Defects Engineering

Outline of Presentation:
Defects with classifications
Case study
Graphene & Perovskite ABDUL SAMI
PhD Student

Department of Chemical Engineering

Crystal: IDEAL vs. Reality

Ideal Crystal: An ideal crystal can be described in terms a three-

dimensionally periodic arrangement
arrangement of points called lattice and an atom or
group of atoms associated with each lattice point called motif:

Extrinsic Defects Intrinsic Defects

Crystal = Lattice + Motif (basis)

Diffused atoms Vacancy

Real Crystal: Deviations from this ideality.

These deviations are known as crystal defects.
Therefore, defects engineering is major field of novel research.
CLASSIFICATION
CLASSIFICATION OF DEFECTS BASED ON DIMENSIONALITY

0D 1D 2D 3D
(Poi n t de
deff ects
cts)) (L i ne def
def ects
cts)) (Sur
(Sur f ac
ace
e / I nte
nterr f ac
ace
e) (Volu
(Vol u me def
def ects
cts))

Vacancy Dislocation Surface Twins

Interphase Precipitate
Impurity Disclination
boundary
Faulted
Frenkel Dispiration Grain
defect boundary region

Twin Voids /
Schottky
boundary Cracks
defect

Stacking
faults Thermal
vibration
 Point Defects: Vacancy
Guess: There may be some vacant sites in a crystal

Surprising Fact
There must be a certain fraction of vacant sites in a crystal in equilibrium.

Gibbs Free Energy G

G=H–TS

1. Enthalpy H=E+PV
2. Entropy S=k ln W
T Absolute temperature
E internal energy
P pressure
V volume
k Boltzmann constant
W number of microstates

Equilibrium means Minimum Gibbs free

f ree energy G at constant T and P

A crystal with vacancies has a lower

low er free energy G than a perfect crystal

What is the equilibrium concentration of vacancies?

 Vacancy increases H of the crystal
crys tal due to energy required to
break bonds
bonds

Enthalpy H =E +PV

H=n f
Vacancy increases S of the crystal due to configurational
entropy

Entropy S=k ln W
 Vacancy increases S of the crystal due to configurational
entropy

Number of atoms: N
Number of vacancies: n

Total number of sites:

sites : N+n

The number of microstates:

N n (N  n) !
W Cn 
n N
! !
Increase in entropy S due to vacancies:

( N  n)!
DS  k ln W  k ln
n! N!
 k[ln( N  n)! ln n! ln N!]
Change in G of a crystal due to vacancy

DG DH
DH  n DH f
G of a
perfect
crystal DG = DH  TDS
neq
n

TDS
DS  k[( N  n) ln( N  n)  n ln n  N ln N ]
Equilibrium concentration of vacancy
DS  k[( N  n) ln( N  n)  n ln n  N ln N ]
DH  n DH f

DG  nDH f  Tk [( N  n) ln( N  n)  n ln n  N ln N ]

DG
0
n nn eq

neq  DH f 
 exp  
N  kT 
With neq<<N
9
 Contribution of vacancy to thermal expansion

Increase in vacancy concentration increases the volume of a crystal

A vacancy adds a volume equal to the

volume associated with an atom to the
volume of the crystal.

Thus vacancy makes a small contribution

to the thermal expansion of a crystal

Thermall expansion =
Therma
lattice parameter expansion + Increase in
volume due to vacancy
 Contribution of vacancy to thermal expansion

Increase in vacancy concentration increases the volume of a crystal

V=volume of crystal
V N
Nv
v v= volume associated with one atom
N=no. of sites (atoms+vacancy)

DV  N Dv  V DN

DV  Dv  DN
V v N

Total Lattice vacancy

expansion parameter
increase
Point Defects

vacancy Interstitial
impurity

Substitutional
impurity
Defects in ionic solids

Frenkel
defect
Cation vacancy
cation interstitial
+

Schottky
defect
Cation vacancy
+
anion vacancy 13
Line Defects:
Also called
EDGE DISLOCATION
Defect
An extra half plane…

…or a missing half plane

16
An extra half plane…

Edge
Dislocation

…or a missing half plane

17
Relationship between the directions of b and t?
Edge dislocation

b t
1 2 3 4 5 6 7 8 9

Burgers vector Line vector

Slip plane
b
slip t
no slip

1 2 3 4 5 6 7 8 9
In general, there can be any angle between the Burgers
vector b (magnitude and the direction of slip) and the line
vector t (unit vector tangent to the dislocation line)

b  t  Edge dislocation

b  t  Screw dislocation

b t , b  t  Mixed dislocation
Screw Dislocation

b  t

Slip plane
t
unslipped
slipped

3
 2

b is a lattice translation

Surface defect

If b is not a complete lattice translation then a surface

defect will be created along with the line defect.
Elastic strain field associated with an edge dislocation

N+1 planes

Compression Elastic energy per unit length of a dislocation line

Above the slip plane

 1
E  b 2

2
 Shear modulus of the crystal
b Length of the Burgers vector
Unit: J m1
Tension
Below the slip plane

N planes
 A dislocation line cannot end
abruptly inside a crystal

Slip plane Slip plane

slip no slip

n
Dislocation:
o
i
t
slip/no slip
a
c
o
l
s
boundary slip no slip
i
d
b
 A dislocation line cannot end
abruptly inside a crystal
C Q
Q

D
B
P P
A A

Dislocation Line AB Dislocation Line APQ

It can end on a free surface

 Dislocation can end on a grain boundary

Grain
Boundary

Grain 1 Grain 2

It can end on Free surfaces or Grain boundaries

A nice diagram showing a variety of crystal
defects

a) Interstitial
Vacancy, impurity of
e) Precipitate atom, b) Edge
impurity dislocation,
atoms, c) Self
f) Vacancy typeinterstitial
dislocationatom,
ato m, d)
loop, g)
Interstitial type dislocation loop, h) Substitutional impurity
imp urity atom
Graphene gets designer defects
An extended one-dimensional defect that has the potential to act as a conducting wire has been embedded in
another perfect graphene sheet.
One-dimensional defects in graphene have
a strong influence on its physical
properties, such
as electrical charge transport and
mechanical strength.
Detect can tune the properties of
Graphene. Atomic layer deposition allows
us to deposit Pt predominantly on
graphene’s grain boundaries, folds and
cracks due to the enhanced chemical
reactivity
directly of these line by
confirmed defects, which is
transmission
electron microscopy imaging.
Application: Sensing
 Graphene require the ability to tune its electronic structure at the
nanoscale.

The approach is ‘self-doping, in which extended defects are

introduced into the graphene lattice.

The controlled engineering of these defects represents a viable

approach to creation and nanoscale control of one-dimensional
charge distributions with widths of several atoms.
at oms.

Here, the realization of a one-dimensional topological defect in

graphene, containing octagonal and pentagonal sp2-hybridized
carbon rings embedded in a perfect graphene sheet.

By doping the surrounding graphene lattice, the defect acts as a

quasi-one-dimensional metallic wire. Such wires may form
building blocks for
for atomic-scale, all-c
all-carbon
arbon electronics.

Defect structure and superimposed

defect model
 The DFT relaxed geometry of the defect
structure,
including bond lengths (in Å) and bond angles

Defect structure and superimposed

defect model
New Generation of Solar Cells: 2012~2014

Perovskite Materials. PUBLISHED ONLINE: 31 AUGUST 2014 | DOI: 10.1038/NNANO.2014.181

 Defects Engineering

ABDUL SAMI
PhD Student

Department of Chemical Engineering