Materials Characterization

MT21005

Transmission Electron Microscopy

  Imaging and contrast formation in TEM
 Bright field imaging
 Mass-thickness contrast
 Atomic number contrast
 Dark field imaging

Topics Covered  Diffraction contrast

 HAADF mode
 STEM mode
 Electron diffraction patterns
 Electron Scattering from amorphous, crystalline materials
 Braggs law
 Zone = Zonal planes + Zonal axis
Image formation in TEM
Imaging methods
• Imaging methods in TEM use the information contained
in the electron waves exiting from the sample.
• The projector lenses allow for the correct positioning of
this electron wave distribution onto the viewing system.
• The observed intensity of the image, assuming a
sufficiently high-quality imaging device, can be
approximated as proportional to the time-averaged
squared absolute value of the amplitude of the electron
wave functions.
• The observed image depends not only on the beam’s
amplitude but also on the phase of the electrons
(although phase effects may often be ignored at lower
magnifications).
Imaging methods
• Higher resolution imaging requires thinner samples and
higher energies of incident electrons, which means that
the sample can no longer be considered absorbing
electrons.
• Instead, the sample can be modeled as an object that
does not change the amplitude of the incoming electron
wave function, but instead modifies the phase of the
incoming wave; in this model, the sample is known as a
pure phase object.
• For sufficiently thin specimens, phase effects dominate
imaging, complicating the analysis of observed
intensities.
 Contrast generation in electron microscope
• The simple model of elastic scattering by Coulombic interaction of
electrons with the atoms in a material is sufficient to explain basic
contrast mechanisms in electron microscopy.
• The contrast between two adjacent areas in a TEM image can be
defined as the difference in the electron densities in image plane.
• Due to the scattering of the incident beam by the sample, the
amplitude and phase of the electron wave change, which results
in amplitude contrast and phase contrast, correspondingly.
• Most of the images have both contrast components.
• Amplitude contrast is obtained due to removal of some electrons
before the image plane.
• During their interaction with the specimen some of electrons will
TEM high-resolution micrograph of
be lost due to absorption, or due to scattering at very high angles
Au/TiO 2 catalyst.
beyond the physical limitation of microscope or are blocked by
the objective aperture.
 Bright field imaging in TEM
• In the bright field (BF) modes of the TEM and the STEM, only
the direct beam is allowed to contribute to image formation.
• This is experimentally achieved in two different ways.
• In the TEM, a small objective aperture is inserted into
the back focal plane of the objective lens in such a way
that exclusively the direct beam is allowed to pass its
central hole and to build up the image
• Scattered electrons are efficiently blocked by
the aperture.
• The direct beam is utilized for image formation in an
analogous way in a STEM: here, a bright field detector is
placed in the path of the direct beam.
• Resultantly, scattered electrons are not detected
by BF-STEM.
Mass contrast
• The likelihood that an electron is deviated from
its direct path by an interaction with an atom
increases with the number of charges that the
atom carries.
• Therefore, heavier elements represent more
powerful scattering centres than light
elements.
• Due to this increase of the Coulomb force with
increasing atomic number, the contrast of areas
in which heavy atoms are localized will appear
darker than of such comprising light atoms.
• This effect is the mass contrast.
Thickness contrast
• The number of actually occurring
scattering events depends on the
numbers of atoms that are lying in the
path of the electron.
• As a result, there are more electrons
scattered in thick samples than in thin
ones.
• Thick areas appear darker than thin
areas of the same material.
• This effect leads to thickness contrast.
 Mass-thickness contrast

𝑵𝒐 𝝈𝑻𝝆𝒕
𝑸𝑻𝒕 =
𝑨
• Together, these two effects are called mass-
thickness contrast.
• This contrast can be understood quite
intuitively since it is somehow related to
the contrast observed in optical
microscopy.
• However, instead of absorption of light, it
of course is the local scattering power that
determines the contrast of TEM images.
• Mass-thickness contrast is important to
understand bright field TEM and STEM
images.

