Advanced Material Characterization
Transmission Electron Microscopy
Maoshuai Li
School of Chemical Engineering & Technology
Tianjin University
2024/10/8
实事求是
Chapter 5
Transmission Electron Microscope
(TEM)
Basics of TEM
Types of TEM & Related Spectroscopy
Application of TEM and Practices
In situ TEM: Theory and Practices
实事求是
What is TEM
TEM utilizes energetic electrons to provide
morphologic, compositional and
crystallographic information on samples.
TEM is an electronic optical instrument with
high-resolution capabilities and high-
magnification factors, which uses a very
short-wavelength electron beam as the
illumination source and focuses the
electrons that penetrate the sample (i.e.,
transmitted electrons) into an image using
electromagnetic lenses.
实事求是
Imaging Principles
TEM Components
Electron gun: produces the electron beam
Condenser system (including condenser
lens): focuses the beam onto the object.
Lens: objective lens (most important lens,
determines the resolution), intermediate
lens, projector lens: focus the electrons
passing through the specimen to form a real,
highly magnified image.
Image recording system: converts the
electron image into some form perceptible
by eye.
Vacuum system.
实事求是
Imaging Principles
Electromagnetic lenses
Electromagnetic lens: the magnetic field generated by the
electromagnetic coil; To control electron beam (condenser
lens) and to form images (objective lens).
The electron beams in electromagnetic satisfies the following
properties: [1] no refraction; [2] principal axis: focus on focal
point (F); focal plane; [3] secondary axis: focus on the
intersection of the secondary axis and the focal plane after
passing through the lens.
Adjustable focal length by excitation current
Four types of lenses used in TEM: condenser lens, objective
lens; intermediate lenses; projector lenses.
实事求是
Imaging Principles
TEM imaging principle
Consist of condenser lens, objective lens, intermediate lenses
and projector lenses.
Project the diffraction pattern or image onto the fluorescence
screen.
By adjusting the lens current of the intermediate lens, the
object plane of the intermediate lens overlap with the back
focal plane of the objective lens, allowing the diffraction
pattern to be obtained on the fluorescence screen.
If the object plane of the intermediate lens overlap with the
image plane of the objective lens, a microscopic image is
obtained.
The resolution of the transmission electron microscope mainly
depends on the objective lens.
实事求是
Imaging Principles
TEM imaging principle
Diffraction mode: the object plane of
the intermediate lens overlap with
the back focal plane of the objective
lens.
Imaging mode: the object plane of
the intermediate lens overlap with
the image plane of the objective
lens。
实事求是
Resolution
Resolution
Resolving power is the ability of an optical instrument
to distinguish or separate two points. The better the
resolving power, the finer the image obtained through
microscope.
When an ideal object point is imaged through a lens,
due to diffraction effects, it no longer forms a single
point on the image plane. Instead a central bright spot
surrounded by alternating bright and dark rings is
formed.
Image of the electron beam appeares as a disk
comprised of concentric circles, called Airy disk. This
Airy disk generates primary, secondary, and tertiary
wave.
实事求是
Resolution
Resolution
The resolution is usually estimated by the
distance between first-order peaks and its
trough, denoted by “r”. If distance between
two points is more than “r”, then peaks
observed by the two points will be emerged
as a single point
Abbe’s equation provides mathematical
expression for resolution of a perfect optical
system:
实事求是
Electron diffraction
Electron diffraction
Scatted electron waves (scattered by atoms in
a crystal) interfere constructively with each
other, resulting in diffraction.
Similar to X-ray diffraction. Requirement:
Bragg Law
In electron diffraction, the Bragg equation is
always described in the form of first-order
diffraction.
2d hkl sin θ = λ
实事求是
Electron diffraction
Electron diffraction vs. XRD
10-3 nm 10-1 nm
实事求是
Contrast
Contrast
Image contrast: the difference in brightness
between different regions on an image.
The definition of contrast: the difference in
electron beam intensity between two adjacent
parts.
I 1 − I 2 ∆I
C= =
I2 I2
When electrons escape from the lower surface of the sample, the intensity of the electron beam
transmitted to the fluorescent screen is uneven due to the interaction between the sample and the
electron beam. This unevenly intense electron image is referred to as a contrast image.
