Course T2 Electron Microscopy and Analysis

T2: Electron Microscopy and Analysis
1
Course T2: Electron Microscopy and Analysis

Synopsis

Aim

The purpose of this course is to introduce the student to electron microscopy and its
capabilities. The structure of an electron microscope will be introduced to develop an
understanding of the operation of scanning and transmission electron microscopes in the
formation of images and diffraction patterns. The signals generated in the electron
microscope are discussed, and their use for analysis of different materials problems is
highlighted.

Scanning electron microscopy (4 lectures)

1. Introduction
Basic design of SEM; choice of filament; structure of the electron gun; action of
electron lenses; scanning system; lens aberrations; spatial resolution; image contrast;
choice of objective aperture

2. Beam-specimen interactions
Signals generated and detected in the SEM; electron range; electron detectors

3. Image formation
Sample preparation; image formation with secondary electrons; image formation
with backscattered electrons; channelling contrast; backscattered diffraction patterns;
cathodoluminescence; voltage contrast

4. X-ray microanalysis
X-ray generation by electron beams; electron transitions in atoms; chemical analysis
with X-rays; energy dispersive spectroscopy; wavelength dispersive spectroscopy;
common artefacts; quantitative analysis and ZAF corrections; detectability limits

Transmission electron microscopy (4 lectures)

5. Introduction
Design of a TEM; sample requirements and preparation

6. Beam-specimen interactions in a thin film
Brief overview of beam-specimen interactions; atomic scattering factor; scattering
from a unit cell; elastic scattering; diffraction patterns from polycrystalline and
amorphous materials

7. Image formation
Formation of images and diffraction patterns; bright field and dark field images;
selected area and convergent beam electron diffraction patterns; kinematic scattering
approximation; bend contours; thickness fringes; defects in materials; stacking faults;
dislocations; high resolution TEM

2
8. Microanalysis in the TEM/STEM
Energy dispersive X-ray spectroscopy; electron energy loss spectroscopy; comparison
of techniques for chemical analysis and detection

Recommended text books

Two books cover most aspects of the course:

Electron Microscopy and Analysis (3
rd
Edition) by P. J. Goodhew et al. (Mb262)
Electron Beam Analysis of Materials (2
nd
Edition) by M. H. Loretto (Mb231)

The Mb section of the departmental library contains many other, more specialised texts
that may be useful for aspects of this course, including:

SEM
Practical Scanning Electron Microscopy by J. I. Goldstein et al. (Mb141)
Scanning Electron Microscopy by L. Reimer (Mb237)

TEM
Transmission Electron Microscopy A Textbook for Materials Science by D. B.
Williams and C. B. Carter (Mb309-312, 4 volumes)
Electron Microscopy of Thin Crystals by P. B. Hirsch et al. (Mb165)

Supplementary information

DoITPoMS Teaching and Learning Packages www.doitpoms.ac.uk
Matter software (available on the computers in the teaching laboratory and in college
computer rooms), with some modules available online at www.matter.org.uk

Acknowledgements

Thanks to Dr. P. Midgley, Dr. J Barnard and Dr. S. Friedrichs for providing images that
have been reproduced in this handout.
3
Scanning Electron Microscopy

1. Introduction

Electron microscopy techniques provide very powerful methods for examining
materials to much higher resolution than can be achieved using light microscopy. The
interaction between the electron beam and the specimen generates many signals that can
be used to develop a greater understanding of the chemical and physical properties of
materials.

The structure of an electron microscope can be compared to that of a light microscope,
with many similar features:

Light microscope Electron microscope

We can also use ray diagrams to illustrate schematically the operation of electron
microscopes.

4
Basic structure of a scanning electron microscope (SEM)

Schematic diagram of an SEM.

The main components of an SEM are the electron gun, which generates a beam of
electrons that are accelerated by an electrostatic potential of ~ 1 - 40 kV, and electron
lenses (usually electromagnetic) are then used to focus the electron beam into a fine
spot on the surface of the specimen. The interaction between the electron beam and the
specimen generates a wide range of signals that can be collected by detectors and used
to analyse the properties of the specimen. The beam is rastered over the surface of the
specimen using electrostatic coils to create a 2-D image formed using the chosen signal.

1.1 The electron gun

The electron gun is chosen to produce as bright a source of electrons as possible to
maximise the number of electrons hitting the specimen surface (per unit area). This
generates the maximum signal for detection.

The brightness, , of the electron source is dependent on the emission current, i
e
, the
source size, D
0
, and the angle,
0
, that the source makes with the anode:

2
0
2
0
2
0
2
4

e e
J
D
i
= = (1.1)
5

Schematic diagram of a thermionic electron gun

For high brightness, an electron source with a high emission current (i
e
) and small
source size (D
0
) are required. A small D
0
leads to a small spot on the sample, and
therefore a high spatial resolution.

Thermionic emission sources are typically made from either a tungsten wire or a LaB
6
crystal. The current can be high, but the current density (J
e
) is relatively low due to
large source size (D
0
).

A field emission gun uses a strong electric field to enable electrons to tunnel out of a
very fine W needle. They have very high brightness with high emission current but
small source size.

1.2 The condenser lens

Electron lenses used in modern electron microscopes are usually electromagnetic, and
act to deflect a beam of electrons by the Lorentz force experienced by a moving,
charged particle in a magnetic field. They can be used to focus a beam of electrons into
a probe, and the strength of the lens (focal length) can be changed by varying the
magnitude of the electromagnetic field.

In an SEM, the condenser lens is used to choose the spot size. This lens collects
electrons emitted by the gun that are subsequently used to form a probe on the specimen
surface. By increasing the strength of the condenser lens, electrons can be selected
from progressively smaller regions on the filament, thereby reducing the source size
D
0

6
(demagnifying). This allows a smaller spot to be formed, thus increasing the spatial
resolution.

For fixed gun brightness, this reduces the current in the beam, and therefore the
available signal will reduce in strength. [There is always a compromise between
resolution and signal intensity.]

1.3 The objective lens

This lens is used to focus the beam onto the specimen surface, and should be adjusted to
achieve the minimum spot size (as chosen by the condenser lens). This gives the
maximum spatial resolution in the final image.

The magnification is given by the ratio of the image distance, v, to the object distance,
u, i.e.
u
v
M =

Lens diagram showing the demagnifying effect of the electromagnetic lenses modelled
as a simple convex lens.

The distance v is known as the working distance and should be kept to a minimum to
achieve the best spatial resolution. The working distance is approximately the distance
from the bottom of the objective lens to the specimen, and is typically 10 mm.

1.4 Scanning

The scan coils used in any electron microscope are electrostatic and act in pairs to shift
or tilt the electron beam. The coils raster the beam, usually in a rectangular array, such
that an image is built up sequentially. The electron beam is aligned such that it always
passes through the centre of the objective lens. For a TV rate image (30 Hz) of 1200
800 pixels, the beam dwell time is only ~ 35 ns at each pixel.

u v
f
7
1.5 Aberrations

Electromagnetic lenses are far from perfect, and suffer from many aberrations which act
to reduce the minimum achievable probe size, and therefore reduce the spatial
resolution. Chromatic and spherical aberrations can only be minimised by careful
design of the objective lens, but astigmatism is usually corrected by the operator during
the experiment.

We can consider the contributions of different aberrations to the total spot size by
adding in quadrature (assuming that all contributions are Gaussian):

(1.2)

(1.3)

(1.4)

(1.5)

(1.6)

N.B. through the action of the lenses, d
0
is about 10 smaller than D
0
. This is simply
because not all of the electron beam which passes through the condenser lens can enter
the objective lens (see 1.7).

In these equations is the convergence semi-angle (half-angle) onto the specimen of
the beam with current i. The solid angle of the beam,
2
, is
2
.

Typical values for an SEM are:
= 10
-2
rad.
E = 40 kV
C
s
= 20 mm
C
c
= 8 mm

For a thermionic source: ~ 10
9
Am
-2
sr
-1

For a LaB
6
source: ~ 10
10
Am
-2
sr
-1

For a FEG source: ~ 10
13
Am
-2
sr
-1

1.6 Beam current

To achieve the best spatial resolution, the signal strength must be sacrificed. In
practice, when imaging in the SEM, the contrast, C, defined as S/S, must be optimised
(where S is the signal and S is the change in signal).

(1.7)
2 2 2 2
0 d s c tot
d d d d d + + + =
2 2 0
4

i
d =
c c
C
E
E
d
|
\
|
=
3
2
1
s s
C d =
22 . 1
=
d
d
Probe size (see earlier
equation for brightness)
Chromatic aberration
Spherical aberration
Diffraction limit
S
S
C
=
8
The changes in signal must be greater than 5 times the noise level, , in the image to be
able to detect the difference.
(1.8)

For Poisson statistics, the noise, , can be expressed as n, where n is the average
number of electrons detected at a particular point (i.e. the signal, S). This leads to the
equation:
(1.9)

and therefore (1.10)

If we start to consider the formation of a scanned image, with a frame rate of f (Hz) and
N
p
pixels, then the beam dwells on each pixel for a time t given by:

(1.11)

In the time t that the beam dwells on each pixel, the number of electrons entering the
specimen, n
0
, is

(1.12)
The number of electrons actually detected, n, depends on the beam-specimen interaction
and the efficiency of the detector, say n = qn
0
. Therefore, to discern a contrast, C, in the
specimen, we require a minimum current of
(1.13)

Therefore the spatial resolution (small spot size, small I) must be compromised for
image contrast (better quality images, large I).

1.7 The objective aperture

The objective aperture controls the convergence angle and is in a plane conjugate with
the objective lens. A small aperture will reduce the effect of spherical aberration
(through a small) and increase the depth of focus, but will limit the beam current.

