Ruska and Knoll, Berlin, Germany, 1930

Structure-Property correlation

Microstructure : Atomic configuration.

Properties: Materials Response to an environment.

Mei et al. Prog. Mat. Sci. 52 (2007) 1175.

 What are Electron Microscopes?

Electron Microscopes are instruments that use a beam of highly energetic

electrons to examine objects on a very fine scale.

This examination can yield the following information:

Topography
The surface features of an object "how it looks", its texture; direct relation between
these features and materials properties (hardness, reflectivity...etc.).

Morphology
The shape and size of the particles making up the object; direct relation between these
structures and materials properties (ductility, strength, reactivity...etc.).

Composition
The elements and compounds that the object is composed of and the relative amounts of
them; direct relationship between composition and materials properties (melting point,
reactivity, hardness...etc.)

Crystallographic Information
How the atoms are arranged in the object; direct relation between these arrangements
and materials properties (conductivity, electrical properties, strength...etc.)
Electron Microscopes are instruments
that use a beam of highly energetic
electrons to examine object’s relative
structural and compositional attributes
on a very fine scale.
 Phase stability in Ultrafine Particles

Ag-Ni system exhibits negligible miscibility.

Is single phase Ag-Ni solid solution: a nanoparticle
size effect?

Physical Mixture
Ag-Ni nanoparticles of all compositions
Representative Ag-Ni Nanoparticle
present in solution synthesized
Showing single phase solid solution
Nanoparticle dispersion
Solid Solution

AB (AB interface energy) SS (surface energy

Extent of energetic of solid solution) and  (surface energy of
contribution pure components) are all particles size
from surfaces/interfaces dependent
changes with size
Size dependent microstructure criterion

Within the nano-scale regimen

Surface energy increases with surfaces/interfaces play a vital role in
decreasing size; rate of changes deciding stability of phases.
increases with decreasing size

Size Effect Studies and Electron Microscopy Group

Department of Materials Engineering, Indian Institute of Science, Bangalore
 Synthesis and Ordering in Nanoparticles

50 nm

Size Effect Studies and Electron Microscopy Group

Department of Materials Engineering, Indian Institute of Science, Bangalore
 Phase Stability and Transformations in Positive Enthalpy of
Mixing Systems: Electrodeposited Nanowires
•C. Srivastava and R. K. Rai, “Transmission Electron Microscopy Study of Ni-rich, Ag-Ni Nanowires” Chemical Physics Letters (2013).
•C. Srivastava and R.K. Rai, “Two phase microstructure for Ag-Ni nanowires” Chemical Physics Letters 561, 101 (2013).

Size Effect Studies and Electron Microscopy Group

Department of Materials Engineering, Indian Institute of Science, Bangalore
 Nanowire Microstructure

Size Effect Studies and Electron Microscopy Group

Department of Materials Engineering, Indian Institute of Science, Bangalore
 Nanowire Microstructure

Size Effect Studies and Electron Microscopy Group

Department of Materials Engineering, Indian Institute of Science, Bangalore
 How do Electron Microscopes Work?

Electron Microscopes(EMs) function exactly as their optical counterparts

except that they use a focused beam of electrons instead of light to
"image" the specimen and gain information as to its structure and
composition.

The basic steps involved in all EMs:

• A stream of electrons is formed (by the electron source ) and accelerated

toward the specimen using a positive electrical potential

• This stream is confined and focused using metal aperture and magnetic
lenses into a thin, focused, monochromatic beam.

• This beam is focused onto the sample using a magnetic lens.

• Interaction occur inside the irradiated sample, affecting the electron

beam
 Single lens system

Magnified, real and inverted

image
Object

Image
Achieving high magnification using a single lens is not possible so a combination
of lenses is used. Also to get a upright image.

Two lens system

Objective lens
Projector lens
Three Lens System
Transmission Electron
Microscope
Scanning Electron
Microscope
Magnification
Single lens system
Magnified, real and inverted
image
Object

Image

For a convex lens of focal distance f

Magnification = v/u =
Magnification
Simple lenses are subject to the optical aberrations. In many cases these aberrations can be
compensated for to a great extent by using a combination of simple lenses with
complementary aberrations. A compound lens is a collection of simple lenses of different
shapes and made of materials of different refractive indices, arranged one after the other
with a common axis.

