X-ray Diffraction IX : Electron Diffraction

蔣酉旺 教授
中山大學材料與光電科學學系
 Transmission Electron Microscope (TEM)

■Historically, TEMs were developed because of the limited image resolution in light
microscopes, which is imposed by the wavelength of visible light. Only after electron
microscopes were developed was it realized that there are many other equally sound
reasons for using electrons, most of which are utilized to some extent in a modern TEM.

visible-light microscope
δ smallest distance that can be resolved:

λ is the wavelength of the radiation, μ

the refractive index of the viewing
medium, and β the semi-angle of
collection of the magnifying lens.
The electron microscope built by Ruska
(in the lab coat) and Knoll, in Berlin in the
As λ=550nm, δ is 330 nm.
early 1930s.
 Wavelength-Dependent Resolution
Louis de Broglie’s equation
E is in electron volts (eV) and λ in nm
For a 100 keV electron, λ~ 4 pm (0.004 nm),
which is much smaller than the diameter of an
atom.
■The advantages of shorter wavelengths led in
the 1960s to the development of high-voltage
electron microscopes (HVEMs), with accelerating
potentials between 1 and 3MV.
■An attempt to simulate nuclear-reactor
environments
■Only one HVEM (1 MV) for HRTEM imaging
was constructed in the 1980s and three 1.25MV
machines in the 1990s.
■Corrections of spherical aberration and
chromatic aberration allow us to produce sharper
atomic-resolution images.
 Spherical Aberration

The margins of the lens have a shorter focal length than the center.

optic axis

C A B

C A B
 Chromatic Aberration

The refractive index decreases with increasing wavelength.

optic axis

Chromatic aberration of a single lens causes different

wavelengths of light to have differing focal lengths
 Wavelength of Electron Beam

Momentum (p) to the electron mass (m0)

the velocity (v)
Relativistic effects cannot be ignored at
energies > 100 keV

The inverse relationship betweenλ and V.

 Electron Sources
Thermionic Guns Field-Emission Guns

LaB6 crystal

High Vacuum is job number one!

Electron Sources
 TEMs
JEM 1.25 MeV HVEM Zeiss HRTEM with a Cs corrector
and an in-column energy filter

Nion 200 keV ultrahigh

FEI Titan
vacuum Super STEM

Hitachi 200 keV dedicated STEM JEOL 200 keV TEM/STEM

TEM Illustration
 TEM for Soft Matters

JEOL
JEM-2100
Equipment

JEM-2100(HT)
200KV Electron Microscope (LaB6)
Range: 200KV,160KV,120KV,100KV,80KV
Point image: 0.23 nm
Lattice image: 0.14 nm
Magnification: 50X to 1,200KX
Tilting angle: X:±40°; Y:±30°
High tilt specimen retainer: X:±80°
Vacuum Pressure: 2 x 10-5 Pa or better
■ Beam size for TEM Mode:
20~200nm diameter
■ Nanobeam
■CCD 780: for diffraction observation
1 Million pixel CCD sensor
(1300 x 1030 pixels)
■ CCD 831: for high resolution imaging
7 Million pixel CCD sensor
(2672 x 2672 pixels)
active area: 24mm x24mm
■ 3D Tomography Function
 Electron/Specimen Interaction

X-ray Backscattered Electrons

Incident Beam Atomic number &
Structural &
compositional Topographical
information information
Cathodo Luminescence
Auger Electrons Electrical information
Surface analysis
& compositional Secondary Electrons
information Topographical information
Specimen

Specimen Current
Electrical information
Elastic Scattered Electrons
Surface analysis & Transmitted Beam
Structure information
Inelastic Scattered Electrons
Compositional information
 Electromagnetic Lens

Electrons can be focused easily as compared to X-ray!

 Electron Diffraction in the TEM

■Thompson, Reid, Davisson, and Germer independently showed that electrons could be
diffracted when passing through thin crystals of nickel.
Performing electron diffraction in TEMs was first realized by Kossel and Mollenstedt (1939).

■An electron diffraction pattern may contain information of crystal structure

(and particularly crystal defects), lattice repeat distance, and specimen shape.