Contrast mechanisms can be categorized into three types, i.e., mass thickness, diffraction, and phase-
contrast mechanisms
实事求是
Contrast
Contrast mechanisms - Mass thickness contrast
Mass Thickness Contrast: differences in atomic
number or thickness in different micro-regions
Defined as the mass of the column above a unit
area on the lower surface of the sample.
A larger value of mass-thickness indicates a
stronger absorption and scattering effect on
electrons, resulting in more electrons being
scattered outside the aperture and
corresponding to a darker contrast. Conversely,
a smaller value of mass-thickness corresponds
to a brighter contrast.
The mass-thickness contrast is related to the
atomic number Z, density ρ, and thickness t.
实事求是
Contrast
Contrast mechanisms – Diffraction contrast
Diffraction Contrast: formed by differences in
the diffraction intensity of the sample.
Diffraction contrast is mainly due to the
differences in the degree to which the crystal
sample satisfies the Bragg reflection
conditions and the variation in structural
amplitude, which lead to contrast in the
electron image.
Exclusive to crystalline structures and does
not exist in non-crystalline samples.
Bright field imaging: if aperture is at the center
and allows unscattered beam to pass; Dark
field imaging: diffracted beam to pass
aperture.
实事求是
Contrast
Contrast mechanisms - Diffraction contrast
Bright (a) and dark (b) field imaging
（a） （b）
实事求是
Contrast
Contrast mechanisms - Phase contrast
Phase contrast: When the sample is very thin, the difference in transmission amplitude between
adjacent crystal columns exiting the sample is insufficient to distinguish between two adjacent
image points. In this case, amplitude contrast cannot be obtained. However, phase contrast can be
utilized by exploiting the phase inconsistency of the electron beam on the exit surface of the sample,
converting phase differences into intensity differences to form contrast. This type of contrast is
known as phase contrast.
transmitted beam diffracted beam
Bright field imaging Dark field imaging High resolution imaging
实事求是
Contrast
Contrast mechanisms - phase contrast
Principle of phase contrast imaging: If, one or more diffraction beams are allowed to participate in
the imaging process with together the transmitted beam, lattice (stripe) images and crystal structure
(atomic) images can be obtained due to the phase coherence effect of these beams.
Lattice images: projections of crystal planes.
Crystal structure (atomic) images: two-dimensional projections of the electric potential fields of
atoms or atomic groups in the crystal.
The more diffraction beams used for imaging, the richer the details of the crystal structure obtained.
The resolution of diffraction contrast images cannot be better than 1.5 nm (the limiting resolution of
weak beam dark-field images), while phase contrast images can provide details smaller than 1.5 nm.
Therefore, this type of image is referred to as high-resolution imaging.
实事求是
Contrast
Contrast mechanisms - phase contrast
Lattice fringe image: When two waves on the
back focal plane of the objective lens are
selected for imaging using an objective
aperture (one transmitted wave and one
diffraction wave), interference between the two
waves results in a fringe pattern with
periodically varying intensity in a one-
dimensional direction. This is referred to as a
lattice fringe image.
Since the diffraction conditions during lattice
fringe imaging are not fixed, it is not possible
to obtain information about atomic positions
from the lattice fringe image.
实事求是
Contrast
CeO2 Octahedron CeO2 Rod, Cube
实事求是
Chapter 5
Transmission Electron Microscope
(TEM)
Basics of TEM
Types of TEM & Related Spectroscopy
Application of TEM and Practices
In situ TEM: Theory and Practices
实事求是
Conventional TEM Imaging
Conventional Imaging
Normally an acceleration voltage of 100–200
kV. To get better resolution & transmission,
200–500 kV
Conventional TEM has three modes: low
magnification, high magnification, diffraction
mode
Bright-field, dark-field imaging, selected area
electron diffraction, micro- & nano-diffraction,
and high-resolution imaging
实事求是
Contrast
Conventional Imaging
Provide two-dimensional projection of three-dimensional objects with clear information of size, shape,
and structure
实事求是
Contrast
Aberration Corrected Transmission Electron Microscopy
Aberration difference between an image formed by
an actual electron-optical system and an ideal one
Types: spherical aberration, astigmatism and
chromatic aberration
Spherical aberration: different capabilities of
converging electrons in central zone & peripheral
zone of electromagnetic lens
Astigmatism: refers to axis astigmatism and it
happens in case of asymmetry of a magnetic field
of magnetic lens
Chromatic aberration: a failure of a magnetic lens
to focus all electrons emitted from an electron gun
to the same convergence point Conventional Spherical aberration
实事求是
Contrast
High-Resolution Transmission Electron Microscopy
HRTEM images are created by interference of
both scattered and transmitted beams
Scattered elastically electrons play a major
role in the formation of high-resolution
bright-field micrographs.
