AP621 Advanced Electron

Microscopy: Theory and

Practice
Dr. Zhao Jiong(趙炯)
Office: CD609; Tel: 27665692
Email: jiongzhao@polyu.edu.hk
 Today’s topics

 Lec-04: Crystal defect analysis

Refs: J. Yuan, R. Yu, Electron microscopy analysis, lecture notes, Tsinghua,

2005-2009; & Journal publications: Science, Nat. Mater, Ultramicroscopy, etc.
Bright field imaging in dual beam condition

0 g

I I
’
0 0
Dark field imaging
in dual beam condition

0 g

I I
’
g g
Central dark field imageing

0 g

I I
’
g g
Analysis of Diffraction in Dark field
 Identification of Unknown Superlattice diffraction
spots

 When diffraction pattern

contains unknown spots which
can not be readily explained
by the know structure of the
specimen, it is worthwhile to
form an image using these
spots
 The example shows a double
positioning boundaries in a
(111) gold films containing
two twin related orientations,
the bright lines in the dark
image formed with the
diffraction spot P (indexed
(422)/3) is the incoherent
twin boundaries separating
the two orientations. The
contrast arises from imperfect
structure (Pashley and
Stowell, 1963)
 Point defect : Diffuse scattering
 Point defects causes
diffuse scattering,
ordered point defects
causes regular diffuse
scattering pattern
 From diffraction pattern,
which is 2D projection in
reciprocal space, one can
work out the 3D pattern
in the reciprocal space
associated with point
defects
 Sample:
Steel
 Imperfect crystal
 imperfect crystals
 Incomplete unit cell，atomic defects（surface、
impurity）
 Change of Fhkl
 Strain induced replacement

rn ' = rn + Rn
 rn’=the nth unit cell position
 rn = the nth unit cell ideal position
 Rn＝deviation vector
Kinetic theory of electrons in imperfect crystal

 Contribution of each unit  In perfect crystals

cell in each diffracted
beam iπa iπa
e −iq•r'
e −iq•r
ξg ξg
 Additional phase factor：

e − ig • R e − is • r ' e −is•r '

Due to strain field
 Diffracted beam in exit caused by defects
wave

iπ iπ
φg = ∫e φg = ∫ dz
−ig • R −isz −isz
e dz e
ξg ξg
Column assumption

12
 Amplitude phase diagram
 To calculate the diffracted beam amplitude：
 We need to know dependence of R / ∆g on z
 Integration over z

iπ
φg = ∫ e dz
−ig • R −isz
e
ξg

Amplitude phase diagram

 Dual beam dynamical scattering theory
(Howie-Whelan) in imperfect crystals
 g＝ diffraction vector
 R＝ deviation vector
 Exclude adsorption and multibeam effects
dφ 0 i π iπ
= φ0 + φg exp[isz + g.R ]
dz ξ 0 ξg
dφ g iπ iπ
= φg + φ0 exp[− isz − g.R ]
dz ξ0 ξg
 In dynamical theory, contrast still controlled by phase
angle change, so kinematical theory still viable
sometimes.
 Setting value of s
 Controlled by beam tilt
 Determine if one or
both of the Bloch
waves are equally
excited
 Diffraction contrast of defects
 Planer defects
 Defects with pure translation shift
 Line defects
 Dislocations
 Secondary particles
 Coherent precipitates
 Planner defect
 Boundary between same crystal
grains
 Translation boundary Crystal 1
 Stacking fault v
 Antiphase boundary
θ
 Twin boundary crystal 2
 Twist boundary R(r）＝0
 Normal grain boundary
 Phase boundary：Boundary
between different phases and
 R, θ，and lattice mismatch
 Surfaces
 Translational Planer Defect

 Contrast distinction condition：

g ⋅ R = 2mπ
 Nominal contrast need to be over
10％－15％, so we need
g⋅R
m − 0.02 ≤ ≤ m + 0.02
2π
 Intensity：

iπ
φg = ∫ e − ig • R − isz i π 

t1
− isz
t
e dz = ∫ e dz + ∫ e e dz  =
− iα − isz
 i − ist1 / 2  t1s
+ − iα (t − t1 )s 
e sin e sin 
ξg ξ g  0 t1 
 ξ g s  2 2 

 cos function dependence on

thickness
iπ 1  2  ts α  2α α  ts α  (t − t1 )s 
I g = φg = ∫ e dz =
−ig•R −isz
sin  +  + sin − 2 sin sin  +  cos 
(ξ g s )2
e
ξg  2 2 2 2 2 2 2 
 Layer stacking in fcc materials