Illustration of how the
objective aperture
changes the depth of
focus for a fixed
resolution. The depth
of focus is the
distance from the
plane of optimum
focus within which
the beam diverges by
no more than the disc
of least confusion.
5 > S
n
C
5
>
2
25
C
n =
f N
t
p
1
=
fe N
I
e
t I
n
p
= =
.
0
2
min
25
qC
fe N
I
p
=
Objective
aperture
Disc of least
confusion
Disc of least
confusion
Depth of focus
9
2 Electron beam-specimen interactions

Electrons are charged particles and as such interact much more strongly with matter
than X-rays or neutrons. A variety of signals can be collected from the interaction of an
electron beam with a specimen, and these are summarised in the schematic diagram
below.

A schematic diagram illustrating a range of signals that may be generated when an
electron beam is incident on a specimen.

For SEM, the strongest signals are usually the backscattered and secondary electrons,
and therefore only these signals will be discussed further in this section.

2.1 The scattering process

The incident electron beam suffers many elastic and inelastic scattering events. The
elastic scattering of the primary beam leads to a spread of the incident electrons within
the specimen.
(a) A Monte Carlo simulation of the
electron trajectories in Cu at 30 kV
(b) Illustration of the variation of the
electron scattering with atomic number and
voltage.

Low Z High Z
Low
voltage
High
voltage
R
(a)
(b)
10
The electron range is defined as the average total distance travelled by the electron
within the specimen and is approximately the diameter of the spread. The table below
shows the range, R (in m) as a function of incident energy for different materials.

2.5 kV 5 kV 10 kV 15 kV
Al 0.12 0.4 1.25 2.4
Cu 0.046 0.15 0.47 0.9
Au 0.027 0.088 0.28 0.54

2.2 Backscattered electrons

Backscattered electrons (BSE) are those of the primary beam that have escaped the
surface, usually after elastic and inelastic scattering events.

Elastic scattering results from the deflection of the electron beam by the positive
charges of atomic nuclei in the sample. This can be analysed simply using the classic
Rutherford scattering model. In this model, the differential scattering cross section,
d/d, is given as a function of the scattering angle and the atomic number, Z, by the
expression

(2.1)

To estimate the fraction of electrons that are backscattered, , we must consider the fact
that the electrons must reach the surface after undergoing scattering events. Monte-
Carlo simulations are a very powerful method for modelling such electron beam-
specimen interactions.

The dependence of the backscattered electron yield on the accelerating voltage and the
atomic number is illustrated in the figures below.

Variation of as a function of atomic number.
|
\
|
2
sin
4
2
Z
d
d
11

Variation of backscattered coefficient, , as a function of beam energy.

The yield of backscattered electrons is also dependent on the angle of incidence of the
electron beam on the specimen surface. Empirically, we can express this dependence
as
(2.2)

where is the tilt angle and (Z, 0) is the value of at zero tilt angle ( (Z, 0) ~ 0.25
from example below).

Variation of with tilt angle.
Beam energy (keV)

Tilt angle (deg.)

( )
( )

cos
89 . 0
0 ,
89 . 0 , |
\
|
=
Z
Z
12

Angular distribution of BSE for different incident beam directions.

2.3 Secondary electrons

At the other end of the energy spectrum, low energy secondary electrons (SE) are
generated as a result of the excitation of the loosely bound atomic (valence) electrons.
The energy of secondary electrons lies in the range 0-50 eV. The secondary electron
yield, , can be related to the primary energy of the incident electron, the number of
outer shell electrons and to the atomic radius. The angular distribution is similar to that
for BSE.

The probability of escape of a secondary electron,

where z is the depth from the surface and is the mean free path of the secondary
electrons. For metals ~ 5 and for insulators 100 . Thus, nearly all of the
secondary electrons that escape originate near the specimen surface.

As the primary beam energy increases, the number of secondary electrons generated
increases, but more are generated deeper in the sample, and therefore the secondary
electron yield actually falls (for incident electrons of energy greater than 2 3 keV)
with increasing beam energy.

(2.3)

5 kV 20 kV 50 kV
Al 40% 10% 5%
Au 70% 20% 10%

( )
z
e p
8 . 0
E
13
2.4 Specimen charging

At energies > 2 - 3 keV, the total electron yield + < 1, i.e. more electrons enter the
specimen than leave it by backscattering and secondary electron emission.

The total electron yield, + is dependent on the incident beam energy
The backscattered yield, , is always smaller than 1
The secondary electron yield, , shows a peak at ~ 2 - 3 keV and then decays
rapidly with increasing beam energy
This results in a peak in the total electron yield that rises above 1

Schematic diagram illustrating the effect of accelerating voltage on the total electron
yield.

If there is a good conducting path to earth, a current flows within the specimen to enable
the specimen to remain electrically neutral. However, if the specimen is an insulator,
the surface may become charged:

For + = 1 No specimen charging occurs
+ < 1 The number of electrons that enter the specimen is larger
than the number that leave
Specimen develops a negative charge
+ > 1 The number of electrons that enter the specimen is smaller
than the number that leave
Specimen develops a positive charge

At low energies it is possible to choose an accelerating voltage where + = 1 to give
conditions where the specimen (even if insulating) will not charge. Modern SEMs are
optimised to operate in this low energy range.

E
1
E
2
+
1
Accelerating
voltage
14
2.5 Detecting electrons

The detection system for electrons in the SEM depends on the energy of the electrons
emitted from the specimen.

Energy distribution of the secondary (S) and backscattered (B) electrons generated by
an incident electron beam of energy E
0
.

2.5.1 Backscattered electron detection

Two types of electron detector are commonly used to collect the high-energy BSE
emitted in an SEM.

(a) Scintillator detector
These are composed of a scintillator (phosphor) with a light pipe and a
photomultiplier. They have a fast response time and high gain, which makes them
suitable for use at TV rates. However, they are bulky and may restrict the working
distance of the microscope.

(b) Solid state detector
These comprise of a Si p-n junction which forms electron-hole pairs on the
impingement of a BSE. These are separated by the application of a reverse bias
across the junction, giving a detectable current. The detector is much smaller than a
scintillator, and therefore can be permanently attached to the objective lens without
obstructing normal microscope operation. These detectors are cheap to make, but
their slow response time makes them unsuitable for operation at TV scan rates.

Schematic diagram illustrating (a) a scintillator and (b) a solid state BSE detector.
15
2.5.2 Secondary electron detection

The secondary electron signal is detected using an Everhardt-Thornley detector, which
is based on a scintillator-photomultiplier system.

Schematic diagram illustrating an Everhardt-Thornley detector.

The energy of the secondary electrons is too low to be detected directly, and therefore
they are accelerated by applying a bias of ~ +10 kV to a thin Al film on the scintillator.
A collector grid which is biased to ~200 V is also used to attract the secondary electrons
This collector screens the scintillator from the incident beam and improves the
collection efficiency of the detector.

When the secondary electrons strike the scintillator, light is produced that is guided into
a photomultiplier. The light is converted into pulses of electrons which are amplified
and used to modulate the intensity on a CRT.

16
3 Image formation

3.1 Topographic images

One of the principal uses of an SEM is to form an image of the surface topography.

For both SE and BSE the yield is at a minimum when the specimen is perpendicular to
the beam ( = 0
o
). As the specimen is tilted, electrons are more likely to be scattered out
of the specimen rather than further into it.

For SE

where
0
is the yield at = 0
o
and is the tilt of the specimen. To improve topographic
contrast specimens are often tilted 20 - 40
o
towards the detector.

We can draw an analogy between
topographic imaging in the SEM and
imaging with light:

(a) Diffuse and (b) direct illumination
with light, viewed from above.

Secondary electron imaging (c) is
equivalent to (a).

Backscattered electron imaging (d) is
equivalent to (b).

Topographic images formed using secondary electrons.
sec
0
=
17
Topographic images formed using BSE will, by analogy to viewing an object with
direct light, contain many more shadows than an equivalent image formed using SE as
they are formed only by BSE that are emitted towards the detector, i.e. line of sight
BSE. The multi-element nature of the backscattered detector allows the topography of
almost flat specimens to be enhanced by looking at a difference signal.

The sampling volume for BSE is much larger than that for SE, and therefore the spatial
resolution is much lower.

3.2 Compositional images

The secondary electron signal is not very sensitive to composition, but may be affected
by the surface condition and the electronic structure of the material.

The backscattered electron yield, , is strongly dependent on the atomic number and is
almost independent of the accelerating voltage (see 2). It is found empirically that for
an element of atomic number, Z, the backscattered yield can be calculated using

(3.1)
The backscattered yield for a compound can be calculated using a rule of mixtures
based on weight fraction, i.e.

(3.2)

where W
x
refers to the weight fraction of element x. The atomic number contrast, C,
can be determined between two phases or elements using

(3.3)

Phase 1 Z
1
Phase 2 Z
2

1

2
Contrast
(%)
Al 13 Mg 12 0.153 0.141 7.6
Al 13 Cu 29 0.153 0.304 49.4
Al 13 Pt 78 0.153 0.485 68.4
Cu 29 Zn 30 0.304 0.310 2.3
-brass 29.4 -brass 29.5 0.305 0.306 0.2

The contrast is, in general, relatively small and therefore to obtain good compositional
images the surface topography must be kept to a minimum by polishing to a fine finish.
Unetched, polished metallographic specimens are ideal.

For compositional images (formed using BSE), the signals from the two (or four) solid
state detectors are added, e.g. A+B, to optimise the contrast arising from different
backscattered yields across the specimen. If the contrast is low (e.g. brass), then a
high beam current is required to maximise the signal, and therefore the spatial
resolution is reduced.