TEM images of uniform double-shell hollow

microspheres with different shell thicknesses.
 Bright field imaging in TEM: Mass-thickness contrast
• It is essentially the weakening of the
BF-TEM image of a SiO2 particle on a carbon foil. direct beam’s intensity that is detected
by both types of BF imaging.
• A main component of this weakening
is the mass-thickness contrast.
• Thin areas of the particle appear
brighter than thick ones.
• At the supporting C foil: in thin areas
close to the hole in the foil, the C foil is
thin and therefore its contrast is light
grey.
• It is darker in the middle of the foil
(area marked by “C”).
 Bright field imaging in TEM: Atomic number contrast
𝒁𝒆
𝒓𝒆𝒍𝒂𝒔𝒕. =
𝑬𝜽

• The particles with a size of several 10 nm appear

with black contrast since Au is by far the heaviest
element in this system and therefore scatters many
electrons.
• Au particles are crystalline, and as a result, Bragg
contrast contributes to the dark contrast as well.
• The titania support appears with an almost uniform
grayscale.
• However, the thickness of the area in the upper
right corner of the image is greater as indicated by
the darker contrast there (thickness contrast).

BF-TEM image of Au particles (black patches) on a TiO2 support

Superimposition of contrast sources in BF

TEM micrographs of PANI capsules decorated with gold nanoparticles

 Dark field imaging in TEM
• In DF imaging mode, the objective aperture is inserted in a back focal plane (BFP) of the objective lens
(where diffraction spots are formed).
• If using the objective aperture to select only the central beam, the transmitted electrons are passed through
the aperture while all others are blocked, and a bright field image (BF image) is obtained.
• If we allow the signal from a diffracted beam, a dark field image (DF image) is received.
Dark field imaging
Bacteria
specimen
after
incubation
with 4 nm
Au NPs,
imaged
using
bright
field (a),
(c), and (e)
or dark
field (b),
(d), and (f)
TEM.
 Diffraction contrast
• If a sample is crystalline, then diffraction contrast appears in BF and DF TEM and STEM images.
• If a crystal is oriented close to a zone axis, many electrons are strongly scattered to contribute to
the reflections in the diffraction pattern.
• Only a few electrons pass such areas without any interaction; therefore, dark contrast appears in the
BF image (diffraction contrast).

• On the other hand, such

diffracting areas may appear
bright in the DF image if they
diffract into the area of
reciprocal space selected by the
objective aperture.
 Diffraction contrast
• Diffraction contrast occurs due to a specific
crystallographic orientation of a grain.
• The crystal is in a so-called Bragg
condition, whereby atomic planes are
oriented in a way that there is a high
probability of scattering.
• Thus, diffraction contrast provides
information on the orientation of the
crystals in a polycrystalline sample.
• In case of diffraction contrast exists, the
contrast usually cannot be interpreted as
due to mass or thickness variations.

• One should be aware that coherent and incoherent mechanisms of contrast generation, namely mass-
thickness and Bragg contrast, co-occur in real specimens that are at least partly crystalline.
• This renders the interpretation of BF and DF TEM and STEM images in many cases complex and quite
difficult.
 • TEM image (a) and the corresponding diffraction pattern (b)
of Pt polycrystalline film taken without an objective
aperture.
• In order to enhance the contrast in the TEM image the
number of scattered beams as visible in the diffraction
pattern should be reduced.

• This can be done by selecting a

certain area in the diffraction plane
like only the central beam or a
diffracted beam, or combinations of
beams with objective aperture to
form BF.

• (c) in case the central beam is included or DF (d-e) images in case the central beam is blocked.
• DF images (d-e) are obtained using the diffracted beams indicated in diffraction pattern with circles (b).
• Grains from which electrons are scattered into these diffraction spots appear brighter.
 High angle scattering: HAADF mode
• The Coulomb interaction of the electrons with the
positive potential of an atom core is strong.
• This can lead to scattering into high angles
(designated as Rutherford scattering).
• The probability of such scattering events rises for
heavier atoms, i.e. atoms with a high number of
protons and consequently a high atomic number
𝒁, offers the possibility for obtaining chemical
contrast.
• Areas or particles containing high 𝒁 elements
scatter stronger and thus appear bright in images
recorded with electrons scattered into high
angles.

