Some observations are related to the existence of dislocations: 1. Metal are generally much softer than expected 2. Malleable and ductile properties of metals 3. Process of work-hardening of metals 4. Spirals on the surface of well-formed crystals

Edge Dislocations

line of the dislocation

Movement of dislocations: slip Dislocations are characterized by Burgers vector, b.

Screw Dislocations

S-S represents the line of the screw dislocation

Burgers vector is parallel to the line of the dislocation (SS) and perpendicular to the direction of motion of this line

Dislocation Loops

The generation of dislocations involve the formation of dislocation loops Two dislocations change direction inside the crystal and meet up to form a quarter dislocation loop. (pure edge at one end and pure screw at the other)

Observation of Dislocations
Techniques: optical and electron microscopy Example of pits formed by corrosion on the surface of LiF
The number and distribution of dislocations in a crystal can be assessed The movement of dislocations can be studied

Dislocations in single crystal GaN thin film

Movement of Dislocations
There is usually a preferred plane or set of planes on which dislocations can occur and also preferred directions for dislocation motion

E ~ b2

The direction of motion of dislocations is usually parallel to a direction of close packing in the structure

Mechanical Properties of Metals

fcc metals are generally more malleable and ductile than either hcp or bcc metals fcc: six cp direction hcp: three cp direction bcc: four cp direction

Tensile strength curve of Mg

Stress: SA = F/Asp = F(cos/Arod) Shear stress: SB = SAcos = (F/Arod)coscos

Relation Between Dislocations & Vacancies

Climb Cluster of vacancies

Relation Between Dislocations & Stacking Faults

In terms of the energy barriers to be surmounted, two small passes are easier than one big hump formation of partial dislocations E1 ~ b2 E2 ~ 2/3b2

E2 < E1

Dislocations & Grain Boundaries

The dislocation in a similar orientation and position will introduce an angular misorientation between the two halves of the crystal low angle grain boundaries