J Electron Microsc (Tokyo) 2005 Liu 251 78

The Author 2005.
Published by Oxford University Press

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Journal of Electron Microscopy 54(3): 251278 (2005)

doi:10.1093/jmicro/dfi034
...................................................................................................................................................................................................................................................................................................................
Scanning transmission electron microscopy and

its application to the study of nanoparticles
and nanoparticle systems
Jingyue Liu*
Monsanto Company, U1E, 800 North Lindbergh Boulevard, St Louis, MO 63167, USA
*E-mail: jingyue.liu@monsanto.com
............................................................................................................................................................................................................................................
Abstract
Scanning transmission electron microscopy (STEM) techniques can

provide imaging, diffraction and spectroscopic information, either
simultaneously or in a serial manner, of the specimen with an atomic
or a sub-nanometer spatial resolution. High-resolution STEM imaging,
when combined with nanodiffraction, atomic resolution electron energyloss spectroscopy and nanometer resolution X-ray energy dispersive
spectroscopy techniques, is critical to the fundamental studies of
importance to nanoscience and nanotechnology. The availability of
sub-nanometer or sub-angstrom electron probes in a STEM instrument,
due to the use of a field emission gun and aberration correctors, ensures
the greatest capabilities for studies of sizes, shapes, defects, crystal and
surface structures, and compositions and electronic states of nanometersize regions of thin films, nanoparticles and nanoparticle systems. The
various imaging, diffraction and spectroscopy modes available in a
dedicated STEM or a field emission TEM/STEM instrument are reviewed
and the application of these techniques to the study of nanoparticles and
nanostructured catalysts is used as an example to illustrate the critical
role of the various STEM techniques in nanotechnology and nanoscience
research.
............................................................................................................................................................................................................................................
Keywords
electron microscopy, STEM, Z-contrast microscopy, nanodiffraction,

SEM, EELS, EDS, Auger, nanoparticle, supported catalyst, surface
............................................................................................................................................................................................................................................
Received
23 December 2004, accepted 13 March 2005, online 25 August 2005
............................................................................................................................................................................................................................................
Introduction
Advanced electron microscopy techniques, especially
scanning transmission electron microscopy (STEM) techniques, are indispensable for characterizing interfaces
and defects, nanodevices, nanoparticles and catalysts, and
other nanosystems. The single most important feature of a
STEM instrument is its versatility: atomic resolution images,
diffraction patterns from nanometer regions and nanometerscale spectroscopy data can be obtained either simultaneously or sequentially from the same region of the specimen.
The availability of the various imaging, diffraction, and
spectroscopy techniques within a single instrument makes
Dedicated to the memory of the late Professor John M. Cowley.
STEM the most powerful microscope for characterizing

the physicochemical nature of nanoscale systems.
When an electron nanoprobe interacts with a specimen
inside a STEM instrument, a variety of electron, electromagnetic and other signals can be generated. Figure 1 shows
a schematic diagram illustrating the common signals that
are used in a dedicated STEM instrument. All these signals
can be used to form images or diffraction patterns of the
specimen or can be analyzed to provide spectroscopic
information. For example, by collecting high-angle scattered
electrons with an annular detector, high-angle annular
dark-field (HAADF) images (also called Z-contrast images)
can be formed to provide information about structural
variations across the sample on an atomic level. Electron
energy-loss spectroscopy (EELS), which is based on the
252 J O U R N A L O F E L E C T R O N M I C R O S C O P Y , Vol. 54, No. 3, 2005
Fig. 1 Schematic diagram illustrates the various signals generated inside a scanning transmission electron microscope that can be used to
form high-resolution images, nanodiffraction patterns or spectra of the region-of-interest. X-ray energy dispersive spectroscopy (XEDS);
Auger electron spectroscopy (AES) and scanning Auger microscopy (SAM); secondary electron spectroscopy (SES) and secondary electron
microscopy (SEM); annular dark-field (ADF) and high-angle annular dark-field (HAADF); coherent electron nano-diffraction (CEND);
parallel electron energy-loss spectroscopy (PEELS); bright-field (BF) and dark-field (DF).
energy analysis of the inelastically scattered electrons, can