Objective lens
Projector lens
Resolution

Closest spacing between two points which can clearly be seen

through a microscope to be separate entities
Resolution

50 mm 100 mm
Resolution

When the maximum intensity

of one Airy disc coincides
with the minimum of the
second, the two points can
just be distinguished
Resolution

The Rayleigh criterion for resolution indicates how close

together two points can be brought together before they
can no longer be distinguished as separate.
DEPTH OF FIELD

The depth of field (D) refers to the range over which the object plane
can vary relative to the theoretical best focus while the image appears
to remain in focus. Specimen movement in Z direction.

D = /msin2a + 1/7m sina

 : wave length of the source
m: refractive index of the medium
a: aperture semi angle
m: magnification

The depth of field of a particular microscope depends critically on its

resolution and on the magnification to be employed: as the resolution
is improved and the magnification is raised the depth of field
becomes smaller
DEPTH OF FOCUS
ABERRATIONS
Chromatic Aberration

• for electrons can be controlled by KV.

• but  of electrons can change by interaction with specimen !
ABERRATIONS
Spherical Aberration

Disc of minimum confusion has diameter given by

d = C a
{C = constant}
hence reducing a gives a large reduction in d, but for optimal resolution we need
large a !. best compromise is with a = 10-3 radians (= f/500) gives resolution = 0.1
nm - can not be bettered
ABERRATIONS .
Astigmatism

•Astigmatism occurs when a magnetic lens is not perfectly round. Inherent

inhomogeneities in magnetic properties of pole piece.
•Build-up of contamination on bore of pole-piece and on apertures gives rise to non-
conducting deposits which become charged as electron strike them.
• Cannot be ‘designed out’.
• Inevitably requires continuous correction.
 GENERATING A BEAM OF ELECTRONS
Electron Gun: a source of high energy primary electrons. to produced a fine beam of electrons of precisely
controlled energy (i.e. velocity) all coming from a small source region.

Thermionic Gun
Filament: Filament is made from a
High melting point material with a low
work function in order to emit many
electrons.

Tungsten: work function: 4.5 eV

Lanthanum Hexaboride : work function:

3 eV.
Bias Resistor: The resistor is used to
set a negative bias on the Wehnelt
cylinder.

Wehnelt Cylinder: It is a biased grid

with few hundred volts difference in
potential from the filament. This
causes the electron path to cross
over from the anode hole. The
diameter of beam at this cross over
is the effective source of
illumination.

Crossover: It is the effective source

of illumination for the microscope.

Anode: Anode is a positively

charged plate. It accelerates the
electrons to the HT potential.
ELECTRON GUN
A field emission gun is a type of electron
gun in which a sharply-pointed emitter is
held at several kilovolts negative
potential relative to a nearby electrode,
so that there is sufficient potential
gradient at the emitter surface to cause
field electron emission.

Emitters:

(a) Cold-cathode type: usually made of

single crystal tungsten sharpened to a tip
radius of about 100 nm.

(b) Schottky type: thermionic emission is

enhanced by barrier lowering in the
presence of a high electric field. Made
by coating a tungsten tip with a layer of
zirconium oxide, which has the unusual
property of increasing in electrical
conductivity at high temperature.
ELECTRON GUN
Field emitting tip: In order to get high
field strength with low voltages, the field
emitting tip has a strong curvature. This
is done by etching a single crystal
tungsten wire to a needle point. The
emitting region can be less than 10 nm.

Grid: the grid provides the field that

extracts the electrons by a tunneling
mechanism from the filament tip. The
combination of modest potential with a
Very small tip radius gives a very high
field strength (109-1010 V/m).

Anode: Anode is a positively charged

metal plate. Its function is to accelerate
the electrons to the HT potential.

Crossover: crossover is the effective

source of illumination for the
microscope.
ELECTRON GUN
A field emission gun is used to
produce

An electron beam that is smaller in

diameter more coherent and with
up to three orders of magnitude
greater current density or
brightness than can be achieved
with conventional thermionic
emitters such as tungsten or
lanthanum hexaboride (LaB6)-
tipped filaments.