HRTEM
HR imaging always perform in the bright-field
imaging mode
实事求是
Contrast
High-Resolution Transmission Electron Microscopy
A phase contrast imaging technique
CeO2 nanoparticles
实事求是
Contrast
High-Resolution Transmission Electron Microscopy
Provide micrographs of crystal surfaces at atomic resolution with chemical composition at 1 nm
spatial resolution
(a) MoO3 hollow nanorods. (b) Iron oxide hollow structures. (c) Iron oxide-gold nanodimers. (d) Iron oxide nanoflowers
实事求是
Contrast
High-Resolution Transmission Electron Microscopy
HRTEM is used successfully for the
determination of stacking faults, interference,
dislocations, point defects, surface structure,
and precipitates
Stacking faults: the stacking of one atomic
plane out of sequence with another while the
lattice on either side of the fault is perfect.
实事求是
Contrast
High-Resolution Transmission Electron Microscopy
Dislocations: defects whose motion produces plastic deformation of crystals at stresses well below
the theoretical shear strength of a perfect crystal
实事求是
Contrast
High-Resolution Transmission Electron Microscopy
Point defect: localized disruptions in an otherwise perfect
arrangement of atoms in a crystal lattice structure. A point
defect involves a single atom or pair of atoms, and thus is
different from extended defects such as dislocations and
grain boundaries (which are described later).
Vacancies, Interstitial defects, Substitutional defects
HREM images of point-defect clusters formed in a strained SiGe/Si
heterostructure with a 0.5% misfit at various stages of irradiation a ͒ after 1
min; ͑ b ͒ after 10 min; ͑ c ͒ after 45 min. The inset in ͑ b ͒ corresponds to the
part of the defect shown by the white rectangle.
实事求是
Contrast
Scanning Transmission Electron Microscopy
Inelastic signals used in STEM imaging
Transmitted beam with low-angle scattered electrons are collected using a BF detector to form a
STEM BF image
Scattered electrons are collected using an annular DF (ADF) detector to form a STEM-ADF image
Scattered electrons are collected using different detectors depending on the scattering angle
STEM BF image: Scattering angle < 10 mrad + BF detector
STEM ADF image: Scattering angle < 50 mrad (Bragg Diffraction) + ADF detector
STEM HAADF image: Scattering angle > 100 mrad + high angle ADF detector
STEM mode is more efficient for energy-dispersive spectroscopy (EDS) analysis at nanoscale
实事求是
Contrast
HAADF-STEM
A Z-contrast imaging technique, depends on the square of atomic number Z
better contrast than better detectability directly interpreted at
diffraction contrast Than conventional atomic resolution
实事求是
Contrast
STEM-BF
HAADF image is sensitive to the absolute numbers of atoms (Nb41→bright，Al13 →dark)
STEM-BF image (phase-contrast) shows lattice images of both film and substrate
实事求是
Contrast
Energy-Dispersive Spectroscopy (EDS/EDX)
It is referred as simple technique used for
compositional analysis with TEM.