3 7 2 4
10 30 . 8 10 86 . 1 016 . 0 0254 . 0 Z Z Z

+ + =
( )
2 1 1 1
1 W W
compound
+ =
1
2 1

= C
18

Backscattered images from a polished silver soldered joint
(a) Topographic contrast arising from different abrasion resistance obtained from the
difference in the signals received by detectors A and B
(b) Compositional contrast showing atomic number Z differences obtained from the
sum of the signals in detectors A and B.

(a)
(b)
19
3.3 Crystallographic images

3.3.1 Channelling contrast

The backscattered coefficient, , for a crystalline specimen, is dependent on the
orientation of the electron beam with respect to the crystal. This effect is known as
channelling.

Channelling contrast is low and may only be obtained satisfactorily from a specimen
with a surface that is free from large surface deformations. The beam must be
reasonably parallel (by using a small aperture and a large working distance). A large
current is required to obtain reasonable contrast, but this results in poor spatial
resolution

BSE intensity as a function of crystal orientation (rocking curve) for Si at 30 kV

Crystallographic channelling contrast from fine grained material. Such contrast is very
sensitive to the specimen tilt

20
3.3.2 Diffraction patterns

The orientation of a crystal can be determined from a selected area channelling pattern
(SACP). By varying the angle of the incident beam, the variation in backscattered
electron yield, , can be mapped out as a function of angle, thereby forming a SACP.
The electron beam is scanned through a rocking angle whilst staying focused on a single
area of the specimen. However, due to aberrations in rocking the beam, the area from
which the pattern is formed tends to be quite large (~13 m), and can be larger than a
single grain.

An alternative geometry is also used for obtaining diffraction patterns in the SEM where
the electron beam is fixed at a point, and the backscattered electrons are collected on a
position sensitive detector (e.g. film or CCD camera)
called electron backscattered diffraction (EBSD)
the pattern that is formed is known as an electron backscattered
diffraction pattern (EBSP)

The variation of with angle is recorded directly without needing to rock the electron
beam. The specimen is tilted to 70
o
to increase the backscattered electron yield. This
technique can demonstrate better resolution (~1 m) than SACP.

The series of lines observed in an EBSP are Kikuchi lines and are similar in appearance
to the channelling contrast observed in SACPs. Kikuchi lines are formed by a series of
scattering events in the crystal:
(i) the electrons are inelastically scattered
(ii) they are subsequently Bragg scattered by a series of parallel planes (as
shown schematically in the figures overleaf). If the specimen is thick then
some of the forward scattered electrons will be re-scattered back towards the
surface or will be inelastically scattered again. (For thin specimens, forward
scattered electrons may be seen in a transmitted signal see later in the
course.)

SACP of a grain in a copper specimen
Schematic diagram showing the
formation of a SACP
21

Diagrams showing the origin of Kikuchi lines and the cones of rays due to the
elastic scattering of diffuse inelastically scattered electrons.

By scanning the beam across the sample and recording and analysing the pattern at each
point a data set is produced in which each point can be coded according to its
orientation. This is the basis of orientation imaging microscopy (OIM). Such analysis
can give the position of grain boundaries, twins and show the relative orientation of
each grain to reveal any preferred growth or texture.

3.4 Other imaging modes

Many other images can be formed from signals that arise from the electron beam
interaction. Some are listed below:

(i) Cathodoluminescence (CL) images
These are formed from visible or near-visible radiation that is emitted from a
specimen. This signal is very sensitive to specimen strain and the presence
of defects. CL imaging has been used extensively in the study of diamond,
silicon and other semiconductors.

(ii) Magnetic contrast images
The internal magnetic field in a ferromagnetic specimen will deflect the
electron beam and under certain conditions this can lead to image contrast
which can be used to examine the magnetic structure of the specimen.

(iii) Electron beam induced current images
The specimen current is detected as the beam is scanned across the specimen
surface. This current is sensitive to the electrical properties of the material
and is good for imaging semiconductor junctions, for example.

(iv) Voltage contrast images
The SE yield is altered by the potential of the specimen. This method is
used in the semiconductor industry to examine voltages on interconnects, for
example.
22
4 X-ray microanalysis

The X-ray signal that is emitted from a specimen contains characteristic peaks whose
energy can be related to an atomic transition and thus to a particular chemical species.
Hence X-ray microanalysis can be used to investigate the chemistry of a specimen.

There are two electron-beam specimen interactions that must be considered when using
X-ray microanalysis: core scattering and inner shell ionisation.

Core scattering occurs when an incident electron excites an X-ray without knocking out
an inner shell electron. When this occurs, the electron can lose any amount of energy
(up to its total kinetic energy), and the X-ray is not characteristic of any particular atom.
This is called Bremsstrahlung and leads to a background of X-rays in any electron
generated X-ray spectrum.

Inner shell ionisation gives rise to the characteristic peaks in an X-ray spectrum. The
figure below shows a schematic diagram illustrating the process of X-ray emission by
inner shell ionisation.

Schematic diagram illustrating the ionisation process whereby an inner shell electron is
ejected from the atom by a high energy incident electron. The hole in the K shell is
filled by one from the L shell, and an X-ray is emitted.

If an incident electron beam has sufficient energy to knock an inner shell electron out
into the vacuum, this creates an excited atom in an energetically unstable state. The
atom is relaxed by an electron in a higher energy shell falling into the lower shell and a
photon is emitted. The energy of this photon is the difference between the two energy
levels and will typically be in the X-ray spectrum.

The Auger process may also occur. In this process the emitted photon knocks another
electron out from its shell. These Auger electrons can be detected under UHV
conditions and form the basis of another analytical technique Auger Electron
Spectroscopy (AES).

Energy
E
L3
E
L2
E
L1
E
K
K

L
1
L
2
L
3
Valence band
Conduction band
Vacuum
Characteristic
X-ray
Energy loss electrons
Incident
electron beam
23
Some of the more common transitions are shown in the diagram below. Of the
numerous possible transitions, the strongest are the lines for each series, e.g. K

which is 7-8 times stronger than the K

line.

The electron transitions between the K, L, M, N and O shells leading to K, L and M
characteristic X-ray emission.

24
4.1 X-ray nomenclature

Atomic energy levels can be classified according to their quantum numbers. According
to the Pauli exclusion principle, each electron state has a unique set of quantum
numbers, n, l, m
l
and m
s
.

The principle quantum number, n, describes the quantised energy and gives the
volume of an orbital, with n = 1, 2, 3 etc.

The orbital angular momentum quantum number, l, describes the angular
momentum of an orbital (i.e. its geometry), with l = 0, 1, 2, 3. n-1 (when l = 0, the
orbital is spherically symmetrical and denoted as an s-state)

The magnetic quantum number, m
l
, gives the orientation of the angular momentum of
the orbital, with m
l
= -l, -l+1, -l+2,., 0, ., l-2, l-1, l

The spin quantum number, m
s
, describes the spin of the electron, and can take the
value of +1/2 or -1/2

According to these rules, each electron shell can contain only a limited number of
electrons, because no two electrons are allowed to have the same quantum number
combination,

e.g. the n = 1 shell has a l = 0 electron state (the 1s state) which can be occupied by a
maximum of 2 electrons, one with m
s
= 1/2 and one with m
s
= -1/2

When discussing atomic spectra, it is convenient to define allowed combinations of
quantum numbers as n, l, j and m
j
, where j = l m
s
is the total angular momentum
quantum number, and m
j
= -j, -j+1, -j+2, 0, j-2, j-1, j.

Electrons with the same n, l and j have the same energy (in the absence of an external
field). For each given l, the j state ranks the relative energy of the energy level the
state of lowest j lies lowest in energy.

Allowed transitions between energy levels must obey electric-dipole selection rules:
The principle quantum number must change in order to create an excited
state, n 0
Angular momentum must be conserved l = 1 only
Spin-orbit coupling must be considered j = 0, 1 only

The possible electron transitions and associated X-rays can be assigned quantum
numbers, and the total number of electrons in each level can be specified:
25

X-ray
energy
level
n l j No. of
electrons
s-p-d
designation
K 1 0 2 1s
1/2

L
1
2 0 2 2s
1/2

L
2
2 1 2 2p
1/2

L
3
2 1 3/2 4 2p
3/2

M
1
3 0 2 3s
1/2

M
2
3 1 1/2 2 3p
1/2

M
3
3 1 3/2 4 3p
3/2

M
4
3 2 3/2 4 3d
3/2

M
5
3 2 5/2 6 3d
5/2

The designation of lines in terms of
1
,
2
etc. is a recognition of the relative intensities
of the X-ray lines. The intensities depend on the relative probabilities of the transitions
and the extent to which a particular state is filled with electrons.

4.2 Practical aspects of X-ray analysis

The most efficient production of X-rays generally occurs when the incident electron
beam has about 3 times the energy of the characteristic X-ray of interest. The table in
appendix 1 shows that there is at least one strong characteristic peak for all elements in
the 0 - 10 keV range and therefore there is no problem for an SEM operating at
25 30 kV.

X-rays (perhaps generated by electrons) can themselves excite atoms and generate
further X-rays of lower energy, a process known as fluorescence. It is a rather
inefficient process and only a few % of X-rays are generated in this way, but it can alter
the relative amounts of characteristic radiation generated from alloys and compounds,
particularly if elements of similar atomic number are present, e.g. -brass.

The interaction volume is smallest for low energy electrons and heavy elements. It is
difficult to reduce the sampling volume to less than 1 m
3
without reducing the beam
energy to a level at which few useful X-rays are emitted. The volume of the specimen
from which X-rays are generated is similar to that sampled by the electron beam, but if
fluorescence occurs, then the sampling volume can be larger than the interaction
volume.