The result in both scanning and

transmission electron microscopy
is significantly improved signal-to-
noise ratio and spatial resolution,
and greatly increased emitter life
and reliability compared with
thermionic devices.
BRIGHTNESS
In context of electron microscopy, brightness is defined as the beam current density per unit
solid angle (Am-2sr-1). Brightness (B) is a measure of how many electrons per second can be
directed at a given area of the specimen.

Jc : Beam current density (Am-2)

b: Beam convergence angle

For thermionic gun

T: temperature of the filament

: Thermionic work function of the filament material

Filament material with high melting point and low

work function should be used
BRIGHTNESS

For Field emission gun

Brightness in this case depends strongly on the

applied field F

J : Current density, Ef : Fermi energy,  : work function

For high field the source has to prepared as a sharp

tip (diameter < 100nm) . For the tip to be
preserved in use the vacuum in the gum chamber
much be very high.
MAGNETIC LENSES
If an electron moving with a velocity v experiences a magnetic field of strength B, then it
suffers a force F = Bev in a direction perpendicular to both the direction of motion and the
magnetic field.

A magnetic lens consists of a

coil of copper wires inside the
iron pole pieces. A current
through the coils creates a
magnetic field (symbolized by
red lines) in the bore of the pole
pieces. The rotationally
symmetric magnetic field is
inhomogeneous in such a way
that it is weak in the center of
the gap and becomes stronger
C: soft iron core close to the bore
W: A coil consisting of
Large number of turns of wire
A strong magnetic field
is generated by passing
a current through a set
of windings. This field
acts as a convex lens,
bringing off axis rays
back to focus.

The image is rotated, to

a degree that depends
on the strength of the
lens.

Focal length can be

altered by changing the
strength of the current.
CONDENSER SYSTEM
Condenser lenses are positioned
below the electron gun assembly.
Their function is to demagnify
the electron beam emitted by the
gun and control its diameter as it
hits the specimen. This
demganifications enables the
user to control the area on the
specimen that is hit by the beam
and thus the intensity of the
illumination. The condenser
aperture present between the
condenser lenses and the
specimen is used to control the
convergence angle of the
electron beam. A schematic of a
two condenser illumination
system is shown in the figure.
the first condenser lens (C1)
often labeled as ‘spot size’ sets
the demagnification of the gun
crossover. The second lens (C2)
often labeled as ‘intensity’
provides control of the
convergence angle of the beam
leaving the condenser assembly.
SPECIMEN CHAMBER

Specimen chamber lies below the condenser system. Two main requirements of the
specimen chamber design are (a) a very small (typically 3mm in diameter) sample must be
held inside the objective lens in precisely the correct position (b) it should allow the
movement of specimen by several millimeters in X, Y and Z directions and tilt by large
angles. Figure show a side entry double tilt holder and its range of movement inside the
specimen chamber respectively.
THE OBJECTIVE AND INTERMEDIATE LENSES

The objective lens forms the first intermediate image and the diffraction pattern, one or the other of which
is enlarged by the subsequent projector lenses. The diffraction pattern is formed in the back focal plane of
the lens. The diffraction lens (first projector lens) can be switched between two settings; image mode and
diffraction mode. In the image mode it is focused on the image plane of the objective. In the diffraction
mode the intermediate lens is focused on the back focal plane of the objective projecting the diffraction
pattern on the viewing screen
THE OBJECTIVE AND INTERMEDIATE LENSES
Objective Aperture

An essential feature of the objective system is the apertures. These apertures can be inserted into the
column in the back focal plane defining the angular range of the scattered electrons which can contribute
to the image. The diameter of the aperture thus controls the ultimate resolution of the TEM set by the
equation:
d = 0.61l/µsinb
Where b is the smallest distance that can be resolved, l is the wave length of radiation, µ is the refractive
index of the viewing medium and b is the semi convergence angle of the magnifying lens. For a high
resolution image a larger aperture is needed. However, for many purposes high resolution is not needed
and the objective aperture then serves a different function of controlling the contrast which seen in the
image.
SELECTED AREA DIFFRACTION (SAD)

Selected Area Aperture

▪ To record a diffraction pattern from a selected area of the specimen.