HAADF-STEM image of Au particles (bright) on TiO2.

• This effect is employed in high-angle annular dark field
(HAADF) STEM (also called 𝒁-contrast imaging).
• By the HAADF-STEM method, small clusters (or even single
atoms) of heavy atoms (e.g. in catalysts) can be recognized
in a matrix of light atoms since contrast is high
(approximately proportional to 𝒁𝟐).
Comparison of TEM and HAADF-STEM images

• As in TEM, thickness effects contribute to the image contrast in

HAADF-STEM.
• Ball-like Pd particles on SiO2 are partly overlapping.
• At the intersections, the thickness and resultantly the scattering
power as well of two particles sums up and is thus increased
compared to that of the a single ball.
• In the TEM image, this leads to a darker contrast whereas in the
HAADF-STEM image the contrast in the intersections becomes
brighter than in the single balls.
 Scanning transmission electron microscopy
• STEM is a typical mode of imaging in TEM. As with a
conventional TEM, images are formed by electrons passing
through a sufficiently thin specimen.
• Unlike C-TEM, in STEM the electron beam is focused to a fine
spot (with the typical spot size 0.05 – 0.2 nm) which is then
scanned over the sample in a raster illumination system
constructed so that the sample is illuminated with the beam
parallel to the optical axis at each point .
• The rastering of the beam across the sample makes STEM
suitable for analytical techniques such as 𝒁-contrast annular
dark-field imaging, and spectroscopic mapping by energy
dispersive X-ray (EDS) spectroscopy, or electron energy loss
spectroscopy (EELS).

• These signals can be obtained simultaneously, allowing direct correlation of images and spectroscopic data.
• A typical STEM is a conventional TEM equipped with additional scanning
coils, detectors and necessary circuitry, which allows it to switch between
operating as a STEM, or a C-TEM; however, dedicated STEMs are also
manufactured.
• High resolution scanning transmission electron microscopes require
exceptionally stable room environments.
• In order to obtain atomic resolution images in STEM, the level of
vibration, temperature fluctuations, electromagnetic waves, and acoustic
waves must be limited in the room housing the microscope.
 Electron diffraction pattern
• An electron beam that has passed through a thin specimen contains two components: elastically scattered
electrons and inelastically scattered electrons.
• Electron diffraction pattern: Spatial distribution of the elastically scattered electrons (Special type of
scattered electrons).
• It helps to deduce information about the arrangement of the atoms in the specimen.
• To explain diffraction, regarding the electron as a particle is insufficient and its wave properties must be
considered.

Single crystal of NaCl

 Scattering of electrons
• Solely incoherent scattering of the incident, nearly coherent electrons takes place if the scattering
centers are arranged in an irregular way, especially in amorphous compounds.
• Although the scattering happens predominantly in forward direction, the scattered waves have
arbitrary phases in respect of each other.
• An enhancement of the wave intensity because of constructive interference in certain directions can
not happen.
 Scattering of electrons
• Intensity of elastic scattering from a particular atom species is a maximum when the scattering angle is zero
and decreases monotonically as 𝜽 increases.
• The variation of scattered intensity is more complex as there are some diffuse maxima in the intensity.
• Figure (a) is a diffraction pattern from a thin film of amorphous carbon, and Figure (b) is a graph of
intensity as a function of scattering angle.
Scattering of Electrons in crystalline material
• If a crystalline specimen is transmitted by electrons with a certain
wavelength, then coherent scattering takes place.
• All atoms in such a regular arrangement act as scattering centers that
deflect the incoming electron from its direct path.
• This occurs in accordance with the electrostatic interaction of the nucleus
with the negatively charged electron.
• Since the spacing between the scattering centers is regular, constructive
interference of the scattered electrons in certain directions happens and
thereby diffracted beams are generated.
 Scattering of electrons in crystalline material
• When the atoms are close together, there is
a strong interaction between the scattered
electrons from different atoms.