electrons from inner shells can knockout and
result into a transition from higher levels to
core level with the emission of an X-ray. The
energy of these characteristic X-rays can tell
the chemical nature of the material. X-ray
energy-dispersive detectors are available
commercially which can collect the X-ray
signals and display in the form of spectrum
实事求是
Contrast
Electron Energy-Loss Spectroscopy (EELS)
Fast-moving electrons lost energy during interaction
with sample. The amount of electrons at each
energy loss can be measured using an electron
energy-loss spectrometer
An EELS spectrum typically consists of three parts:
zero-loss region, low-loss region, and core-loss
region
STEM-BF image (phase-contrast) shows lattice
images of both film and substrate
实事求是
Contrast
Electron Energy-Loss Spectroscopy (EELS)
An EELS spectrum consists of three parts: zero-loss region, low-loss region, and core-loss region
实事求是
Contrast
Chemical Mapping
Used for analyzing the compositional changes of a subset of atomic lattice at atomic occupancy that
can be achieved by proper recording of angle of reflection for diffracted electrons in TEM
Characterization of sharpness of interfaces among hetero-epitaxial layers and structural analysis
Exact location of specified elements in samples
实事求是
Chapter 5
Transmission Electron Microscope
(TEM)
Basics of TEM
Types of TEM & Related Spectroscopy
Application of TEM and Practices
In situ TEM: Theory and Practices
实事求是
Application of TEM
TEM can be utilized for:
Morphology of nanomaterials
Nanomaterials-polymer interface
Localized chemical composition
Crystal structure, microstructural defects
Differentiating phases of nanomaterials by
using electron energy-loss spectroscopy
Chemical mapping of an area of interest of
the sample
TEM images
实事求是
Contrast
Morphology
SiO2
实事求是
Contrast
Particle Size
40 nm
Pd particle size distribution analysis of Pd/C
Size distribution analysis of SiO2 nanoparticles
实事求是
Contrast
Core-shell Structure
The HAADF-STEM image and FT image of Pt(core)-Pd(shell)
nanoparticles, with zone axis being [001] and [110] respectively Pt-Pd nanoparticles characterized using Cs-STEM and EELS
实事求是
Contrast
Atomic-Resolution Measurement of Oxygen Vacancies
Concentration in Oxide Materials
By combining computer image
simulation & quantitative intensity
measurement, oxygen vacancy in
single lattice defect region can be
measured
Oxygen vacancy concentration
estimated by measured intensity
is between 0.4−0.7
The average oxygen vacancy
concentration obtained through
data analysis from all six
boundaries is 0.68 ± 0.02, with
[a] High-resolution image of Σ =3{111} twin boundary plane of BaTiO3 [110] crystal, [b] he amplified
standard deviation of 0.16 figure, from which we can see oxygen atom column lies between two Ti atom columns
实事求是
Contrast
Surface reconstruction
In vacuum, the distance between outermost
layer and second outermost layer of {100} plane
is 0.2 nm, which is the same with the {200}
planes spacing of bulk gold; the atomic distance
near the outermost layer is 0.29 nm, which is the
same with {100} plane spacing of bulk gold
In reaction atmosphere (CO oxidation at room
temperature), both Au atomic distance and plane
spacing are 0.25 nm, which is the result of the
surface reconstruction of Au {100} plane
实事求是
Contrast
Experimental: Sample Preparation Methods for Powder Samples
TEM commonly uses sample loading tools
in the form of rods, referred to as sample
rods. Different sample rods are available
for various testing requirements.
The samples are mounted on support
grids, and placed at the front end of the
rod. Each sample rod can accommodate a
maximum of 1-2 copper grids.
The advantage of using sample rods for
loading is that the tools are compact,
occupying minimal space.
实事求是
Contrast
Experimental: Sample Preparation Methods for Powder Samples
TEM Grids
实事求是
Contrast
Experimental: Sample Preparation Methods for Powder Samples
Solution Dispersion-Drop Method
Step 1: Choose a suitable support film based on the sample characteristics and testing requirements.
Step 2: Select a dispersant. Typically, anhydrous ethanol is used based on the nature of the sample.
Step 3: Disperse the powder in the dispersant using ultrasound or stirring to create a suspension. Note: The powder
density in the suspension should not be too high.
Step 4: Load the sample onto the support film using either the drop or pick-up method.
Step 5: Once the droplets on the support film are thoroughly dried, the sample preparation is complete, and electron
microscopy observation can be carried out.
实事求是
Chapter 5
Transmission Electron Microscope
(TEM)
Basics of TEM
Types of TEM & Related Spectroscopy
Application of TEM
In situ TEM: Theory and Applications
实事求是
Contrast
In situ TEM: Theory and Applications
Observe/monitor/record the dynamic responses
and microstructural evolution of specimen
resulting from external stimuli including
heating, electricity, mechanical property etc.
Characterization of sharpness of interfaces
among hetero-epitaxial layers and structural
analysis
To apply these external stimuli, different types
of TEM holders capable of straining, lasing,
heating/cooling, electric are available
commercially or are fabricated in the laboratory.
实事求是
Contrast
In situ TEM: Theory and Applications
In situ TEM holders: nano-chip controls heating/cooling, gas and biasing
实事求是