▪ Selected area diffraction is achieved by inserting a aperture in the

plane of the first image produced by the objective lens.
Electron Diffraction
Electron Diffraction
GEOMETRY OF ELECTRON DIFFRACTION

The electron beam is incident

on a specimen it will be
elastically scattered by some
of the constituent atoms
(marked A and B). we can
think of the electron beam as
a wave motion and apply the
similar arguments used to
explain the diffraction of X-
rays
GEOMETRY OF ELECTRON DIFFRACTION

The incident electron beam is coherent. Any scattered wave which are also in phase with one
another will reinforce leading to a strong beam of electrons, whereas the waves which are out
of phase will not reinforce each other.

The scattered waves at D will be in phase if

CB + BE = n

Where

 is the wavelength of the incident electrons

CB=BE = d sinθ

Condition for reinforcement is thus

Bragg’s Law
GEOMETRY OF ELECTRON DIFFRACTION

d is the spacing of atoms that are scattering the

electrons. In a crystalline array, d is the spacing of
lines of atoms. In a three dimensional crystal d is
the spacing of planes of atoms-the interplanar
Bragg’s Law spacing.

For a cubic crystal the interplanar spacing of

planes with indices (hkl) is given by
Where a is the
lattice parameter.

n is the order of diffraction and for a particular

plane the diffraction occurs when n= 1,2,3…etc. It
is convenient to consider only the first order of
diffraction and to deal with higher order using the
corresponding multiples of miller indices. Thus
when dealing with the second order diffraction
from the (131) plane, we imagine planes to be
present with half the spacing and call this first
order diffraction from (262) plane.
GEOMETRY OF ELECTRON DIFFRACTION

If we substitute typical values of θ and d in bragg’s

equation, say = 0.0037 and d= 0.4 nm (the spacing
for planes in aluminum crystal), we find that sin θ =
0.0046 and hence θ = 0.0046 rad, since for such
Bragg’s Law small angle we can approximate sin θ for θ. This
small angle approximation is valid for angles up to
at least 5 degrees.

Taking the above argument into account the bragg’s

equation becomes

There will only be strong diffraction

from planes of atoms which are
almost parallel to the electron beam-
concept of zone axis in diffraction
GEOMETRY OF ELECTRON DIFFRACTION
The theoretical treatment of electron diffraction relies on the kinematical
theory of electron diffraction with the following assumptions

(a) The incident electron beam is monochromatic.

(b)The crystal is free from distortion.

(c) Every atom in the crystal receives an incident wave of the same
amplitude.

(d)The incident and scattered waves are plane waves.

(e) There is no attenuation of the electron beam with increasing depth in the
crystal; no absorption.

(f) There is no interaction between the incident beam and the scattered
wavelets.

(g)There is no re-scattering of the scattered waves.

RECIPROCAL LATTICE
r.p0 = OP; r.p = OD

POD = r.(p-p0)

Defining a scattering vector P = p-p0

POD = r.P=n (criterion for constructive interference)

Resolving r vector

P.a = h; P.b = k; P.c = l

Where a, b and c are the repeat distance of atoms along the crystal
axes and h, k and l are integers.

P/ = ha* + kb* + lc*

Where a* , b* and c* are vectors defined such that

a.a* = b.b* = c.c* = 1 and a*.b= 0 etc.

Therefore a*mag = 1/amag -origin of reciprocal lattice (g)

(1) The vector g(hkl) to the point (hkl) of the reciprocal lattice is
normal to the plane (hkl) of the crystal lattice
(2) The magnitude of g(hkl) is 1/dhkl where dhkl is the
interplanar spacing of the family of (hkl) planes
RECIPROCAL LATTICE

In reciprocal lattice each plane of the real lattice is represented by a

point laying at a distance of 1/d from the origin (O) on the
perpendicular to the plane.

The vector describing the position of the reciprocal lattice point

relative to O is denoted by g known as the diffraction vector.

If we apply the same transformation to the reciprocal lattice we can

reconstruct the real lattice.
DIFFRACTION IN TEM

Ray diagram of a two-stage

projection microscope showing
the positions of the diffraction
pattern (DD’ and EE’) and
image BB’ and CC’

L is the camera constant

Distance of a diffracted spot, r,

from an undiffracted spot is
inversely proportional to the d
spacing of the diffracting plane
RECIPROCAL LATTICE

If we consider lattice planes of figure ‘(a)’ then we can

construct the reciprocal lattice ‘(c)’ and see that it is a row
of points of spacing ‘1/d’ laying perpendicular to the
plane. The diffraction pattern is a scaled section through
the reciprocal lattice normal to the beam.
EWALD SPHERE

The diffracting crystal is represented by

its reciprocal lattice

The electron beam is represented by a

vector of length ‘1/’ parallel to the beam
direction and terminating at the origin of
the reciprocal lattice

A sphere (Ewald sphere) of radius ‘1/’

is drawn about A.