• The effects of atomic arrangement on

electron scattering: The two parameters of
importance in electron diffraction
 Angular distribution of the scattered
electrons
 Intensity of the scattering

• From a knowledge of the geometry of electron diffraction patterns we can deduce a great deal of
information about the structure of a crystal and its orientation.
• A knowledge of the factors which determine the intensity of electron scattering enables us to derive
more detailed information from a diffraction pattern, and enables us to understand and interpret the
images of crystalline materials in the transmission electron microscope.
 Braggs law
• A quantitative expression for the relation between diffraction angle, (electron) wavelength and interatomic
distance, by considering diffraction of an incoming (electron) wave at a set of equidistant lattice planes.
• In this simplified model, the diffraction is treated as a reflection of the (electron) wave at the lattice planes.
• This description leads to a general equation that is valid not only for diffraction of electrons but for that of
X-rays and neutrons as well.

• The conditions for constructive interference for two

electron waves diffracted at two parallel lattice planes 𝒏𝝀 = 𝟐𝒅𝒔𝒊𝒏𝜽
• The two incident electron waves are in phase with
each other; after reflection at the lattice planes,
the two waves have to be in phase again for
constructive interference.
• The distance that the wave with the longer path
follows needs to be an integer multiple of the
electron wavelength.
 • For 300 kV electrons, 𝝀~𝟎. 𝟎𝟎𝟏𝟗𝟕 nm; for a 𝒅-value of 0.2 nm, 𝜽~𝟎. 𝟐𝟖°.
• 𝑺𝒊𝒏𝜽 ≈ 𝜽 for electron diffraction so that diffracting planes are almost parallel to the incident electron
beam.
• Incident electron beam represents approximately the zone axis of the reflecting lattice planes.
• Scattering angles in X-ray reflection: 𝟎° > 𝜽 >𝟏𝟖𝟎°, due to the larger wavelengths (e.g 𝝀~𝟎. 𝟏𝟒 𝒏𝒎 for
CuKα radiation).

• From Braggs equation: The angle between the direct and the diffracted beam (diffraction angle) increases with
• Decreasing interatomic distance
• Increasing wavelength
 Zone = Zonal planes + Zonal axis
• There will only be strong diffraction from planes of atoms which are nearly parallel to the incident electron
beam.
• The condition for the
direction [uvw] to lay on [001] (-110) • Zone axis: It is the
(-210)
the plane (hkl) is (210) Zone axis common direction lying on
(100)
the family of planes. For
𝒉𝒖 + 𝒌𝒗 + 𝒍𝒘 = 𝟎 example [001] direction is
(-100)
[𝒖𝒗𝒘] = 𝒁𝒐𝒏𝒆 𝒂𝒙𝒊𝒔 contained by various
(𝒉𝒌𝒍) = 𝒁𝒐𝒏𝒆 𝒑𝒍𝒂𝒏𝒆 planes.
• When the incident
𝒖 = 𝒌𝟏𝒍𝟐 − 𝒌𝟐𝒍𝟏 electron beam comes
𝒗 = 𝒍𝟏𝒉𝟐 − 𝒍𝟐𝒉𝟏 along zone axis, then all
𝒘 = 𝒉𝟏𝒌𝟐 − 𝒉𝟐𝒌𝟏 the corresponding parallel
𝒖 𝒗 𝒘 planes to zone axis will
All shaded planes belong to the same zone i.e. diffract.
𝒉𝟏 𝒌𝟏 𝒍𝟏 parallel to an axis called zone axis.
𝒉𝟐 𝒌𝟐 𝒍𝟐
Capturing the diffraction pattern