 Stacking sequence in FCC

A
C
B
A A A
C
B C
A
 Stacking fault：stacking sequence B
disordering a
A
 Fcc，hcp，diamond－cubic，
layered material
 Control the mechanical properties
 FCC materials：
 Ni，Cu, Au, Ag, Stainless steel，
Ni3Al, Ti3Al

a
Layer stacking in fcc materials and stacking fault

 Translational vector R in
stacking fault A
C
 Shear deformation A
B

parallel to layers B
A
1
[ ]  1 1 
R = ± 1 1 2 = ± − [111] + [110]
R=+
1
[111]
6  3 2 
3
 Insertion or loss of layer A
C
vertical to stacking direction B
B
 loss(+) R = ± [111]
1 A

 insertion(-) 3
R = − [111]
1
3
Layer stacking in fcc materials and stacking fault

 Phase factor of
stacking fault (g[kkl])
2π
α =± (k + k + l ) = 2nπ
3 3
 Cannot distinguish
inservation or loss
types
[ ]
g = 220
 No contrast at:
g⋅R = 0
 Need the following
diffraction beam to
study SF
[ ]
g = kk l

SF in stainless steel
 Antiphase boundary
 Translational vector：
1 A
R = [111]
2 C

 Phase factor B
a
A
α = g ⋅ R = nπ
Ordered alloy CuAu in CsCl type lattice
Pi-fringes
 Inteface in Ni3Al
showing a pi-
phase shift
 APB in an (001) film of CuAu
 Pashley and Presland, 1959
 Allowed superlattice
reflection is always of the
type (odd,odd,even) or
(even, even, odd), so the
alpha phase factors
associated with all possible
antiphase boundary
displacement vectors odd
multiple of pi, hence all
faults are visible
 Absorption effects
 Absorption selectively
attenuates one of the
Bloch beam
 A fault may change
the channeled wave
into an dechannelled
wave or visa visa
Analysis of the contrast due to absorption
Beware of artifacts
 Diffraction contrast of dislocations
 Types of dislocations
 g.b visaibility rule
 Absorption effect (thickness effect)
 Surface relaxation
 Dislocations

 Why crystals deform

so easily
 Taylor, Orowan and
Polyani (1934): Plastic
deformation is due to
motion of dislocations
(c.f. diffusion by
vacancy mechanism)
 Screw and Edge dislocations

u=direction of the line defect

u
 Line defect

Dislocation
b
 Continuous strain
field in crystals
 Edge dislocation
produces both
tensile and
compressive and
shear stress
 Screw dislocation
only produces shear
stress
 Edge dislocations
 Invisibility criteria
g.b = 0
and
g.(b × u ) = 0
Weak Beam Imaging

 Diffraction condition
Edge Dislocation network due to interface misfit,
showing g.b=0 effect
Screw dislocation
b
Visibility test

g.b = 0 g
Relaxation
 Strain field cause lattice
planes to buckle, hence
g.b=0 is not strictly valid

Edge-on screw dislocations are

visible because of surface relaxation
Physical meaning for additional phase factor

 Imperfection in crystals
 Rotation or distance change of
reciprocal lattices locally
 If g’ is the local reciprocal vector
of defects

g '⋅rn ' = g ⋅ rn
g ⋅ R n + ∆g ⋅ rn = 0

α = g ⋅ R n = −∆g ⋅ rn
Imaging extended strain field
 The extended strain
around a dislocation
can causes a local
lattice distortion as
well as a local lattice
rotation

dR ∂Rg
s => s + g. +θB g
dz ∂xg
 Calculation of dislocation contrast
 Column approximation
 Displacement R from elastic
theory for a general
dislocation of burger vector
b, line direction u, at
disturbance (r,φ) from the
column in a material with
Poisson coefficient v:

1  sin 2φ  1 − 2ν cos 2φ 
R= bφ + b + (b × u) ln r + 
2π  4(1 −ν ) 1(1 −ν ) 4(1 −ν ) 
 Dynamical effect in dislocation contrast