The Ewald sphere passes through a reciprocal lattice point at a distance 1/d from the origin.
From geometry

Diffraction occurs when the

Ewald sphere touches a reciprocal
lattice point
DIFFRACTION FROM A FINITE CRYSTAL

Crystal not oriented exactly at the

Bragg angle

The thinner the

crystal,
The further the
crystal may
deviate form
The Bragg
condition and yet
diffract

Electron diffraction
Pattern from a single
crystal.
a-d increasing
thickness. Zone axis
[110]
DIFFRACTION FROM A FINITE CRYSTAL
In terms of the Ewald sphere the relaxation of
the diffraction condition corresponds to the
extension of the reciprocal lattice points in the
direction normal to the plane of the specimen.

Since the length of the rod is inversely

proportional to the specimen thickness, the
thinner the specimen the more diffraction spots
will occur in the pattern.

Diffraction condition at the

reciprocal lattice point at any
point is extended in each
dimension by an amount
proportional to the thickness of
the crystal plate in that direction
DIFFRACTION FROM A FINITE CRYSTAL
DARK FIELD IMAGING
KIKUCHI LINES
In a crystalline specimen some of the inelastically scattered electrons may subsequently be
scattered elastically this gives rise to kikuchi lines
KIKUCHI LINES

More forward scattering – higher

intensity

Higher angle scattering – lower

intensity

Trace of the plane (halfway between

the lines)

Since kikuchi lines show us the trace

of lattice planes, they can give
information about the zones. They
also provide the relationship between
Excess line – farther Deficit line –
closer to origin the planes to allow us to orient that
from origin
crystal and identify the interface
relationships
If we tilt the crystal through a very small angle, the Kikuchi lines will
move but the intensities of the diffraction spots will hardly change and
the positions of the spots will not change. So Kikuchi lines are much
more sensitive to beam/specimen tilts than spots in SADPs.

Kikuchi lines can be used to set up specific diffraction conditions

exciting specific reflections as we tilt the specimen.

The distance in reciprocal space

between the Kikuchi lines is g
because the angle between the two
Kossel cones is 2θB. When the g
Kikuchi line passes through the
reflection G, sg = 0 (i.e., the Bragg
condition is exactly satisfied) and the
-g Kikuchi line passes through O.
Kikuchi line spacing in the diffraction pattern is directly related to the spacing of the operative
crystal planes by the equation

Dd = L

Can be used to identify the planes forming the kikuchi band. A better measure of the d spacing
than the spot pattern.

The angle between the kikuchi lines from different {hkl} planes correspond to the angles
between the planes because kikuchi lines are parallel to the trace of the plane.
Since the Kikuchi lines are ‘rigidly attached’ to the crystal, they give us a very accurate measure
of the excitation error sg
When sg is negative, the g Kikuchi line is on the same side of g as O; when sg is positive, the
line lies on the opposite side of g.
If you look at the figure you’ll see
that the bright diffraction spot at
the top LH corner of the DP is
under sg positive conditions (excess
Kikuchi line outside the spot), the
bright spot at the middle/upper RH
side is under sg zero conditions (the
excess Kikuchi line through the
spot) and the bright spot toward the
bottom of the DP is under sg
negative conditions (the excess
Kikuchi line inside the spot).
DIFFRACTION IN TEM

Ring Pattern Spot pattern

Identification of the phases; The foil orientation can be determined;
Analysis of texture; Identification of phases;
Determination of the camera constant L. The orientation relationship between
structures can be determined.
INDEXING DIFFRACTION PATTERN
Spot diffraction pattern
1) Choose a parallelogram with smallest R1,
R2, R3.

2) Measure distances R1, R2, R3 and angles 1,

2.

3) Calculate d1,d2,d3 (using the rule rd=L).

h1k1l1
h3k3l3 4) Correlate the measured d-values with dhkl
R3
R1 2 taken from the list of standard interplanar
1 distances for the given structure and ascribe
R2 h1k1l1 and h2k2l2 and h3k3l3 indices for the
h2k2l2
chosen three spots.