A thin foil of Al-Li-Cu containing various

precipitate phases, shown in the inset image.
The central spot (X) contains electrons that
come directly through the foil and the other
spots and lines are diffracted electrons which
are scattered from the different crystal planes.
 Electron Diffraction in the TEM

■The diffraction patterns (DPs) give direct crystallographic information about small areas of the
specimen.
■This capability is one of the most important features of the TEM, because we can relate the
crystallography to the images we see.
■ To a materials scientist, perfect crystals are often pretty boring and can usually be better studied
using such techniques as X-ray diffraction (for structural characterization), the electron microprobe
(for chemical characterization), etc., although new EM techniques
may change this situation.
■ The TEM is the instrument of choice when the specimen is not perfect, particularly when the
feature of interest is what makes the material imperfect or, paradoxically, useful!
 Why Use Diffraction in the TEM

■ Is the specimen crystalline? Crystalline and amorphous materials have very different
properties.
■ If it is crystalline, then what are the crystallographic characteristics (lattice parameter,
symmetry, etc.) of the specimen?
■ Is the specimen monocrystalline? If not, what is the grain morphology, how large are the
grains, what is the grain-size distribution, etc.?
■ What is the orientation of the specimen or of individual grains with respect to the electron
beam?
■ Is more than one phase present in the specimen? If so, how are they oriented?

An experimentally observed DP showing the

central, intense, direct beam and an array of
diffraction spots from different atomic planes.
Such a pattern, with sharply focused spots, is best
obtained by underfocusing the beam.
 Diffraction in the TEM and XRD

■ We will be talking about positions of spots and not their intensities. This type of
analysis differs from many X-ray studies. The reason those beam intensities are not
measured in TEM is that the electron beams are diffracted many times in a typical TEM
specimen.
■ A similar, but not identical, the situation actually occurs when producing powder
patterns by X-ray diffraction (XRD); diffraction then occurs in many different grains at
the same time.
■ In the X-ray case, if you have a single crystal, then you either have to rotate the
crystal to ‘see’ all the beams or use ‘white’ radiation. Electron diffraction is very
different. We can use a single wavelength and still see many diffracted beams.
■ XRD takes minutes or hours unless you have a synchrotron or a position-sensitive
detector to count every photon, while electron-diffraction patterns can be recorded in
<1 second although longer is usually better because it means
you will have ‘spread the beam’ (made the incident beam more parallel); for the
photographic film you’ll use several seconds to a minute or more.
■ Electrons have a much shorter wavelength than the X-rays commonly encountered
in the research lab.
■ Electrons are scattered more strongly because they interact with both the nucleus
and the electrons of the scattering atoms through Coulomb forces.
■ Electron beams are easily directed because electrons are charged particles.
E-beam

19
 Bragg’s Law

Length scale
destructive interference
Wavelength of excitation

θ θ
θθ
d
2θ constructive interference
d

200KeV, λ=0.0251A
sinθ=0.0125n/d

Assume d=2A, n=1,

sinθ=0.0063, θ=0.36
θ is small, so only the angle between 2d sinθ = nλ
the incident e-beam and crystal plane is
small and satisfies Bragg’s law!
The structural factor is also needed to be considered.
 Ewald sphere

g =│k0-k1│= 2k0×(1/λ) ×sin θ= 2k1×(1/λ) ×sin θ =2 ×(1/λ) ×sin θ

g is reciprocal-lattice vector
= ha1*+ ka2* +la3*
A
│g│ =1/dhkl
g : [h k l]
k1 g
θ
θ
Incident beam: [u v w] k0 P
O

Radius= 1/λ
 2-D ED Pattern: single crystal, fiber and powder patterns

Jacodine, R. Nature (London)

1955, 176, 305.
Polymers 2015, 7, 1871 Adv. Funct. Mater. 2009, 19, 448.
polyethylene

poly(nonamethylene pimelate) poly(L-lactide)

Single Crystal Patterns

121
111
101 021
011
001 121
111
101
b3 120
110
020
100
000
b2 010
O b1 120
C 1/λ 100
110