 Oscillatory
effect near
surface
 Absorption effect
 Top-bottom effect
Information about dislocations
 The direction and magnitude of Burgers vector (i.e.
whether it’s presence is sufficient in relieving the strain)
 Is it interacting with other defects ? (work hardening)
 Is the dislocation jogged, kinked or straight
 What is the density of dislocations in that materials (high
density dislocation normally degrades the luminescence
in semiconductor, but GaN is an exception, not sure
why?)
 Has the dislocation adopted some special configurations,
i.e. helix
Dislocations in fcc crystals
 If g.b=0, the dislocation is
still visible when
g.(bxu)>0.64.
 For fcc matyerials, this rule
can be useful when the foil is
not parallel to a {111} plane
 g.b effect
 Exact for screw
dislocation
 Approximate
because also
requires
g(b×u)=0
Dislocation loop
 Can form when point defects
coalesces
 Study of their sizes, evolution
and critical conditions leads to
understanding of irradiation
effect in materials
Structure of
dislocation loops
with respect to their
diffraction planes
 Intrinsic and extrinsic
 Dislocation dipole type determination

Dipoles are elongated

dislocation loops,
important in heavily
deformed metals and in
some semiconductors
Stacking fault energy calculation
 Diffraction contrast of precipitates

 Strain field analysis of coherent

precipitates
 Line of no contrast
 Precipitates

 Coherent
and
incoherent
 Embedded Strained quantum dots

 Strained Quantum dots embedded inside

a semi conducting quantum well

(a) (b) 20 nm

FIG. The comparison of centered dark field from TEM (a) and ADF from STEM (b)
 Plane view sample

 Coherent dot g=022

showing butterfly
contrast
 Incoherent dot
showing large
lattice
displacement due
to complete
lattice relaxation
100nm 100nm

In100P-022BF&WB-50K.ppt Bright Field Weak Beam

Dark Field g/3g
 Incoherent particles

g=022 50 nm
(a) (b)
FIG. Bright field(a) and weak beam dark field (g/3g) from plan view
 Lattice Imaging
 Formed when both the non-
scattered beam and the diffracted
beam are used for image
formation
 In two beam diffraction condition
 Simple fringe like contrast
 Imaging of density wave of a
given spatial frequency
 In few beam zone diffraction
condition
 Intersection of non-parallel
fringe produces dots
 Imaging of density waves of
different spatial frequency and
orientations
 Many beam zone diffraction
conditions
 Fine structure determination of
dot structures
 Equivalent to high resoution
electron microscopy
 Lattice image and Lattice Plane
 Bending of the lattice
imaging at the edge

 The lattice image is the

interference of
transmitted and Bragg
diffracted beam.

 The relative position of

the fringe is a function of
the phase difference
between the two beam.
This is thickness
dependent, so the
apparent bending of the
fringe at the specimen
edge is not necessary due
to bending of the real
crystal.
Moiré Imaging: overlapping lattice images
Exfoliation between layers: hyperdislocations

Structure of h-MoTe2
The hyperdislocation in exfoliated h-MoTe2

20 nm 30 nm

30 nm 20 nm
Strain distribution of hyperdislocation
Hyperdislocation in few-L MoTe2

40 nm

Edge dislocation in diamond

exx in MgO dislocations

Atomic origins of hyperdislocations

60
Dislocation theory applied to hyperdislocation


few-L MoTe2 50 nm
Cs corrected HREM: toward
defect atomic structures

Graphene, mono-vacancy

62
HRTEM,DFT and multislice simulation

63
HRTEM of defects (applications)

64
STEM applications on GaN screw
dislocations

65
STEM plus EELS of defects (applications)

WSe2 3-fold defect

66
67
68
Carbon atomic defects in graphene

69
Ferroelectric
domain
boundary

70
Pr segregation on ZnO GB

71
Amorphous phases: diffraction
short range orders produces diffused rings in DP

72
 Summary
 Strain field bends the atoms away from the diffraction
condition for perfect crystals

 Strain field can be imaged by tilting the crystal slightly

away from Bragg reflection condition and then watch the
defect bends the lattice plane back into diffraction
condition. The bigger the bend, more close is the strain
field to the defect, hence the narrower width of the
defect in diffraction contrast imaging (weak beam
method)

 Depends on the symmetry of the defects, certain lattice

plane intersecting the defect will be unaffected. There is
no diffraction contrast involving Bragg diffraction from
these plane, hence the selection rule for diffraction
contrast can be used to distinguish different defects