5) Check the condition that h1+h2=h3;

k1+k2=k3; l1+l2=l3.

6) Compare the measured angles (both 1 and

2) with the calculated angles.

Zone axis of the ED pattern = (h1k1l1)X(h2k2l2)

INDEXING DIFFRACTION PATTERN
Ring diffraction pattern
1) Measuring ring diameters D1, D2, D3 …….
2) Calculation of the dhkl (using the expression: rdhkl=L)

Ring Ratio Method

(a) Measure the ring diameter

(b) Determine the ratio of square of the diameters of

the outer ring to that of the first or second ring

(c) check the ratios against the table of ratios of the

interplanar spacings of the crystal structure of interest.

D
CONTRAST MECHANISMS
Mass Thickness Contrast The objective aperture is located in
the back focal plane of the objective
lens. It prevents any electrons which
have been scattered (elastically or
inelastically) by the specimen
through an angle larger than a from
passing down the column and
contributing to the image- Bright
Field Imaging.
The scattering of electrons from different regions of a
thin specimen. In a thin area (to the left) only a few
electrons are scattered and perhaps 47 of the original
50 incident electrons continue undeflected. In a thicker
region of the same materials(center) more are scattered
and perhaps only 43 remain in the undeflected beam.
For a region of the same thickness but higher density
even more scattering will take place and perhaps only
37 electrons continue to pass through the objective
aperture
For a constant value of s the intensity varies periodically with t, becoming zero each time
the product ts is an integer.
Why do you see thickness fringes at s=0?
Dynamical Theory

• Electrons may be re-diffracted back from the diffracted into the transmitted beam

• Absorption of electrons by the specimen.

The theory allows for the contribution back to the

transmitted beam from the diffracted beam. There is a
coupling between the diffracted and the transmitted beam
 The depth of variation of the transmitted intensity in a perfect crystal under dynamical
diffraction condition is given by

The term x describes a critical distance in the

perfect crystal at which the transmitted
intensity falls to nearly zero before increasing
again.
Column Approximation: intensity at one point in the image (x, y) which arises from one
column (x, y, z =0 to t) in the specimen is independent of the behavior of the electron beams
in the adjacent column.

The term g.R incorporates the effect which the defect has
on the operating plane. When g.R is zero the defects do not
disturb the operating plane and so the defect is invisible:
Invisibility criterion.
COLUMN APPROXIMATION

The column is narrower than the image but

contains but wide enough to contain both
diffracted and the transmitted amplitudes.

There is no contribution to the waves in the

column from rest of the specimen and
conversely no loss from the column to the
specimen

If the crystal is distorted that is when a crystal

defect is present the distortion occur down but
not across the column

Only plane waves exist the column

Only one diffracted beam exists (two beam

condition)
A stacking fault can be seen as the boundary between two wedge shaped crystals which are
in direct contact, but with a displacement R along the wedge.
The characteristic contrast of the stacking fault consists of fringes
running parallel to the intersection of the fault with the specimen
surface. Fringes can be though as resulting from the interference
between the beams diffracted from the upper part of the crystal and
those diffracted below that fault. The diffracted waves suffer a phase
change at the fault and the fringes are thus the usual manifestations of
the interference between two sets of waves that are slightly out of
phase.
If the product g.R is zero the crystal containing a stacking fault will
give contrast identical to that from a perfect crystal. The condition fro
g.R to be zero is that the fault vector Is perpendicular to the operating
reflection. In figure the fault is invisible because the fault vector is
1/6[112] and the operating reflection is (2-20). This invisibility
criterion can be used to identify the displacement vector of the
stacking fault.
Grain Boundary
Dislocations
Imaging of dislocation is performed by setting the sample
just off a strong diffracting condition (operating reflection)
and allowing the lattice distortion around the defect to bring
them into the strong diffracting condition and hence appear
dark.
CONTRAST MECHANISMS-DIFFRACTION CONTRAST

Extinction Contour: Most real specimens are not perfectly flat

and are elastically buckled to some extent. The image then contains
dark regions that corresponds to those regions of the specimen
which are at the Bragg angle, together with light regions
corresponding to parts of the specimen that are not strongly
diffracting.