Basic Electron-Matter Interaction

• Characterization, when used in materials science, refers

to the use of external techniques to probe into the
internal structure and properties of a material.
Characterization can take the form of actual materials
testing, or analysis, for example in some form of
microscope.

• Analysis techniques are used simply to magnify the

specimen, to visualise its internal structure, and to gain
knowledge as to the distribution of elements within the
specimen and their interactions.
• Magnification and internal visualization are
normally done in a type of microscope, such as:

* Optical Microscope
* Scanning Electron Microscope (SEM)
* Transmission Electron Microscope (TEM)
* Field Ion Microscope (FIM)
* Scanning Tunneling Microscope (STM)
* Atomic Force Microscope (AFM)
• Elemental analysis of the specimen can also be done in
a number of ways:

* Energy-Dispersive X-ray spectroscopy (EDX)

* Wavelength Dispersive X-ray spectroscopy (WDX)
* Mass spectrometry
* Impulse excitation technique (IET)
* Secondary Ion Mass Spectrometry (SIMS)
* Electron Energy Loss Spectroscopy (EELS)
* Auger electron spectroscopy
* X-ray photoelectron spectroscopy (XPS)
 The TEM Column
• Gun emits electrons
• Electricfieldaccelerate
• Magnetic(andelectric)field
controlpathofelectrons
• Electron wavelength @ 200KeV
2x10-12 m
• Resolution normally achievable
@ 200KeV 2 x 10-10 m  2Å
when electrons hit matter ..
incident electrons
backscattered
electrons

secondary
electrons
X-rays :
characteristic

continuum

transmitted electrons
 when electrons hit matter ..
(1) they may collide with an inner shell electron, ejecting same
> the ejected electron is a low-energy, secondary electron
- detected & used to from SEM images
> the original high-energy electron is scattered
- known as a ‘back-scattered’ electron (SEM use)
> an outer-shell electron drops into the position formerly
occupied by the ejected electron
this is a quantum process, so a X-ray photon of precise
wavelength is emitted - basis for X-ray
microanalysis
when electrons hit matter ..
incident electrons
backscattered
electrons

secondary
electrons
X-rays :
characteristic

continuum

transmitted electrons
 when electrons hit matter ..
(2) they may collide or nearly collide with an atomic nucleus
> undergo varying degree of deflection (inelastic scattering)
> undergo loss of energy - again varying
> lost energy appears as X-rays of varying wavelength
> this X-ray continuum is identical to that originating from
an X-ray source/generator (medical, etc)
> original electrons scattered in a forward direction will
enter the imaging system, but with ‘wrong’ λ
> causes a ‘haze’ and loss of resolution in image
when electrons hit matter ..
incident electrons
backscattered
electrons

secondary
electrons
X-rays :
characteristic

continuum

transmitted electrons
 when electrons hit matter ..
(3) they may collide with outer shell electrons
> either removing or inserting an electron
> results in free radical formation
> this species is extremely chemically active
> reactions with neighbouring atoms induce massive change
in the specimen, especially in the light atoms
> this radiation damage severely limits possibilities of EM
> examination of cells in the live state NOT POSSIBLE
> all examinations need to be as brief (low dose) as possible
when electrons hit matter ..
incident electrons
backscattered
electrons

secondary
electrons
X-rays :
characteristic

continuum

transmitted electrons
 when electrons hit matter ..
(4) they may pass through unchanged
> these transmitted electrons can be used to form an image
> this is called imaging by subtractive contrast
> can be recorded by either
(a) TV-type camera (CCD) - very expensive
(b) photographic film - direct impact of electrons
Photographic film
> silver halide grains detect virtually every electron
> at least 50x more efficient than photon capture !
 when electrons hit matter ..
‘beam damage’ occurs:

• light elements (H, O) lost very rapidly

• change in valency shell means free radicals formed
• . . .& consequent chemical reactions causing further damage

• beam damage is minimised by use of

• low temperatures (-160°)
• minimal exposure times
Transmission electron
microscope
Transmission electron microscopy (TEM)
is a microscopy technique whereby a beam
of electrons is transmitted through an ultra
thin specimen (10-100 nm) thick, interacting
with the specimen as it passes through.

An image is formed from the interaction of

the electrons transmitted through the
specimen; the image is magnified and
focused onto an imaging device, such as a
fluorescent screen, on a layer of
photographic film, or to be detected by a
sensor such as a CCD camera.
 Size effects are known since the Boudart’s discovery of the
structure-sensitive and structure-insensitive reactions and have
been studied for a long time