The volume analysed and the fraction of X-rays emitted depends critically on
(i) The energy of the electron beam
(ii) The energy of the X-ray studied
(iii) The local atomic weight
Values of the energy and associated wavelengths of the strongest K, L and M lines of
the elements are shown in appendix 1. X-rays are electromagnetic rays that travel at the
speed of light, and therefore E (keV) = 1.24/.
26
4.3 X-ray detection

There are two types of X-ray detector systems using either energy dispersive
spectroscopy (EDS) or wavelength dispersive spectroscopy (WDS).

4.3.1 Energy dispersive spectroscopy (EDS)

This is by far the most widely used detector system. The detector is based on a p-i-n
junction in silicon. Each incoming X-ray creates a number of electron-hole pairs where
the number generated is proportional to the energy of the X-ray.

e.g. each electron-hole pair in Si has an energy of 3.8 eV, and therefore, for example, an
Al K
X-ray will give rise to 392 electron-hole pairs.

By putting the junction under an applied bias, these electron-hole pairs generate a
current, which is amplified and analysed. The junction is doped with Li and cooled to
77 K to ensure that the natural conductivity of the Si does not swamp the X-ray
generated signal.

The outer surface of the detector is normally coated with a polymer film (or Be) to
prevent contamination (mainly hydrocarbons) from condensing onto the cold detector,
but these films absorb low energy X-rays, making EDS detectors very poor at detecting
these.

Each X-ray pulse only lasts for a very short time (~1 s), and the current arising from
the pulse is amplified and passed to a multi-channel analyser which decides into which
of the 1024 channels to place the signal. The channels typically represent energies in
the ranges of 0-10, 0-20 or 0-40 kV.

Several thousand pulses can be processed per second, and therefore an EDS spectrum
can be obtained in a short time. The detector resolution is only at best 100 eV, and
therefore fine spectral features cannot be discriminated, and lines from different
elements can overlap.

A typical X-ray spectrum taken on a SEM from the high-T superconductor
Bi-Sr-Ca-Cu-O.
27
4.3.2 Wavelength dispersive spectroscopy (WDS)

If higher energy resolution is required, then wavelength dispersive spectroscopy (WDS)
is used. In WDS, X-ray radiation is filtered such that only X-rays of a certain
wavelength are incident on the detector. The X-rays are filtered using a crystal
spectrometer arranged to allow diffraction to separate the X-rays according to their
wavelength (i.e. using Braggs law).

To count as many X-rays as possible, the sample-crystal-detector geometry must be
engineered to fall on the arc of a circle the Rowland circle. To cover the range of
X-ray wavelengths, typically 4 crystals with different d-spacings are used because the
range of accessible is limited by the geometry of the system.

A crystal X-ray spectrometer for WDS. X-rays are collimated by the two slits S
1
and
S
2
, diffracted by the crystal and focused onto the detector.

Although the energy resolution is excellent (~ 10 eV), the collection efficiency is very
poor (~2% of an EDS system). However, the background intensity is negligible and
very high count rates are possible. Light elements can be detected very easily (unlike
EDS).

WDS systems are generally found on dedicated electron probe microanalysers (EPMAs)
and rarely on conventional SEMs.

Electron
beam
Detector
S
3
S
1
S
2
X-rays
Rowland
circle

R

Curved
crystal

28
4.4 Quantitative X-ray mapping in the SEM

To estimate the amount of an element present in a sample, the number of counts in a
fixed time interval, N
spec
, can be compared with those from a standard of known
composition, N
std
.

If the concentration of an element within a compound is C, then

Each value of N represents the net count in the window of interest (after background
subtraction). For this to hold true, the conditions must be identical when collecting each
N.

However, complications arise because the specimen is unlikely to be a pure element,
and therefore 3 correction factors are needed for
(i) Atomic number (Z)
(ii) Absorption (A)
(iii) Fluorescence (F)
Together, these contributions are known as the ZAF corrections:

k
Z
, k
A
and k
F
all require some knowledge of the specimen concentration, and therefore
the process is iterative. These factors are usually set to a value of 1, and C
spec
is
estimated. This is then used to estimate the k factors and determine a better value for
C
spec
. This refinement usually only takes 3 - 4 iterations.

(i) Z-correction

This is a correction which accounts for the differences in the efficiency of X-ray
generation which depends on

(a) how far the electrons can penetrate the specimen before losing too much
energy to excite X-rays
(b) how many electrons are backscattered without exciting any X-rays.

For analysis of a heavy element in a light element matrix, k
Z
> 1 (and vice versa)
e.g. Sulphur (Z = 16) in stainless steel (mean Z = 27), k
Z
= 0.87

(ii) A-correction

The amount of absorption by a specimen depends strongly on the elements present in a
specimen through their mass absorption coefficient, .
R
e I I

=
0

where I
0
is the intensity at a depth R in the specimen, and I is the intensity of the X-ray
at the surface.

std std
std
spec
spec
kC C
N
N
C = =
std F A Z spec
C k k kk C =
29
It is likely that the specimen and standard will have different absorption coefficients,
and therefore this must be considered when quantifying X-ray emission. The magnitude
of this correction can be large, particularly for K lines of light elements emitted from
specimens also containing heavy elements.

(iii) F-correction

Only a small fraction of high energy X-rays excite low energy fluorescent radiation. It
is an inefficient process but can be important in samples with elements of similar atomic
number, e.g. Cr in Fe (k
F
= 0.85).

To determine these factors accurately, the specimen-detector geometry must be well
characterised, and samples must be polished flat. An accuracy of ~ 3% in EDS and ~1
% in WDS is achievable.

4.5 Artefacts and problems

Three common situations can occur where a false reading of local composition can be
obtained:

4.6 Detectability limits

If the mean background count is B, then assuming Poisson statistics, the noise is B.
We can define a peak as being detectable if it rises above the background by 2B. If the
count rate of the background gives b counts per second, and the counting time is t, the
background count, bt B = , giving a smallest detectable peak height,
( ) bt B P 2 = above the background level.

If p is the peak count rate from the standard of known composition, it follows that the
minimum detectable concentration (MDC) is given by

Therefore,
(weight %)

For most elements, MDC is ~ 0.1% for EDS and ~0.01% for WDS
In a region apparently
consisting only of
element A, an area of
element B below the
surface can emit B X-
rays.

Near the boundary of A
and B, both types of X-
ray are excited even
though the beam is
focused onto the surface
of A.
In a rough specimen (e.g.
fracture surface), B X-
rays can be excited by
fluorescence from the A
region.
( )
( ) ( )t b p
bt
B P
B P
MDC
std
spec

=
100 2
100
( ) t b p
b
MDC
=
200
30
4.7 X-ray mapping

If the electron beam is scanned across the specimen surface and an X-ray spectrum is
acquired at each point then a 2-D map can be built up. Subsequent data analysis would
allow the chemical composition and distribution of elements to be determined to high
spatial resolution. Many signals can be acquired at once, allowing a multi-dimensional
data set to be acquired containing X-ray spectra, backscattered and secondary electron
information.

Digital X-ray maps obtained
simultaneously from a polished
specimen of an alloy (the data were
acquired in 60 mins.).
(a) Si K

(b) Mo L

(c) Cr K

(d) Co K

(e) Detail of (d) showing the
individual pixels.
(f) Backscattered image of the
same area.
31
Transmission electron microscopy

5. Introduction

The upper half of a TEM is very similar to an SEM. There is an electron gun, an
accelerating voltage (now much larger, typically 100 - 400 kV) and electron lenses to
control, collimate and focus the electron beam. There is a condenser aperture that has a
similar function to the objective aperture in the SEM. In an SEM the final lens before
the specimen focuses the electron beam onto the surface. In the TEM, the specimen is
very thin, and the objective lens is placed after the specimen where it is used to form an
image from the electrons that have passed through the specimen. In a TEM, the first
condenser lens is typically used to adjust the spot size and the second condenser lens is
used to either form a focused probe on the specimen surface (as in SEM) or a parallel
beam (for conventional TEM imaging).

There are many additional lenses and apertures in a TEM (as illustrated below) which
do not have an analogue in an SEM. These will be described in 3.

A cross-section through a modern analytical TEM showing the main components and a
number of detectors.

If scan coils are fitted to the TEM then it can be used as a high voltage, high resolution
SEM if detectors are fitted to examine the backscattered and secondary electron signals.
32
If the transmitted signal is detected from a TEM with a scanned probe, then we call the
mode of operation scanning transmission electron microscopy (STEM).

Many different signals are generated in a TEM (as illustrated on p 9), and if we examine
a thin specimen, the elastically and inelastically scattered electrons that are transmitted
can be analysed to deduce the chemical and physical properties of the specimen.
However, to obtain the high resolution that is often required in a TEM, the specimen
must be placed within the objective lens, and this limits its maximum size, usually to ~3
mm in diameter, and 1 mm in depth (although the area of interest must be much
thinner). A variety of holders are available for inserting the specimen into the TEM,
including straining, heating and cooling stages.

A variety of TEM specimen holders

5.1 Specimen preparation

For TEM we need a specimen that is electron transparent with a thickness and geometry
that are suited to the analysis required. Specimen thicknesses are typically in the range
of 10 - 300 nm depending on choice of material and technique required.

Many different sample preparation techniques are available to prepare such thin
membranes, however none is particularly easy! These include argon ion beam thinning,
mechanical polishing, electropolishing and focused ion beam milling.

Most of these techniques thin a circular disc of material in the centre at a shallow angle
until a hole just forms. The area surrounding the hole is usually electron transparent.

A cross-section through a conventionally thinned specimen

If the material is conducting, electropolishing can be used. However, if the material is
insulating or semiconducting, or if it has a composite structure with different
electrochemical potentials (which would selectively electropolish), then argon ion
thinning is often used. In this method, a low energy beam of argon ions is fired at a
33
low angle at the centre of a rotating disc of material to sputter away material and create
a region of electron transparency.