provide information on the electronic structure, oxidation
states, and chemical composition on an atomic or subnanometer scale. X-ray energy dispersive spectroscopy
(XEDS) can give quantitative data describing changes of
elemental composition associated with inhomogeneous
structures of the sample. The combination of XEDS and
EELS with HAADF imaging technique can provide detailed
information on the composition, chemistry, and electronic
and crystal structure of nanoscale systems with atomic
resolution and sensitivity. By collecting or analyzing secondary electron (SE) and Auger electron (AE) signals
emitted from the specimen surface, we can extract information about the surface topography or surface composition
of the specimen. By positioning an electron nanoprobe
at the area of interest, coherent electron nanodiffraction
(CEND) patterns from individual nanocomponents can be
acquired to provide multitudinous information on the

nanostructure of the specimen. The powerful combination
of high-resolution imaging with nanospectroscopy and
nanodiffraction techniques has proved invaluable in solving
a plethora of materials problems, including challenging
industrial problems.
Professor John M. Cowley dedicated >30 years of his
research effort to exploring, developing and establishing
various imaging, diffraction and spectroscopic techniques
that can be practiced in a dedicated STEM instrument. Using
a heavily modified HB5 STEM instrument from VG Microscopes, Ltd of England (see Fig. 2), Professor Cowley
investigated the various modes of high-resolution STEM
imaging [141], developed optical systems for conveniently
recording nanodiffraction patterns, and established the
nanodiffraction technique as a viable alternative to investigate the structures of nanoscale systems including small
J. Liu STEM of nanoparticles and surfaces 253
Fig. 2 The heavily modified VG HB-5 scanning transmission electron microscope of which Professor John M. Cowley used at Arizona
State University for all his experimental research work. The black box (indicated by the arrow) contained the unique optical system that
transfers the light to the various photomultipliers (PMs) and the low-light sensitivity TV camera. The ADF images were formed by positioning
a light-absorbing mask in the center of the optical system. In the late 1980s, we used to use a US coin of a penny, a dime or a quarter as
the mask of the diffraction pattern and were able to independently vary the inner and outer collection angles of the ADF detector. Other
configured STEM detectors were also tried by masking the various parts of the diffraction pattern displayed on the optical system inside the
black box.
particles, surfaces and biological systems [48,4266].

Throughout his experimental research activities at Arizona
State University, Professor Cowley steadfastly explored
various avenues, including holography, atomic focuser and
diffraction imaging in recent years to improve resolution
in STEM. Not only did he develop theories for various
imaging and diffraction techniques but he also applied these
new methods to the structural study of surfaces and
interfaces, small particles and supported catalysts, localized
defects and disordering, carbon nanotubes and many other
nanosystems.
The incorporation of atomic resolution STEM techniques
into the newer generation field-emission TEM instruments
[6769] and the revival of the experimental dedicated STEM
instruments, especially the ones incorporating the aberration
correctors or monochromators [7077], clearly demonstrated the increasing acceptance and the power of STEM
techniques that Professor Cowley had been championing for
the last 30 years. The recent achievement of sub-angstrom
resolution imaging [72,73,76] and atomic scale spectroscopy
[74,75] in Cs-corrected STEM instruments will undoubtedly
further enhance and expand the impact of STEM techniques

on nanoscience research. Professor Cowley recently stated:
STEM is finally coming into age and will soon become
mainstream.
There have been many reports, in the last decade or so, on
atomic resolution HAADF imaging and EELS techniques as
well as the application of these techniques to the study of
interfaces and defects [69,7881], quantum dots [82], and
nanoparticles and supported catalysts [8390]. Most of these
studies, however, focused primarily on the HAADF and
EELS techniques and capabilities. While the combination of
these two atomic resolution techniques has proved to be
extremely powerful for solving materials problems (especially interface structures), other imaging, diffraction and
spectroscopic techniques readily available in a STEM instrument can provide complementary and unique information
on the specimen of interest. In this paper, we review some
recent developments of the various STEM techniques, which
are pioneered by Professor John M. Cowley, with a focus
on applying these techniques to the fundamental study of
nanoparticles and nanoparticle systems.
STEM imaging: shadow image,