Turnover number, s-1

Positive size effects

Structural insensitive
reaction

Structural sensitive reactions

• Abatement of СО and CHx
• Reforming of gasoline
• Hydrogenation of unsaturated CxHy
• Hydrogen and methanol FC ….
3 10 100 1000
Particle Size, Å
1. Bukhtiyarov V.I. Chemical Reactivity of Metal Clusters at Solid Surfaces, In:
Interfacial Science, “Chemistry for the 21st Century” Monograph (Ed.
M.W.Roberts), Blackwell Science, 1997, 109-128.
2. Bukhtiyarov V.I., Slinko M.G. Metallic nanosystems in catalysis. Russian
Chemical Reviews, 2001, v. 70, n.2, 147-159.
HRTEM study of Pd+Rh/Al2O3+CeO2-ZrO2
automobile catalyst
 Scientific bases of preparation of gold nanoparticles with the mean sizes
of 1–10 nm on high-surface aluminas have been developed

It has been shown, that «deposition-precipitation»: Aumetal

+ NaOH
Au(OH)3—[AuCl4-n(OH)n]-/MOx
∆
[AuCl4]-
+ Al2O3 O2
O 3
Al 2
results in epitaxial growth of gold nanoparticles, that provides the best results
in preparation of the particles with homogeneous size distribution
and improved stability against sintering
The model (molecular dynamics method)
method) of
HRTEM images of gold nanoparticles on Al2O3 epitaxial growth of gold nanoparticles on Al2O3
Au
Au [111] face
O
Al2O3 [111] Al
face

x 600 000
Scanning Electron Microscopy
The scanning electron microscope (SEM) is a type of electron microscope
that images the sample surface by scanning it with a high-energy beam of
electrons in a raster scan pattern.

The electrons interact with the atoms that make up the sample producing
signals that contain information about the sample's surface topography,
composition and other properties such as electrical conductivity.

The types of signals produced by an SEM include secondary electrons,

back scattered electrons (BSE), characteristic x-rays, light
(cathodoluminescence), specimen current and transmitted electrons.

These types of signal all require specialized detectors for their detection that
are not usually all present on a single machine. The signals result from
interactions of the electron beam with atoms at or near the surface of the
sample.
Scanning Electron Microscopy
 SEM
Electron/Specimen Interactions
When the electron beam strikes a sample,
both photon and electron signals are emitted.
Incident Beam Backscattered
electrons
X-rays
- Atomic number
- composition info and topographical

Cathodoluminescence
- Electrical
Secondary electrons
Auger electrons
- Topographical
- Surface sensitive
compositional

Specimen Specimen Current

Electrical
Pollen grains micrograph showing the
characteristic depth of field of SEM
Electron diffraction pattern
 Electron diffraction pattern

Introduction

Electrons can act as waves as well as particles.

A series of electrons hitting an object is exactly equivalent to a beam of electron

waves hitting the object and it produces a diffraction pattern in the same way
as a beam of X-rays does.

The two important differences between electron and X-ray diffraction are:

(1) electrons have a much smaller wavelength than X-rays, and

(2) the sample is very thin in the direction of the electron beam (of the order of
100 nm or less) - it has to be thin so that enough electrons can get through to
form a diffraction pattern without being absorbed. These factors conspire to
have a fortunate effect on the Ewald sphere construction and diffraction
pattern:

1. The thin sample makes the reciprocal lattice points longer in the reciprocal
direction corresponding to the real-space dimension in which the sample is
thin:
 Electron diffraction pattern

1. The thin sample makes the reciprocal lattice points longer in the reciprocal
direction corresponding to the real-space dimension in which the sample is
thin:

2. The small electron wavelength makes the radius of the Ewald sphere very
large (recall its radius is 1/λ). The small electron wavelength also makes the
diffraction angles θ small (1-2°). this can be seen by substituting a wavelength
of 2.51 x 10-12 m into the Bragg equation
 Electron diffraction pattern

These make the Ewald sphere diagram look like this so that whole layers of the
reciprocal lattice end up projected onto the film or screen:

2. The small electron wavelength makes the radius of the Ewald sphere very
large (recall its radius is 1/λ). The small electron wavelength also makes the
diffraction angles θ small (1-2°)
 The large (strong) spot in the middle is the straight-through beam (the beam
which has passed through the sample without diffracting). This always has the
index 000.

Caution 1: systematic (kinetic) absences appear in electron diffraction patterns just

as in X-ray diffraction patterns, for the same reason: the various features of the
lattice or motif diffract electrons in the same direction but the phase factors
from the various features cancel, leaving an absence.

Caution 2: sometimes where there should be a systematic absence, the spot

appears to be still there. This is because of the strong interaction between
electrons and atoms: there is a small but significant probability that an electron
will be diffracted twice, from two planes one after another
 Mathematics relating the real space to the electron diffraction pattern
Relation 1

The distance, rhkl, on the pattern between the spot hkl and the spot 000 is
related to the interplanar spacing between the hkl planes of atoms, dhkl, by the
following equation:
λL
Diagram of part of reciprocal lattice: rhlk =
d hkl

r
From the diagram, tan 2θ =
L
The Bragg condition (which is true for the sets
of variables that produce diffraction spots)
states that:

λ = 2d hkl sin θ
 Mathematics relating the real space to the electron diffraction pattern
Relation 1

