Limits of OM, SEM, SPM and XRD

BT
NN
BT
NN
EDS
G.B.
G.B.

BT-BaTiO
3
NN-NaNbO
3

G.B.-Grain boundary
M.G.J.-multiple grain
junction
Lateral resolution: ~m
Details of microstructure:
e.g., domain structure,
chemical inhomogeneity
phase distribution, grain
boundaries, interfaces,
precipitates, dislocations,
etc.
NN/BT
M.G.J.
0.2m
core
shell
Chemical analysis at a
nanometer scale
Why TEM?
The uniqueness of TEM is the ability to
obtain full morphological (grain size, grain
boundary and interface, secondary phase
and distribution, defects and their nature,
etc.), crystallographic, atomic structural
and microanalytical such as chemical
composition (at nm scale), bonding
(distance and angle), electronic
structure, coordination number data from
the sample.
TEM is the most efficient and versatile
technique for the characterization of
materials.
An Introduction to Transmission Electron
Microscopy (TEM)/Scanning Transmission
Electron Microscopy (STEM)
What is a TEM?
How it works - gun, lenses, specimen stage
Resolution

What can a TEM do?
Imaging and diffraction
Imaging-diffraction and phase contrast
Diffraction-Selected area electron diffraction (SAED)
and Convergent beam electron diffraction (CBED)
Chemical analysis
EDS, Electron Energy Loss Spectroscopy (EELS)
Energy Filtered Imaging

Basic features of A Modern TEM
Electron Gun
EDS Detector
Condenser
Lens
Specimen Holder Objective Lens
Magnifying
Lenses
CM200 (200kV)
SAD Aperture
TV Monitor
Viewing Chamber
Camera
Chamber
Cost: > $4,000,000
Column
Binocular
A simple analogue

A better comparison
Vacuum
The electron microscope is built like a series of
vessels connected by pipes and valves separate
all the vessels from each other.

The vacuum around the specimen is around 10
-7

Torr.
The vacuum in the gun depends on the type of
gun, either around 10
-7
Torr (the tungsten or
LaB
6
gun) or 10
-9
Torr (for the Field Emission
Gun).
The pressure in the projection chamber is usually
only 10
-5
Torr (and often worse). This pressure is
not very good because the projection chamber
holds the negatives used to record images. Even
though we dry the negatives before putting them
in the microscope, they still will give off so many
gases that the vacuum in the projection chamber
never gets very good.


Electron Beam Source
The Lenses in TEM
Condenser lenses(two)-control how
strongly beam is focused (condensed)
onto specimen. At low Mag. spread
beam to illuminate a large area, at high
Mag. strongly condense beam.
Objective lens-focus image (image
formation) and contribute most to
the magnification and resolution of
the image.
Four lenses form magnification
system-determine the magnification
of the microscope. Whenever the
magnification is changed, the currents
through these lenses change.
B
Image Formation in TEM
binocular
negatives
screen
Ray Diagram for a TEM
Control
brightness,
convergence
Control contrast
Why Electrons?
Resolution!
In the expression for the resolution
(Rayleighs Criterion)
r = 0.61/nsino
-wavelength, =[1.5/(V+10
-6
V
2
)]
1/2
nm

V-accelerating voltage, n-refractive index
o-aperture of objective lens, very small in TEM
sino o and so r=0.61/o o~0.1 radians
Green Light 200kV Electrons
~400nm ~0.0025nm
n~1.7 oil immersion n~1 (vacuum)
r~150nm (0.15m) r~0.02nm (0.2)
1/10
th
size of an atom!
UNREALISTIC! WHY?
Resolution Limited by
Lens Aberrations
point is imaged
as a disk.
Spherical aberration is
caused by the lens field
acting inhomogeneously on
the off-axis rays.
point is imaged
Chromatic aberration is
caused by the variation of
the electron energy and
thus electrons are not
monochromatic.
r
min
~0.91(C
s

3
)
1/4
Practical resolution of microscope.
C
s
coefficient of spherical
aberration of lens (~mm)
as a disk.
Beam and Specimen Interaction
(EDS)
(EELS)
SAED & CBED
diffraction
BF
DF
HREM
Imaging
Scanning Transmission Electron Microscopy


In STEM, the
electron beam is
rastered (scan
coil) across the
surface of a
sample in a similar
manner to SEM,
however, the
sample is a thin
TEM section and
the diffraction
contrast image is
collected on a
solid-state (ADF)
detector.



JEOL 2000FX
Analytical Electron Microscope

STEM detector
or EELS
HAADF
Detector
HAADF-high angle
annular dark-field
Scanning
beam
specimen
BF ADF

ADF

BF
DF
(STEM)
Specimen Preparation-Destructive
Dispersing crystals or powders on a carbon film on a grid



3mm
Making a semiconductor specimen with a Focused Ion Beam (FIB)


1. a failure is located and a strip of Pt is placed as a protective cover.
2. On one side of the strip a trench is milled out with the FIM.
3. The same is done on the other side of the strip (visible structure).
4. The strip is milled on both sides and then the sides connecting the
strip to the wafer are cut through.
5. The strip is tilted, cut at the bottom and deposited on a TEM grid.