However, many examples of materials analysis now requires the preparation of a
membrane at a particular point in a specimen, for example a gate structure in a
semiconductor device, quantum dots, or targeting a particular grain in a material.
Focused ion beam (FIB) milling allows a specimen to be imaged (using secondary
electrons) and milled simultaneously to select exactly the area required for TEM
examination. The beam is typically formed of Ga
+
ions that are accelerated to
~ 5 - 30 kV and these are used to sputter material to leave a thin membrane suitable for
TEM examination lying in the area of interest.

(a) A SE image taken in a FIB workstation of a trench prepared in a silicon wafer with
three different thickness membranes separated by trenches (b) A silicon MOSFET
device prepared and imaged in the FIB (c) A SE image taken in a FIB workstation of a
Al polycrystalline film on a Si substrate.

(a) (b)
(c)
34
6. Beam-specimen interactions

The transparent nature of specimens examined in the TEM means that electrons that
have been forward scattered can be detected, and these are the basis of most TEM
analysis. The high accelerating potential means that most of the electrons are scattered
in the forward direction or unscattered by the specimen, with only a very small fraction
being backscattered for typical TEM specimen thicknesses.

The electrons that are transmitted by the specimen can be scattered or unscattered. The
electrons that are scattered can be elastically scattered or inelastically scattered (if we
think of them as particles), and they can also be termed as coherent or incoherent (if we
think of them as waves).

Elastically scattered electrons are usually coherent (i.e. in phase with the incident,
unscattered electron wave) in thin specimens, and are scattered to small angles (1
o
- 10
o
)
in the forward direction. At higher angles, elastic scattering becomes incoherent.

Inelastically scattered electrons are almost always incoherent, and are scattered to low
angles (<1
o
). For thick specimens (e.g. in the SEM) more electrons are backscattered
and incoherent than for thin specimens in the TEM.
(N. B. Kikuchi scattering is an inelastic, incoherent scattering event followed by an
elastic, coherent event.)

6.1 Fundamental properties of electrons

An electron can act as both a wave and a particle, and the TEM utilises both
characteristics. Typical electron beam current is 0.1-1 A (~ 10
12
electrons passing
through the specimen plane each second). Each electron is separated by about 160 m,
which is larger than the thickness of TEM specimens, and therefore there is never more
than one electron in the specimen at any one time. We know that we can see diffraction
effects in the TEM, which arise from electron-electron interactions, and this indicates
wave-like nature of electrons.

Wave particle duality (de Broglie) gives

The momentum of an electron is attained by accelerating through a potential, V to give
kinetic energy
(6.1) (6.2)

But electrons travel at relativistic speeds, and therefore we must consider the
relativistic mass,
0 0
m m , where is the relativistic correction
2
1
1
|
\
|
=
c
(6.3)
0
2
2m
p
eV =
p
h
=
= electron wavelength
h = Plancks constant
p = particle momentum (= mv)
eV m
h
0
2
=
35
This gives a relativistic wavelength for electrons,
|
|
\
|
+
=
2
0
0
2
1 2
c m
eV
eV m
h

(6.4)

A typical electron wavelength is 0.0025 nm for 200 kV electrons.

6.2 The atomic scattering factor

The atomic scattering factor, f
el
() is a measure of the amplitude of an electron wave
scattered from an isolated atom. For X-rays,
( ) ( ) ( ) r K.r d i r
mc
e
f
atom
X

= 2 exp
2
2
(6.5)
where (r) is the electron charge density in the crystal and K is the scattering vector in
reciprocal space, with |K|=2sin/.
For electrons,
( ) ( ) ( )
x
f Z
h
e m
f |
\
|
=
2
2
2
0
sin 2
(6.6)
where Z is the atomic number. The first term in the brackets is due to Rutherford
scattering from the nucleus and the second term is due to scattering from the electron
cloud.

Atomic scattering factors plotted as a function of sin/

6.3 Scattering from a unit cell

We can examine scattering from a crystalline solid by considering scattering from each
unit cell. We simply add up each atomic contribution but must take into account the
relative positions, r
i
, of the atoms (relative to an origin) using a phase factor 2(K.r
i
),
where K is a diffraction vector. This is called the structure factor, F(), and is given by

( ) ( ) ( )
i
i
i
i f F K.r 2 exp =

(6.6)

36
In general we are only interested in the value of F at the reciprocal lattice points, i.e. for
K = g, and so we would normally write

( ) ( )
i
i
i g hkl
i f F F g.r 2 exp = =

(6.7)

The potential of the crystal as seen by the electrons can then be written as
( ) ( )
i
g
g
i F
e m
h
V g.r r
2 exp
2
0
2
=

(6.8)

The choice of a non-primitive Bravais lattice (e.g. F or I) means that, for certain
reflections, F
hkl
= 0. For example, in Cu (c.c.p.), F
hkl
= 0 unless h, k and l are all odd or
even.

A quantity related to the structure factor is the extinction length,
g
, given by

g
C
g
F
V
cos
= (6.9)
where is the Bragg angle and V
C
is the volume of the unit cell. For example, for
100 kV electrons,
111
(Au) = 159 ,
111
(Si) = 602 and
111
(Ge) = 430 .

6.4 Elastic scattering from a perfect crystal

Consider elastic scattering from a crystal unit cell in the far-field condition (with
parallel illumination by the incident electron beam). If we define the wave vector
K = k-k, with |k| = |k| =1/. The path difference between the two scattered waves
from O and B is (OC-DB) = (K.r)., leading to a phase difference of 2(K.r).

Thus, if r is a lattice vector, such that r
n
= n
1
a+n
2
b+n
3
c where n
1
, n
2
and n
3
are integers,
we find that for constructive interference K.r
n
= N, where N is an integer. This is the
Laue criterion, which is equivalent to Braggs law in reciprocal space.

37
6.5 Polycrystalline materials

Diffraction from polycrystalline materials, assumed to be a set of randomly oriented
polycrystals, can be described by rotating the reciprocal lattice about all axes to produce
a set of nested spheres. When intersected by a relatively flat Ewald sphere, we get rings
of reflections. If the specimen is textured, the nested spheres will break up into sections
of preferred orientation, and this will lead to arcs of intensity in the diffraction pattern.

6.6 Amorphous materials

A diffraction pattern from an amorphous material will also be a ring pattern, but the
rings will be diffuse. The Fourier transform of such a pattern can reveal the radial
distribution function (rdf): the probability of finding an atom at a certain distance away
from another. The diffuseness of the rings indicates the lack of long-range order.

7. Image formation

The lenses and apertures in a TEM can be used in different ways to form either an
image or a diffraction pattern.

Ray diagram illustrating the action of the post-specimen lenses to form either an image
or a diffraction pattern on the viewing screen.
38
7.1 Bright field and dark field image formation

The objective lens focuses the scattered beams into the back focal plane and forms a
diffraction pattern in that plane. As we will see later, typically an image is formed with
a number of beams (often only one) selected using an objective aperture which is placed
in the back focal plane of the objective lens. Only those beams are then used to form an
image. The intermediate and projector lenses magnify the image onto the viewing
screen so that the plane of the viewing screen is conjugate with that of the image.

Ray diagrams illustrating how the objective lens and aperture are used to produce (a) a
bright-field (BF) image, (b) a dark-field (DF) by displacing the aperture and (c) a DF
image by tilting the beam. The microscope alignment in (c) is preferred to (b) because
the beam of interest passes along the optic axis and will be less susceptible to lens
aberrations.

(a) (b) (c)
39
7.2 Diffraction pattern formation

To view a diffraction pattern on the viewing screen the intermediate lens (and very
weakly the projector lens) is changed so that the plane of the screen is now conjugate
with the back focal plane of the objective lens. A selected area (SA) aperture is inserted
in a plane that is conjugate with the specimen plane and is used to select the area from
which the diffraction pattern is formed. The SA aperture is demagnified back to the
specimen plane by ~50 times so that a 50 m aperture selects a region of only 1 m in
size.

Ray diagram showing (a) selected area and (b) convergent beam electron diffraction
(CBED)

If the electron beam is focussed to a spot on the specimen a convergent beam electron
diffraction pattern is formed in the back focal plane of the objective lens. This is often
called micro- or nano-diffraction as the volume of the specimen sampled by the electron
beam is much smaller than conventional SA diffraction. The diffraction pattern is
composed of discs (rather than spots) and the detail within the discs is sensitive to the
crystal symmetry and to any strain in the crystal arising from defects.

(a) SAED and (b) CBED pattern from <111> axis of Si taken at 200 kV.

(a)
(b)
40
7.3 Excitation error and finite crystals

An electron passing through a crystal may be unscattered, it may undergo one scattering
event or many. For the purposes of analysing the intensity present in images and
diffraction patterns, it is useful to make an approximation of single scattering, called the
kinematic approximation. In this approximation, the intensity of a reflection in a
diffraction pattern, I
g
|F
g
|
2
. In general this approximation is not valid, but much of the
contrast seen in TEM images can be described (at least qualitatively) within this
approximation. Unless stated otherwise, this approach will be used for the following
analysis.

A TEM sample can be approximated to a rectangular parallelpiped with sides of length
A, B and C:

If we consider the amplitude of a scattered electron wave,
g
, and sum over all of the n
unit cells within a crystal, then
n
i
n
g g
e F
K.r
2
=
(7.1)
where F
n
is the scattering amplitude from the nth unit cell and r
n
= n
1
a + n
2
b + n
3
c and
n
1
, n
2
and n
3
are integers.