projection microscopy and electron
Ronchigrams
The simplest form of imaging in a STEM instrument is
shadow imaging (also called point projection microscopy).
Projection microscopy was proposed as early as 1939 by
Morton and Ramberg [91]. In a projection microscope, the
greatly magnified shadow of an object can be obtained
by using the quasi-radial propagation of a point or small
electron source with the object inside the beam path; it is
essentially a lensless microscope based on the radial propagation of an electron beam from a point source. The
magnification of the shadow image on the observation
screen is determined by the ratio of the distance between
the observation screen and the point source to the distance
between the object and the point source. Magnifications of
106107 can be easily achieved when the object-to-point
source distances are in the range of 10 nm.
The use of a small electron source originating from a fieldemission gun in a STEM instrument guarantees the complete
coherence of the convergent electron nanoprobe impinging onto the specimen. In contrast to conventional highresolution TEM (HRTEM) imaging, the individual incident
rays of different angles within the coherent convergent
nanoprobe can interfere with each other; the diffraction of
the coherent beam by the specimen and the interference
among the incident and diffracted beams can result in
complicated forms of shadow images. In fact, in his original
paper on holography, Gabor [92] proposed that a very small
source of electrons should be placed close to a thin object
to form a highly magnified shadow image that could be
regarded as a hologram; with the correction of the lens
aberrations, the object could be reconstructed thereby resulting in much improved image resolution. To accomplish what
Gabor proposed, a high-brightness, ultra-stable, small electron source is needed; the availability of a nanoprobe in a
dedicated STEM or field emission TEM/STEM instrument
makes this proposal more feasible now. Some early experimental results explored the practicality of this reconstruction process [14]. The principal difficulty of employing this
in-line STEM holography, however, originates from finding
suitable ways of separating the conjugated images [14,27].
With the incorporation of Cs-correctors [70] or the use of
high-brightness nanotips [93], which provide near-point
sources, and the availability of high dynamic-range CCD
cameras and fast computers, Gabors proposal should
become more practical and greatly improved resolution
should be achievable by reconstructing the objects from
in-line holograms.
When a small electron probe interacts with a thin
specimen in a STEM instrument, the high-energy incident
electrons are scattered. The amplitude distribution of the
transmitted electrons at the far-field can be described by a
wave function C(K, X). The variable K is a 2-D vector in
the reciprocal space with |K| 2sin(y/2)/l (where y is the
scattering angle and l is the wavelength of the incident

electrons) and X designates the electron probe position on
the specimen. When the electron probe is scanned across the
specimen, variations of C(K, X) carry information about the
electron beamspecimen interactions. If the wave function
C(K, X) of the transmitted high-energy electrons can be
determined, we can extract structural information about the
specimen. It is, however, not possible to directly measure
C(K, X); instead, the intensity distribution of the transmitted electrons is observed on the detector plane, which
is located at a large distance from the specimen, I(K, X)
|C(K, X)|2. The wave function C(K, X), to first-order
approximation, can be expressed as:
CK, X QK * T Kexpi2pK X
where Q(K) is the Fourier transform of the transmission

function, q(x), of the specimen and the * symbol represents
convolution. The transfer function of the microscope, T(K),
is given by:
T K AKexpfiwKg
where the aperture function, A(K), is given by:
8
< 1 for K < K0
AK
:
0 for K > K0
where K0 is the cut-off wave-vector determined by the

aperture size of the probe-forming lens. The aberration
function of the objective lens, w(K), is approximated by (for a
non-corrected objective lens):
wK pDlK 2 0:5pCs l3 K 4
where D is the defocus value of the electron probe and Cs is

the spherical aberration coefficient of the objective lens. In
the phase object approximation [24], the specimen transmission function q(x) can be approximated as:
qx expisfx
where s p/(lE0) is the interaction constant, E0 is the