1
2
3
4 5
Specimen Preparation-2
Ion-milling a ceramic


3mm
Ultrasonic cut
grind
Dimple center part
of disk to ~5-10m
ion-mill until a hole
appears in disk

Ar (4-6keV, 1mm A)
Jet-polishing metal



Drill a 3mm
cylinder
Cut into disks
and grind

A disk is mounted in a
jet-polishing machine
and is electropolished
until a small hole is
made.

a thin stream of acid
+ -
Ultramicrotomy-using a (diamond) knife blade
Mainly for sectioning biological materials.
To avoid ion-milling damage ultramicrotome can also be used
to prepare ceramic TEM specimens.
Specimen Holder
a split polepiece
objective lens
holder
beam


Heating and straining
Twin specimen holder
Double tilt heating
Rotation, tilting, heating, cooling and straining
Specimen Holder with Electrical
Feedthroughs
Imaging
BF and DF imaging
HREM
BF & DF Imaging Diffraction Contrast


Objective
aperture
C-film
amorphous
crystal
D
T
BF image
C-film
crystal

D
T
C-film

crystal

DF image
Diffraction + mass-thickness Contrast
Objective
aperture
DDF CDF
Beam
tilt
T-transmitted
D-diffracted
Hole in OA
OA OA
Diffraction, Thickness and Mass Contrast
Disk specimen
thickness
thinner
thicker

1
2
3
4
5
6
7
8
G.B.
.
.
.
.
. . .
.
. . .
.
.
.
.
. . ..
.
.
. .
.
.
High
mass
Low
mass
T T
S S
S
Bright Dark
Strong
diffraction
Weak diffraction
8 grains are in different orientations
or different diffraction conditions
thickness
fringes
BF images
Bright Field (BF) and Dark Filed (DF) Imaging



Incident beam
specimen
transmitted beam
diffracted
beam
objective aperture
hole in objective
aperture(10-100m)
BF imaging-only transmitted beam is
allowed to pass objective aperture to
form images.

mass-thickness
contrast
BF
DF
DF
DF imaging
only diffracted
beams are
allowed to pass
the aperture to
form images.


Particles in Al-Cu
Alloy.
thin platelets ll e
Vertical, dark
Particles e.
Phase Contrast Imaging
High Resolution Electron
Microscopy (HREM)
Use a large objective
aperture.
Phases and intensities
of diffracted and
transmitted beams
are combined to form
a phase contrast
image.

T
D
Si
Objective
aperture
Electron diffraction pattern recorded
From both BN film on Si substrate.
BN
Electron Diffraction
Specimen
foil
T D
u e
-
L 2u
r
d
hkl
[hkl] SAED pattern
L -camera length
r -distance between T and D spots
1/d -reciprocal of interplanar distance(
-1
)
SAED selected area electron diffraction
Geometry for
e-diffraction
Braggs Law: = 2dsinu
=0.037 (at 100kV)
u=0.26
o
if d=4
= 2du
r/L=sin2u
as u 0
r/L = 2u

r/L = /d or

r = Lx

1
d
hkl
Reciprocal
lattice
Reciprocal Lattice
A reciprocal lattice is another way
of view a crystal lattice and is used
to understand diffraction patterns.
A dimension of 1/d is used in
reciprocal lattices.
2-D Reciprocal Lattices
Real space:
Unit cell vectors: a,b
d-spacing direction
a d
10
[10]
b d
01
[01]

Reciprocal space:
Unit cell vectors: a*,b*
magnitude direction
a* 1/d
10

b

b* 1/d
01

a


A reciprocal lattice can
be built using reciprocal
vectors. Both the real
and reciprocal construc-
tions show the same
lattice, using different
but equivalent
descriptions.


[01]
[10] (10)
(01)
Note: each point in the reciprocal
lattice represents a set of planes.
a*
b*
01
02
10
11
12
20
21
22
For every real lattice there is an equivalent reciprocal lattice.
3-D Reciprocal Lattice
Real space:
Unit cell vectors: a,b,c
magnitude direction
a d
100
[100]
b d
010
[010]
c d
001
[001]


Reciprocal space:
Unit cell vectors: a*,b*
magnitude direction
a* 1/d
100

b and c

b* 1/d
010

a

and c

c* 1/d
001

a

and b



Note: as volume of unit cell in real space increases the
volume of unit cell in reciprocal space decreases, and
vice versa. a*,b* and c* are parallel to corresponding a,b and
c, and this is only true for the unit cells of cubic, tetragonal
and orthorhmbic crystal systems.
Orthorhombic
Lattice Vectors
Real space lattice vector
corresponds to directions
in crystal and it can be
defined as:


r=ua+vb+wc
a,b and c are unit cell vectors,
u,v and w are components of
the direction index [uvw].
A reciprocal lattice vector
can be written as:

g*=ha*+kb*+lc*
a*,b* and c* are reciprocal
unit vectors, and h,k and l
are the Miller indices of the
plane (hkl).
Effect of Spacing of planes in Real Space on
Length of Reciprocal Vector, g
In a crystal of any structure, g
hkl
is normal to the (hkl)
plane and has a length inversely proportional to the
interplanar spacing of the planes.
(111)
-
d
111
-
[111]