In general, the reflection g from which an image is taken does not lie exactly on the
Ewald sphere but slightly away from it. We can define the scattering vector, K = g + s
for some small value of s that describes the deviation of the vector of the selected
diffracting beam g from the Ewald sphere. Thus we can redefine the scattered
amplitude as
( )
n n
i
n
g
i
n
g g
e F e F
s.r .r s g
2 2 +

= = (7.2)
since all the g.r
n
are integers. Approximating the summation to an integral (since s is
small and slowly varying),
3 2
1
r
s.r
d e F
V
crystal
i
g
C
g
n
(7.3)
Defining r = xa + yb + zc and s = ua* + vb* + wc*, the integral may be evaluated to
show
( ) ( ) ( )
w
Cw
v
Bv
u
Au
V
F
C
g
g
sin sin sin

= (7.4)

The intensity distribution (the shape of the diffraction spot) is given by I = |
g
|
2
and is
a sinc
2
function.
C
A B
41

The intensity distribution along w for u = v = 0. The FWHM w ~1/C where C is the
specimen thickness (defined in the diagram above).

Schematic diagram showing the scattering geometry for a thin film normal to the
incident electron beam. The spike represents the central peak in the sinc
2
function and
shows how that function is mapped out as s varies.

Thus, as the crystal is tilted, the Ewald sphere sweeps through the Bragg condition from
s to + s (or vice versa).

N. B.: The sign of s can be determined using Kikuchi lines (that are generated in a
similar way as in the SEM), as illustrated in the diagram below.

Consider again the parallelpiped and let B and C . Then, for a crystal of thickness t
(i.e. A = t) and for s perpendicular to the crystal surface and perpendicular to g, we find
(for s = |s| = w)

( )
( )
2
2
2 2 2
2
sin
cos
) , (
s
ts
V k
F
t s I
B C
g
g
= (7.5)

C
1
C
2
C
1
C
2
0
w
w ~ 1/C

42
This can be re-expressed in terms of the extinction length,
g
,
( )
( )
2
2
2
sin
) , (
s
ts
t s I
g
g
|
|
\
|
= (7.6)
In this kinematic 2-beam condition, only a single diffracted beam is strong. If the
intensity of the diffracted beam is I
g
, then we can say that the intensity of the
undiffracted beam, I
0
= 1-I
g
(for an incident beam of unit intensity), and it is assumed
that I
0
>> I
g
.

7.4 Breakdown of the kinematic approximation

If we examine the 2-beam condition as we approach the exact Bragg condition,
i.e. s 0, then we see from equation (7.6) that
2
|
|
\
|
g
g
t
I
.
If t >
g
/ then I
g
> 1, and this is absurd! The kinematic approximation is valid at large
values of s, but at small values of s we must use the more exact, dynamical form of
equation (7.6):
( )
( )
2 2 2
2 2 2
2
sin
) , (
+
|
\
|
+
|
|
\
|
=
g
g
g
g
s
s t
t s I

(7.7)

( )
( )
2
2
2
sin
) , (
s
ts
t s I
g
g
|
|
\
|
=
( )
( )
2 2 2
2 2 2
2
sin
) , (
+
+
|
|
\
|
=
g
g
g
g
s
s t
t s I

Plots of intensity as a function of deviation parameter, s, close to the Bragg condition
for both the kinematic approximation and dynamical theory for a specimen of fixed
thickness.

N. B. For the dynamical theory at s = 0:
|
|
\
|
=
g
g
t
I
2
sin and I
g
= 0 when t/
g
= n, an integer.
43
7.5 Bend contours

For a thin TEM specimen of approximately constant thickness, if it is bent or buckled
(e.g. like a saucer or a saddle) then bend contours are observed in the TEM. The
intensity observed in a TEM image can be described using equation (7.6) as the
deviation parameter, s, varies with the bending of the specimen.
(a) Schematic diagram showing scattering at the Bragg angles from a thin, bent
specimen. (b) A bright field image taken from a bent Al crystal near the [215] axis
illustrating strong scattering when the planes are bent at the Bragg angle.

End-on
(hkl)
plane
sg< 0
sg= 0 sg= 0
Increasing
sg
Increasing
sg
{hkl}
planes
{hkl}
planes
Diffracted
beams
-G G 0 -2G 2G
(a)
(b)
44
7.6 Thickness fringes

Thickness fringes are very commonly observed in the TEM because most specimens are
very shallow wedges (from the thinning process). The intensity of the diffracted beams,
I
g
, oscillates as a function of t (s is fixed for a given specimen orientation).

(a) At the Bragg condition, intensities of the direct and diffracted beams oscillate in a
complementary fashion.
(b) For a wedge shaped specimen, the fringe separation shown in (c) is determined by
the wedge angle and the extinction distance
g
.
(d) A BF image of thickness fringes. The arrows mark the position of the specimen
edge.

As above, for the dynamical theory at s = 0:
|
|
\
|
=
g
g
t
I
2
sin and I
g
= 0 when t/
g
= n, an integer. Therefore, the intensity in the dark
field image is a minimum when the thickness, t, is an integer number of extinction
lengths for a given diffraction condition.
(a) (b)
(c) (d)
45
7.7 Contrast from imperfect crystals

7.7.1. Stacking faults

Illustration of a stacking fault running across a specimen causing a displacement R
between the two parts of the crystal.

The stacking fault introduces a relative shift, R, between the atomic positions of the two
regions of crystal that bound the fault, i.e. r
n
= r
p
+ R, where r
p
is the perfect crystal.
This creates a phase shift between the electron beams above and below the stacking
fault and leads to an image composed of fringes whose intensity distribution is given by
( )
( )
(
\
|
+
|
\
|
\
|
+
|
\
|
+ = sz ts ts
s
I
g
g
2 cos
2
sin
2
sin 2
2
sin
2
sin
1
2 2
2
(7.8)

where z is the distance from the specimen centre to the fault and is the phase shift
given by = 2g.R. Therefore, for a fixed s, t, and R, the image is composed of fringes
with a periodicity of z = 1/s.

(a) BF and (b) DF images of a stacking fault with = 2/3 in a Cu-Al alloy near the
<101> zone axis

The stacking fault is invisible if g.R = 0 or an integer value. Thus, R can be determined
experimentally by finding DF images using three linearly independent g vectors that
show no stacking fault contrast.

(a) (b)
[ ] 1 1 1 g [111]
- -
[020]
[101]
-

Fault
plane
Crystal 1
Crystal 2
R
Column is displaced
by distance R
46
[The form of equation (7.8) can be appreciated by imagining the propagation of the
electrons through thin slices of the crystal. After propagation through thickness t, the
amplitude of the scattered wave can be expressed (following equation (7.1)) as
( )
( ) ( )
r
r
r R s g
r s g
d e
d e
p
n
i
i
g
+ +
+
2
2
(7.9)
If R = 0 for t < t
1
(the depth of the stacking fault at the position of interest), and if we
ignore the small term s.R, letting s.r
p
= sz then we can express equation (7.9) as

dz e e dz e
t
t
i isz
t
isz
g

+
1
1
2
0
2
(7.10)

As before, the intensity, I
g
|
g
|
2
, and from this equation (7.8) can be obtained.

7.7.2. Dislocations

Contrast arising from the presence of dislocations in a crystal can be interpreted in a
similar way to that for stacking faults. The displacement vector, R, varies as a function
of position with respect to the dislocation.

For a screw dislocation:

The phase angle is given by = 2g.R, where

(7.11)

If g.b = 0, = 0 and the dislocation is invisible. As with stacking fault contrast, b can
be determined by using three different dark field images with 3 linearly independent g
vectors that show no dislocation contrast.

R
x
y
t
z

u
b b is the Burgers vector
u is the line vector
For a screw dislocation, b // u
For an edge dislocation, b

u
|
\
|
= =
x
y z
1
tan
2 2
b
b R
47

Two BF images taken with different diffraction conditions (a) g = 2 00 and (b) g = 31 3
of screw dislocations in Si.

Edge dislocations are not as straightforward because even if g.b = 0, then there might
still be some component of displacement causing diffraction from a g.(bxu) term.

A schematic illustration of the distortion of a crystal structure around a dislocation core.

On one side of the dislocation, the planes might be bent closer to the Bragg condition
(i.e. s is smaller) such that the intensity, I
g
is higher than the background. On the other
side of the dislocation, the planes would be bent away from the Bragg condition,
therefore I
g
~ I
background
.

Schematic diagram illustrating the position of the dislocation image as a function of the
sign of g and s.
b
u
bu
Dislocation
core
Image line of the
dislocation
48
If the crystal is tilted through the Bragg condition, the distorted planes sweep through
the Bragg condition, and the bright image of the dislocation moves from one side of the
dislocation core to the other. Reversing either g or s will reverse the position of the
image of the dislocation relative to the dislocation core.

We can also observe contrast from dislocation loops, where the Burgers vector b is
constant but the dislocation line, u, varies around the loop. Thus, even if g.b = 0 we see
some contrast except for the positions where g.bxu = 0, where no contrast would be
observed.

7.8 High resolution TEM (HRTEM)

So far we have generally considered images formed from one beam, either a diffracted
or undiffracted beam, and these are examples of amplitude contrast. If more than one
beam is selected in the objective aperture, interference between these beams leads to
image contrast arising from phase differences between the beams. High resolution
images are formed by using the objective aperture to select two or more beams in the
back focal plane of the electron microscope.

If we consider a two beam-condition at exactly the Bragg condition (s = 0), i.e the direct
unscattered beam 000 and one diffracted beam, g, which can be described as plane
waves, ( ) k.r i A 2 exp
1
= and ( ) .r k' 2 exp
2
i B = , then the intensity of the image
formed is given by
g.r 2 sin 2
2 2
AB B A I
g
+ = (7.12)
where r is a real space vector, A and B are the amplitudes of the two waves (assuming
that they are real) and g = k-k. Therefore in the image we see a sinusoidal oscillation
in intensity with a periodicity r = 1/|g|.