accelerating voltage and f(x) is the projected specimen
potential along the incident beam direction.
The amplitude distribution of the coherent incident probe
is represented by:
Z
PR T Kexpi2pK R dK
6
The amplitude distribution of the incident probe, P(R), is
determined by the Fourier transform of T(K), which is
determined by the aperture function A(K) and the aberration function w(K) of the objective lens. The probe size,
therefore, depends on the spherical aberration coefficient
of the objective lens, the wavelength of the incident electrons, the size of the objective aperture and the defocus
value of the electron beam. The integral in eq. (6),
unfortunately, cannot be done analytically and must be
obtained numerically. In practice, the spherical aberration
coefficient of the objective lens and the wavelength of the
incident electrons are not variables during an experiment;

the operator, however, can manipulate the size and shape of
the coherent electron nanoprobe by varying the size of the
objective aperture and the defocus value of the electron
beam.
If no objective aperture or a very large objective aperture
is used, then the stationary incident probe can be very large
depending on the defocus value of the electron beam.
Images formed in this way in the back focal plane are similar
to low magnification TEM images. Depending on the sign of
the electron beam defocus, the image magnification can be
positive or negative and the image contrast can be reversed.
This imaging mode can be conveniently used for the initial
survey of specimen features or for monitoring the specimen
movement when specimen tilt is required. Note that out-offocus shadow images are projection images observed in the
back-focal diffraction plane with a stationary electron beam.
When the third-order spherical aberration is dominant,
as in the round lenses used in electron microscopes, the
projection image of the specimen placed close to the position
of the minimum diameter of the incident probe, as illustrated
in Fig. 3a, is greatly distorted due to the aberrations of the
objective lens. For paraxial rays (e.g. the ray #4 in Fig. 3a),
the beam crossover is after the specimen so that the
magnification of the central part of the projection image is
high but negative (region 4 in Fig. 3b). For marginal rays
(e.g. the ray #1 in Fig. 3a), the crossover is before the
specimen so that for the outer part of the projection image
the magnification is high but positive (region 1 in Fig. 3b).
For a particular set of rays (e.g. the ray #2 in Fig. 3a), the
beam crossover is right at the specimen level so that the
magnification of the projection image of that specimen
region becomes infinity (region 2 in Fig. 3b). Taking into
account of the 3-D nature of the rays and the specimen, we
can deduce that there is one radius of infinite tangential
magnification (labeled as T in Fig. 3b) and another radius of
infinite radial magnification (labeled as R in Fig. 3b).
Note that in the shadow image of Fig. 3b the image
magnification changes continuously along the radius from
the optical axis. Furthermore, each point in the image can be
described by a wave vector K and its intensity I(K, X) is
determined by the wave function C(K, X) given in eq. (1).
The effect of the beam defocus on the final image can be
more appreciated if we imagine that instead of changing
Fig. 3 Schematic diagram (a) illustrates the effect of spherical aberration of the probe-forming lens on the crossover of the STEM probe.
Shadow images of amorphous carbon film at under-focus (b), near-focus (c) and over-focus (d). The tangential (T) and radial (R) circles of
infinite magnification are clearly discernible in (b). The circle in (c) indicates the optimum angular size of the objective aperture to be used for
high-resolution imaging.
the beam defocus we move the specimen along the optical