Interactive volume ~ beam size

23
Fiber Patterns
Fiber direction ~
Polymer chain direction

Edward Sphere
Film
C,C*

1st layer

Crystalline Fibers
S O
Equator
C, fiber axis
Reciprocal
Lattice
b

a
24
Powder Patterns Random orientation

Polycrystal
sample

Diffratometer
Film
2000 6
5
1 7
1500
Intensity
2θ or q 3
1000 2
4
8
500
9

0
q = 2π / d = 4π sinθ / λ 10 20
2θ
30
25 40

∼ 4π θ /λ
 SCATTERING FROM A PLANE OF ATOMS

Scattering from two planes of atoms. WI and WD

are the incident and diffracted wavefronts,
respectively.
 MEANING OF n IN BRAGG’S LAW

■ Diffraction from a set of planes a distance d apart. The planes have been oriented to be
in the Bragg diffracting condition.
■ Note that the planes are not parallel to the incident beam. The resultant diffraction spots
(reciprocal-lattice points) are labeled G, 2G, etc.
■ The vector g from the origin (O) to the first diffraction spot G is normal to the
diffracting plane.
■ These other reflections (ng, where n ≠1), called higher-order reflections
 Laue conditions

■ Bragg’s law gives us a physical picture of the constructive-interference phenomenon, but

it does not really correspond to the actual situation in TEM.
■ Our justification in using Bragg’s law is that we can derive it as a special form of the
Laue equations, which really do describe diffraction in the TEM.

constructive interference will only occur when K=g

Laue conditions:
 Laue Zone

Incident beam r
g．r = hu + kv + lw =N r = ua1+ va2 +wa3
N is an integer.

Zero Laue Zone: θ

g．r = hu + kv + lw =0

gh k l
g = ha1*+ ka2* +la3*

(h k l)
 Application of Laue Zone

g．r = hu + kv + lw =N Zero Laue Zone:

N is an integer. g．r = hu + kv + lw =0
as is the case for Xrays, the sphere can only Zone axis
intersect a few points. When l is much
smaller, r
asfor 100-keV electrons, the radius is much 2θ
larger, the sphere is flatter, and it
intersects many more points.

Eward sphere of Cu KαX-ray

Lattice planes h k l with

hu + kv + lw =0
Laue Zone

2nd
1st
zero
g
Ewald sphere of e-beam at 100kV
 Scattering from a single unit cell

r is the distance from a point P on the bottom of

the specimen to the scattering center and ri defines
Since we are summing over all the atoms in the the position of an atom in the unit cell.
unit cell, we can rename this sum as F(θ), the
structure factor of the unit cell.
 THE ATOMIC-SCATTERING FACTOR f(θ)

fx is the scattering factor for X-rays

a0 is Bohr radius of the scattering atom
The atomic-scattering factor f(θ) depends
on λ, θ, and Z.
 Amplitude of ED

n is unit cells per unit area on a plane parallel to the crystal surface and
a is the distance between these planes.

The volume of a unit cell, Vc, is simply a/n.

The amplitude in a diffracted beam (in the direction identified by θ) is

denoted as ϕg and is given by:
 Characteristic length

characteristic length

Fg is the F(θ) for reflection g

■ ξg is the characteristic length for the diffraction vector g. We call it the

extinction distance.
■ Note that ξ g is a scalar quantity. ξ g depends on the lattice parameters
(through Vc), the atomic number (through Fg), and the kV used (through λ).
 THE EXCITATION ERROR

Because the specimen of TEM is a thin plate,

Nz<<Nx and Ny, the reciprocal lattice in the thin
specimen thus becomes a rod-like shape.

Reciprocal lattice rod (relrod) effect

Ewald sphere

g
DIFFRACTION FROM PARTICLES: Shape Effect

How spots in reciprocal space have different

shapes depending on the shape of the particles
which are diffracting.

Very thin plate-like precipitates (A) cause long

streaks in the DP (B).
THE THIN-FOIL EFFECT

All of the spots in the DP are displaced relative to their

positions on the square grid (the projection of the spots
at zero tilt), but that the magnitude of the displacement
varies depending on the sign and
size of s.
Volume effect on ED
 Volume effect on ED

when 𝐾𝐾 � 𝑎𝑎= n (integer), I has a maximum value

Real and Reciprocal Space in TEM
 Real and Reciprocal Space in TEM

Edward Sphere

2θ
1/λ 1/λ

1/d 1/d
sin2θ ≈ (1/d)/(1/λ)
1/λ : 1/d = L : D
2sinθ ≈ λ/d
dD = L λ = constant
2dsinθ ≈ λ
camera length