If we include an array of reflections centered on the 000 beam, the image formed will be
a cross-grating of sine fringes generated by the interference between all the beams
included in the aperture. These lattice fringes are not necessarily direct images of the
structure because the phase relationship between the beams is distorted by the
aberrations of the lenses.

g
In the
image
plane:
Fringe spacing
1/|g|
In the
back focal
plane:
49
Mathematically, if the object is described by a function, g(r) and the image by f(r), then

) ( ) ( ) ( r r r h g f = (7.13)

where h(r) is a real space function that describes the effect of the electron lenses as it
transmits the information. In Fourier space, equation (7.13) becomes

) ( ) ( ) ( u u u H G F = (7.14)

where H(u) is the contrast transfer function of the electron lenses (mainly dependent on
the aberrations in the objective lens), and can be expressed

) ( ) ( ) ( ) ( u u u u B E A H = (7.15)

where A(u) is the aperture function (there is no information transmitted beyond
the edge of the objective aperture)
E(u) is the envelope function (attenuation of high frequency information)
B(u) is the wave aberration function

( ) [ ] u u i B = exp ) ( (7.16)
where
4 3 2
2
1
) ( u C u f
s
+ = u (7.17)
f = defocus. If f < 0, the image is underfocussed, if f > 0, the image is overfocussed.

A characteristic quantity for the resolution of an electron microscope is the objective
lens transfer function, T(u), often referred to as the contrast transfer function.

A plot of sin (u) for a 300 keV microscope with C
s
= 0.6 mm at Scherzer defocus.

u [nm
-1
]
sin(u)
50
The contrast observed in a HRTEM image depends strongly on the defocus, f, and
spherical aberration, C
s
, and varies for different beams (i.e. with different u). Image
interpretation is therefore not straightforward! It is found that for a particular defocus,
called the Scherzer defocus, that the image can be interpreted with relative ease. At this
value of defocus, d/du = 0, = -2/3 and

2
1
3
4
|
\
|
=
s
Sch
C
f (7.18)
which leads to a resolution limit,
( )
4
1
3
66 . 0
s Sch
C r = (7.19)

HRTEM image of a double walled carbon nanotube filled with crystalline KI.
51
8. Advanced TEM

8.1 Microanalysis in the TEM and STEM

8.1.1. Energy dispersive spectroscopy (EDS)

As in SEM, the X-ray signal generated by the electron-specimen interaction can be
detected using an EDS system. However, the geometry of the objective lens restricts
the collection angle of the EDS detector and therefore X-ray detection is very poor in
the TEM. The generation volume for X-rays is also significantly reduced in the thin
TEM specimens, therefore giving fewer X-rays but higher resolution, which is
described using the beam spread, B (in nm):

2
3
2 1
198 . 0 t
A E
Z
B
|
\
|
=
(8.1)

where Z is the average atomic number of the specimen, is the density (in g cm
-3
), E is
the incident beam energy (in keV), A is the average atomic weight and t is the thickness
of the specimen (in nm).

To perform EDS in the TEM, the beam is normally focussed to a fine spot. In modern
TEMs this can be ~ 0.5 nm, and this is scanned in a raster to produce X-ray line scans or
maps at very high resolution. To achieve a sufficient number of counts from such a
small area then a high brightness gun is required (a FEG is ideal).

STEM X-ray maps taken near a carbide particle in a Al-Ni-Ti alloy

If the film is sufficiently thin, then the three ZAF corrections can be replaced by a single
k factor, such that

B
A
AB
B
A
N
N
k
C
C
= (8.2)

where C
X
is the weight fraction of the element X and N
X
is the number of counts
detected. Normally k is determined experimentally with respect to a common element
such as Si so that
(8.3)

BSi
ASi
AB
k
k
k =
52
8.1.2. Electron energy loss spectroscopy (EELS)

If an inelastic scattering event occurs to an electron passing through a specimen, the
electron loses energy. This energy loss can be measured by using a magnetic field to
deflect the electron beam. Electrons of different energies will be deflected through
different angles and therefore by using either a slit to select electrons of a particular
energy, or a position sensitive detector, the energy loss spectrum from a thin specimen
can be obtained. The electrons are usually detected using a scintillator and diode array
or a CCD camera.

A schematic diagram of an EELS spectrometer for parallel detection (PEELS).

A typical EELS spectrum consists of a zero loss peak (containing elastically scattered
electrons), low loss peaks (mainly valence band excitations) and high energy ionization
edges which correspond to excitations from the inner shell states to the vacuum. The
cross-section for scattering from light elements is large, and so EELS is an excellent
way of detecting light elements such as B, C, N and O which may be difficult to detect
using EDS. The position and shape of the edges are used to determine the chemical
composition of the specimen.

Electron energy loss spectrum obtained from 316 stainless steel.

53
Although it is relatively simple to detect the elements present, it is harder to quantify
their relative proportions within the specimen. If the specimen is sufficiently thin, we
can assume that only single scattering events occur, and therefore some quantification is
possible. We can remove a background count at a particular edge, and calculate the
counts present after the edge, as illustrated below:

Schematic EEL spectrum showing the low-loss region and a single ionisation edge

The elemental concentration, C, can be calculated from
(8.4)

where t is the thickness of the specimen, is the partial cross-section for energy losses
within a range of the ionization threshold, and the other quantities are illustrated in
the diagram above.

The low loss spectrum can be used to determine the electronic nature of the sample, and
a Kramers-Kronig analysis can be used to determine the real and imaginary parts of the
dielectric constant, . The intensity of the EEL spectrum I Im(1/).

EELS can also be used to measure the thickness of a specimen. In most samples,
plasmon scattering is dominant and can be described in terms of Poisson statistics where
the probability of scattering into the n
th
plasmon is given by:
t
n
n
e
t
n
P
\
|
=
!
1
(8.5)
Therefore, by measuring the total spectrum, P = 1, and the zero loss, P
0
= e
-t/
, then the
thickness can be found from
|
|
\
|
= |
\
|
0
ln
I
I t
total
(8.6)
where is a characteristic mean free path for inelastic scattering which can be
determined by other means.

( )
( ) ( )t I
I
C
k
k

=
, ,
,

I
0
I(, , , ,)
I
k
(, , , ,)
I
k
l
(, , , ,)
54
8.1.3. EELS ionisation edge nomenclature

The high energy ionisation edges have a nomenclature that is illustrated schematically
in the diagram below. Some edges, such as the L2 and L3 edges, may not be resolvable
and then are simply called the L2,3 edge. The thresholds for various ionisation edges
are shown in appendix 2.

The range of possible edges and EELS nomenclature arising from inner shell ionisation.

8.1.4. EELS fine structure

The fine structure at the beginning of an edge carries a great deal of information about
the chemical state of the species in question. This means that we can distinguish
between different oxidation states, for example, the fine structure in the Cu L-edge
arising from metallic copper is different from the fine structure seen from Cu
2+
in CuO.
Likewise, we can distinguish between hybridisation states of carbon, as illustrated
below.
55

(a) EELS spectra obtained from CuO (Cu
3d
9
) and from elemental Cu (Cu 3d
10
4s
1
)
(b) C K-edge from a variety of C-
containing compounds.

8.1.5. EDS vs EELS a simplistic comparison for TEM

(a) (b)
56
8.2 Other advanced TEM techniques (a small selection!)

(a) Electron tomography

So far we have only considered imaging specimens in two dimensions in the TEM. By
the very nature of TEM, all images formed are a projection of the properties under
examination through the thickness of the specimen. To characterise the three
dimensional structure of a general object, one single image is generally insufficient. We
use a technique called electron tomography to reconstruct three-dimensional
information from a tilt series of TEM images. Electron tomography has only been
implemented in the physical sciences over approximately the past 5 years due
microscope developments and the need to characterise novel nanoscale 3-D objects
whose properties depend on their 3-D nature, e.g. quantum dots, catalytic structures.

(b) Magnetic imaging

Many recording media including hard discs and tapes use small magnetic regions, and
more recently, discrete single domain nanostructures to store and process information.
The TEM can be used to characterise the local magnetic field to nanometre resolution
within a device. However, standard amplitude imaging techniques cannot be used
because the magnetisation of a device does not alter the amplitude of the electron wave,
it only alters the phase. We must therefore use a phase imaging technique, i.e. we must
interfere more than one electron wave together to form the final image. The most
commonly used techniques are called Fresnel imaging, which allows the interference
between electron waves passing through the specimen by recording an image at a
particular defocus, and electron holography.

(c) Electron holography

The examination of electrostatic and magnetic potentials within specimens is an issue of
significant current interest, with many novel nanoscale materials devices relying on well
characterised properties. It is therefore important to be able to measure these potentials
quantitatively on a nanometre scale. Off-axis electron holography is a TEM-based
technique that uses a biprism to split the electron beam, such that one half of the
electrons pass through the specimen, and the others pass only through vacuum. They
are recombined to form an image, a hologram, which is an interference pattern between
these electrons. This interference pattern can be used to determine quantitatively the
phase change experienced by the electrons passing through the specimen, and therefore
the electrostatic and magnetic potential within the specimen.

(d) Energy filtered TEM

EELS allows us to obtain chemical information at a high resolution by focussing a
probe on the specimen and relating the electron energy losses to particular electronic
transitions and excitations. Energy filtered TEM (EFTEM) uses the same energy losses,
but by using parallel illumination and an energy slit, only electrons that have suffered a
particular energy loss are used to form a 2-D image. A series of images can be acquired
at different energy losses to generate maps of elemental distribution within a specimen.