In electron diffraction, the angle θ is small so that we can make the following
approximations
tan 2θ = 2θ
sin θ = θ

with θ in radians. Hence,

rhlk λ
= 2θ =
L d hkl

and so it follows that :

λL
rhlk =
d hkl
 Mathematics relating the real space to the electron diffraction pattern
Relation 2

Since the diffraction pattern is a projection of the reciprocal lattice, the angle
between the lines joining spots h1k1l1 and h2k2l2 to spot 000 is the same as the
angle between the reciprocal lattice vectors [h1k1l1]* and [h2k2l2]*. This is also
equal to the angle between the (h1k1l1) and (h2k2l2) planes, or equivalently the
angle between the normals to the (h1k1l1) and (h2k2l2) planes. This angle is θ in
the diagram below.
 Surface Composition of Materials
• XRD and TEM measure the structure and/or chemical
composition of catalysts extending below the catalytic
surface.
The composition of the surface is usually different from
that of the bulk.
• It is on these surfaces that the active sites exist and
where chemisorption, chemical reaction, and desorption
take place.
• The tools available for surface composition
characterization are X-ray photoelectron spectroscopy
(XPS), Auger electron spectroscopy (AES), ion
scattering spectroscopy (ISS), and secondary-ion mass
spectroscopy (SIMS).
 Surface Composition of Materials
• XPS is used more widely than the others for studying the
surface composition and oxidation states of industrial
catalysts.
• XPS refers to the technique of bombarding the surface with X-
ray photons to produce the emission of characteristic
electrons.
These are measured as a function of electron energy.
• Because of the low energy of the characteristic electrons, the
depth to which the analysis is made is only ~40Å .
The composition of this thin layer as a function of depth can
be determined by removing or sputtering away top layers and
analyzing the underlying surfaces.
• This technique can provide properties including oxidation
state of the active species, interaction of a metal with an oxide
carrier, and the nature of chemisorbed poisons and other
impurities.
 Why Do EDS X-ray Analysis in
TEM/SEM?
• Spatial resolution
– 2-20 nm (103 times better than SEM)

• Elemental detectability
– 0.1 wt% - 1 wt%, depending on the specimen (~same as SEM/EDS)

• Can use typical TEM specimens (t ~ 50-500 nm)

– EELS requires specimens < 20-30 nm

• Straightforward microanalysis
– Qualitative analysis => Which element is present?
– Quantitative analysis => How much of the element is present?
– Easy x-ray mapping
 Example of an X-ray Spectrum

2 Types of X-rays

– Characteristic x-rays
• elemental identification
• quantitative analysis

– Continuum x-rays
• background radiation
• must be subtracted for
quantitative analysis Example of EDS x-ray spectrum

from Goldstein et al., Scanning Electron Microscopy

and X-ray Microanalysis, Springer, 2003.
 Compute Energy of Sodium Kα Line
Beam
electron
If beam E > EK, then a
K-electron may be ionized: β
X-ray energy is the difference between α
two energy levels:
E Kα1 = E K − E L III K L M
Energy levels EK and EL3 are in Bearden's
"Tables of X-ray Wavelengths and X-ray Atomic
Energy Levels" in older editions of the CRC
Handbook of Chemistry and Physics

For sodium (Z=11): EK = 1072 eV

Beam
EL3 = 31 eV electron
E Na
K a1 = 1072 eV − 31 eV = 1041 eV
loses EK

For Na only see one peak since the Kβ is only 26 eV from the Kα line
 Fluorescence Yield ω
• ω = fraction of ionization events
producing characteristic x-rays

 ω increases with Z
 ωK typical values are:
• 0.03 for carbon (12) K-series @ 0.3
keV
• 0.54 for germanium (32) K-series @
9.9 keV
• 0.96 for gold (79) K-series @ 67 keV
– X-ray production is inefficient for low
Z lines (e.g., O, N, C) since mostly
Augers produced from Goldstein et al., Scanning Electron Microscopy
and X-ray Microanalysis, Springer, 2003.

 ω for each shell: ωK, ωL, ωM

– X-ray production is inefficient for L-
shell and M-shell ionizations since
 Qualitative Analysis
Which elements are present?
• Collect as many x-ray counts as possible
– Use large beam current regardless of poor spatial
resolution with large beam
– Analyze thicker foil region, except if light elements
x-rays might be absorbed

• Scan over large area of single phase =>

avoid spot mode

• Use more than one peak to confirm each

element
Chart of X-ray Energies (0-20 keV)
from Goldstein et al., Scanning Electron Microscopy and X-ray Microanalysis, Springer, 2003

M-series

L-series

K-series
Unknown #1

from xray.optics.rochester.edu/.../spr04/pavel/
 Qualitative Analysis
W Mα
α
Elements present
major: W, Ru
trace: Fe, Cu, C

W Lα
α
Ru Lα
α
W Mζ
ζ W Ll
Fe Kα,β
α,β W Lβ
β1,2

C Cu W Lγγ1,3