-
Why are there so many spots?
The Ewald Sphere and Diffraction Pattern


Reciprocal lattice
High energy
electron case
k wave vector
lkl = 1/
wavelength of electron
Ewalds Sphere
Ewald
circle
0
incident
beam
diffracted
beam
2u
C
k
i
G
g
130
H
Ewalds sphere is built for interpreting diffraction
CG-C0=0G or k
d
-k
i
=g Laue equation
lkl=1/
k
d
Wherever a reciprocal lattice point touches the circle, e.g., at G, Bragg's
Law is obeyed and a diffracted beam will occur. At H, no diffraction.
Construction of Ewalds Sphere
Ewalds sphere is built for interpreting diffraction
patterns and it shows which sets of planes are at (or
close to) their Bragg angle for diffraction to occur.

Incident wave is represented by a reciprocal vector k
(lkl=1/ and points in the direction of wave).
Construct a circle with radius 1/ (i.e., k), which
passes through origin of reciprocal lattice, 0.
Wherever a reciprocal point touches the circle, Braggs
law is obeyed and a diffracted beam will occur.
C0incident beam and CGdiffracted beam. The angle
between C0 and CG must be 2u.
0G is the reciprocal vector g
130
and has magnitude of
1/d
130
.

0G/2=lklsinu, 0G=2/sinu, 1/d
130
=2/sinu
130


=2d
130
sinu
130


Ewalds Sphere Construction in 3D
In a single crystal
only a few sets of
planes are oriented
at their Bragg angle
at any one time.
Polycrystalline sample
ZOLZ
FOLZ
SOLZ
ZOLZ, FOLZ and SOLZ are zero order, first order and second order
Laue zone, respectively.
SAED
A TEM technique to
reduce both the area
and intensity of the
beam contributing to a
diffraction pattern by
the insertion of an
aperture into the
image plane of the
objective lens. This
produces a virtual
diaphragm in the plane
of the specimen.

SAD
aperture
Virtual
aperture
specimen
Objective
lens
Diffraction
pattern
Back focal
plane
Selected Area Electron Diffraction
parallel beam
Focusing SAED Pattern at Fixed Screen
by changing magnetic lens strength
specimen
lens
screen
Transmitted beam
Diffracted beam
Spot pattern
SAED (ZOLZ) gives 2-D information
SAED Patterns of Single Crystal,
Polycrystalline and Amorphous Samples
a b c
a. Single crystal Fe (BCC) thin film-[001]
b. Polycrystalline thin film of Pd
2
Si
c. Amorphous thin film of Pd
2
Si. The diffuse
halo is indicative of scattering from an
amorphous material.
r
1
r
2
200
020
110
Diffraction Spot Intensity
Spot intensity: I
hkl
o lF
hkl
l
2
F
hkl
- Structure Factor
F
hkl
= E f
n
exp[2ti(hu+kv+lw)]
N
n=1
f
n
atomic scattering factor
f
n
o Z, sinu/
h,k,l are Miller indices and u,v,w fractional coordinates
Indexing Diffraction Pattern-ratio technique
Any 2-D section of a reciprocal lattice can be defined by two
vectors so only need to index 2 spots.

1.Choose one spot to be the origin and
measure r1
2.measure the spacing of a second spot r2
3.measure the angle,
|
4.prepare a table giving the ratios of the
spacings of permitted diffraction planes
in the known structure
5.take measured ratio r
1
/r
2
and locate a value close to this in
the table
6.assign more widely-spaced plane (lower indices) to the
shorter r value
7.calculate angle between pair of planes of the type you have
indexed
8.if measured | agrees with one of possible value, accept
indexing. if not, revisit the table and select another possible
pair of planes
9.finish indexing the pattern by vector addition.
Indexing Electron Diffraction Patterns
If we know the index for two diffraction spots
It is possible to index the rest of the spots by
Using vector addition as shown. Every spots
Can be reached by a combination of these two
Vectors.
Zone Axis of A SAED Pattern
Take any two g vectors, g
1
(h
1
k
1
l
1
) and g
2
(h
2
k
2
l
2
)
from the diffraction patter. The zone axis is given by
the vector product:
The zone axis is parallel to the electron beam direction.
Indexing-example
1.Choose T as the origin, r
1
-7.75mm

2.r
2
-12.87mm

3.|~72
O

4.Get a table giving relative reciprocal
lattice spacings

5.r
2
/r
1
=1.66 gives several possible
pair of planes in the table
r
1
r
2

|

T
r=L/d r
2
/r
1
=d
1
/d
2
6.From the table of interplanar angle in cubic, |~72
O
gives only
one matched pair of planes, {100} (or {200}) and {311} for a
face-centered lattice. {100} diffraction is not allowed in a face-
centered structure.

7.Calculating interplanar angles leads to (131) or (113) and (200)
since angle between (311) and (200) is 25.2
O
.
8.Zone axis of pattern: r
1
x r
2
= [013] for (131) and (200) pair


Cubic
200
131 (311)?
_
[013]
_