57
Appendix 1: The Energy and Associated Wavelengths of the Strongest K, L and M
Lines of the Elements.
Atomic Relative
Number Atomic K
1
L
1
M
1

Element Z Mass,
A E(keV) (nm) E(keV) (nm) E(keV) (nm)

Hydrogen 1 1.0
Helium 2 4.0
Lithium 3 6.9 0.05
Beryllium 4 9.0 0.11 11.40
Boron 5 10.8 0.18 6.76
Carbon 6 12.0 0.28 4.47
Nitrogen 7 14.0 0.39 3.16
Oxygen 8 16.0 0-52 2.36
Fluorine 9 19.0 0.68 1.83
Neon 10 20.2 0.85 1.46
Sodium 11 23.0 1.04 1.19
Magnesium 12 24.3 1.25 0.99
Aluminium 13 27.0 1.49 0.93
Silicon 14 28.1 1.74 0.71
Phosphorus 15 31.0 2.01 0.61
Sulphur 16 32.1 2.31 0.54
Chlorine 17 35.5 2.62 0.47
Argon 15 39.9 2.96 0.42
Potassium 19 39.1 3.31 0.37
Calcium 20 40.1 3.69 0.34 0.34 3.63
Scandium 21 45.0 4.09 0.30 0.39 3.13
Titanium 22 47.9 4.51 0.27 0.45 2.74
Vanadium 23 50.9 4.95 0.25 0.51 2.42
Chromium 24 52.0 5.41 0.23 0.57 2.16
Manganese 25 54.9 5.90 0.21 0.64 1.94
Iron 26 55.8 6.40 0.19 0.70 1.76
Cobalt 27 58.9 6.93 0.18 0.77 1.60
Nickel 28 59.7 7.48 0.17 0.85 1.46
Copper 29 63.5 8.05 0.15 0.93 1.33
Zinc 30 65.4 8.64 0.14 1.01 1.23
Gallium 31 69.7 9.25 0.13 1.10 1.13
Germanium 32 72.6 9.88 0.12 1.19 1.04
Arsenic 33 74.9 10.54 0.12 1.28 0.97
Selenium 34 79.0 11.22 0.11 1.38 0.90
Bromine 35 79.9 11.92 0.10 1.48 0.84
Krypton 36 83,8 12.65 0.10 1.59 0.78
Rubidium 37 85.5 13.39 0.09 1.69 0.73
Strontium 38 87.6 14.16 0.09 1.81 0.69
Yttrium 39 88.9 14.96 0.08 1.92 0.64
Zirconium 40 91.1 15.77 0.08 2.04 0.61
Niobium 41 92.9 16.61 0.07 2.17 0.57
Molybdenum 41 95.9 17.48 0.07 2.29 0.54
Technetium 43 98.0 18.36 0.07 2.42 0.51
Ruthenium 44 101.1 19.28 0.06 2.55 0.48
Rhodium 45 102.9 20.21 0.06 2.70 0.46
Palladium 46 106.4 21.17 0.06 2.70 0.44
Silver 47 107.9 22.16 0.06 2.98 0.41
Cadmium 48 112.4 23.17 0.05 3.13 0.39
Indium 49 114.8 24.21 0.05 3.29 0.38
Tin 50 118.7 25.27 0.05 3.44 0.36
Antimony 51 121.7 26.36 0.05 3.60 0.34
Tellurium 52 127.6 27.47 0.04 3.77 0.33
Iodine 53 126.9 28.61 0.04 3.94 0.31
58
Atomic Relative
Number Atomic K
1
L
1
M
1

Element Z Mass,
A E(keV) (nm) E(keV) (nm) E(keV) (nm)

Xenon 54 131.3 29.77 0.04 4.11 0.30
Caesium 55 132.9 30.97 0.04 4.29 0.29
Barium 56 137.3 32.19 0.04 4.46 0.28
Lanthanum 57 138.9 33.44 0.04 4.65 0.27 0.83 1.49
Hafnium 72 178.5 55.78 0.02 7.90 0.16 1.64 0.75
Tantalum 73 181.0 57.52 0 02 8.14 0.15 1.71 0.73
Tungsten 74 183.8 59.31 0.02 8.40 0.15 1.77 0.70
Rhenium 75 186.2 61.13 0.02 8.65 0.14 1.84 0.67
Osmium 76 190.2 62.99 0.02 8.91 0.14 1.91 0.65
Iridium 77 192.2 64.88 0.02 9.17 0.14 1.98 0.63
Platinum 78 195.1 66.82 0.02 9.44 0.13 2.05 0.60
Gold 79 197.0 68.79 0.02 9.71 0.13 2.12 0.58
Mercury 80 200.6 70.81 0.02 9.99 0.11 2.19 0.56
Thallium 81 204.4 72.86 0.02 10.27 0.11 2.27 0.55
Lead 82 207.2 74.96 0.02 10.55 0.12 2.34 0.53
Bismuth 83 209.0 77.10 0.02 10.94 0.11 2.42 0.51
Polonium 84 210.0 79.28 0.02 11.13 0.11 ? ?
Astatine 85 210.0 81.50 0.02 11.43 0.11
Radon 86 222.0 83.77 0.01 11.73 0.11
Francium 87 223.0 96.09 0.01 12.03 0.10
Radium 88 226.0 88.45 0.01 12.34 0.10
Actinium 89 227.0 90.87 0.01 12.65 0.10
Thorium 90 232.0 93.33 0.01 12.97 0.10 3.00 0.41
Protactinium 91 231.0 95.85 0.01 13.29 0.09 3.08 0.40
Uranium 92 238.0 98.42 0.01 13.61 0.09 3.17 0.30
59
Appendix 2: Threshold Energies of Ionisation Edges (in eV) observable by EELS
State 1s 2s 2p
1/2
2p
3/2
3p 3d 4p
Shell K L
1
L
2
L
3
M
23
M
45
N
23

2 He 24.6h
3 Li 55h
4 Be 111h
5 B 188h

6 C 284h
7 N 400h
8 O 532h
9 F 685h
10 Ne 867h 18w

11 Na 1072h 32h
12 Mg 1305h 52h
13 Al 1560h 118h 73d
14 Si 1839h 149h 100d
15 P 2149h 189h 135d

16 S 2472h 229h 165d
17 Cl 2823 270h 200d
18 Ar 3203 320h 246d
19 K 3608 377h 294w
20 Ca 4038 438h 350w 347w

21 Sc 4493 500h 406w 402w
22 Ti 4965 564h 461w 455w 47
23 V 5465 628h 520w 513w 47
24 Cr 5989 695h 584w 575w 48
25 Mn 6539 770h 652w 640w 51

26 Fe 7113 846h 721w 708w 57
27 Co 7709 926h 794w 779w 62
28 Ni 8333 1008 872w 855w 68
29 Cu 8979 1096 951h 931w 74
30 Zn 9659 1194 1043 1020d 87

31 Ga 1298 1142 1115d 105
32 Ge 1414 1248 1217d 125 30
33 As 1527 1359 1323d 144 41
34 Se 1654 1476 1436d 162 57h
35 Br 1782 1596 1550d 182 70d

36 Kr 1921 1727 1675 214 89h
37 Rh 2065 1846w 1804w 239 111d
38 Sr 2216 2007w 1940w 270 134d 20p
39 Y 2373 2155w 2080w 300 160 28p
40 Zr 2532 2307w 2222w 335 181 32p

41 Nb 2698 2465w 2371w 371 207h 35h
42 Mo 2866 2625w 2520w 400 228h 37d
44 Ru 3224 2967w 2838w 472 281h 42d
60
State 3d
3/2
3d
5/2
4p 4d 4f 5p 5d

Shell M
4
M
5
N
23
N
45
N
6
, N
7
O
2
, O
3
O
4
, O
5

45 Rh 312 308d 48
46 Pd 340 335d 50
47 Ag 373 367d 59
48 Cd 411 404d 67
49 In 451 443d 77

50 Sn 494 485d 90
51 Sb 537 528d 99 32
52 Te 582 572h 110 40
53 I 631 620h 123 50
54 Xe 685 672h 147 64

55 Cs 740w 726w 78
56 Ba 796w 781w 93
57 La 849w 832w 99
58 Ce 902w 884w 110
59 Pr 951w 931w 114

60 Nd 1000w 978w 118
62 Sm 1107w 1081w 130
63 Eu 1161w 1131w 134
64 Gd 1218w 1186w 141
65 Tb 1276w 1242w 148

66 Dy 1332w 1295w 154 30, 23
67 Ho 1391w 1351w 161 31, 24
68 Er 1453w 1409w 168 31, 25
69 Tm 1515 1468w 177 32, 25
70 Yb 1576 1527w 184 33, 26

71 Lu 1640 1589w 195 35, 27
72 Hf 1716 1662h 38, 30
73 Ta 1793 1735h 45, 37
74 W 1872 1810h 37, 34 47, 37
75 Re 1949 1883h 47, 45 46, 35

76 Os 2031 1960h 52, 50 58, 46
77 Ir 2116 2041h 63, 60 63, 51
78 Pt 2202 2122h 74, 70 66, 51
79 Au 2291 2206h 87, 83 72, 54
80 Hg 2385 2295h 81, 58

81 Tl 2485 2390h 14p
82 Pb 2586 2284h 21p
83 Bi 2688 2580h 27p
90 Th 3491 3332 83p
92 U 3728 3552 96p

N.B.

The most prominent edges (most suitable for analysis) are shown in italics.
h denotes a hydrogenic edge with sawtooth profile.
d denotes a delayed maximum giving a rounded edge with a maximum at least 10eV above the threshold.
w denotes a sharp white line peak at the edge threshold.
p denotes a low-energy edge that resembles a plasmon peak.

Course T2 Electron Microscopy and Analysis

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Course T2 Electron Microscopy and Analysis

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T2: Electron Microscopy and Analysis

X-ray will give rise to 392 electron-hole pairs.

sin sin sin

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