axis (see Fig. 3a). For example, when the sample is positioned right below the paraxial crossover, shadow images of
amorphous materials similar to Fig. 3d can be obtained. All
the points in the shadow image have a negative magnification and the contrast of the features is reversed (e.g. heavy
scatterers appear bright).
At close to the Gaussian defocus, a position called fusiform
focus (uniform focus) [94] exists; the position of this fusiform
focus is between the paraxial focus and the marginal one.
For a thin amorphous film, an almost featureless disc appears
in the center of the shadow image when the specimen is at
the fusiform focus position as shown in Fig. 3c. The angular
size of the disc is determined by the lens aberrations (primarily third-order spherical aberrations for non-corrected
lenses) and the wavelength of the incident electrons.
The smaller the Cs value of the microscope, the larger the
featureless disc.
The presence of the almost featureless disc in shadow
images of amorphous materials proves to be very useful for
the practical operations of a STEM instrument. First, the
center of the disc defines the coma-free optical axis of the
electron beam so that it can be used as the reference for
alignment of other components [6,7,12,13,68]. Second, the
size of the disc defines the optimum aperture size that should
be used to form the smallest electron nanoprobe. Electrons
arriving at the specimen from larger incident angles (outside
the circle in Fig. 3c) do not contribute to the central peak of
the coherent electron nanoprobe; instead, they add to the
oscillating tails, thereby broadening the electron nanoprobe.
Accordingly, if one desires to have most of the electrons
confined to the smallest central peak, then one should
allow only the electrons with incident angles smaller than
the one defined by the circle in Fig. 3c to enter the objective
aperture. For high-resolution annular dark-field (ADF)
imaging, however, an objective aperture with an angular
size larger than the optimum angle is sometimes used in
order to have a narrower central peak of the electron probe
(at a larger under-focus value), thereby providing higher
image resolution at the expense of the image contrast [25].
Another important use of the shadow image of amorphous
materials is to correct the axial astigmatism in the STEM
imaging mode. If the objective lens has astigmatism, the
circular symmetry of the featureless disc or the circle of
infinite magnification is distorted. The degree and direction
of the distortion are determined by the lens astigmatism.
Similar to the use of a tableaux of diffractograms for
astigmatism correction in a HRTEM instrument, shadow
images of amorphous materials can be effectively used to
correct these aberrations. Figure 4 shows a set of shadow
images of the same region of an amorphous carbon film
demonstrating the use of shadow images to correct the
astigmatism of the probe-forming system. Shadow images
can also be used to monitor the instabilities of the microscope and the specimen; instabilities well below 0.1 nm can
be easily discerned in near-focus shadow images.
Correlation of shadow images, obtained from different

probe positions, can provide the exact magnification of the
selected points in the shadow images. The quantification of
the local magnifications in a large portion of the shadow
image provides an avenue to calculate the axial aberration
coefficients and other parameters that control the performance of the probe-forming systems. The availability of
high-sensitivity CCD detectors and fast desktop computers
makes it now possible to quickly auto-tune Cs-correctors
based on the shadow images [71]. The effective use of
shadow imaging to properly align and tune the electron
optical system clearly contributes significantly to achieve
resolution improvement in STEM instruments by using
Cs-correctors [73].
When the specimen is a thin, crystalline material and
when the beam is aligned along a zone axis or in a direction
for systematic diffraction, the shadow image of a set of
parallel lattice planes is distorted by the lens aberrations
to give a set of loops or serpentine fringes. Such fringes are
also known as Ronchi fringes or Ronchigrams in honor of
Ronchi who observed such fringes when a diffraction grating
was placed near the focus of a large telescope mirror and
who correlated the presence of such fringes to the lens
aberrations [94]. Typical Ronchi fringes in electron shadow
images of crystalline materials are shown in Fig. 5. Similar
to the discussion of shadow images of amorphous materials,
the distortion of the straight lattice planes, especially near
focus, is caused by the lens aberrations. The distortion is
smaller for large defocus values and for lenses that have
smaller Cs values. The Ronchi fringes in the electron
Ronchigrams should have the exact symmetry as that
of the crystal in that particular orientation. Thus, one can
use the electron Ronchigrams to correct astigmatism, to
align the microscope and to center the objective aperture.
Measurements of the dimensions of the fringe features
in electron Ronchigrams of thin crystals can provide
accurate values of the spherical aberration coefficient of
the objective lens and the exact focus value of the electron
probe [13]. The electron Ronchigrams obtained at the
under-focus (Fig. 5a), near-focus (Fig. 5b) and over-focus
(Fig. 5c) settings have very different forms, which provide a
simple and convenient way to align and tune the electron
optical system and to orient the crystalline specimen region
of interest.
Large under-focus electron Ronchigrams of zone axis
crystals can provide a readily interpretable image of the
crystal lattice. Figure 5d shows such an electron Ronchigram
of a GaAs crystal oriented along the [011] zone axis. Fringes
representing the crystal lattice spacings can be seen in all
directions near the optical axis. At large angles, the fringes
are distorted because of the spherical aberration of the
objective lens. Their distortion, as a function of angle from
the coma-free optical axis, is circularly symmetric and their
intensity distribution can be affected by the beam alignment
with the exact zone-axis of the crystal. With the use of the
aberration correctors in a STEM instrument, the regions of
Fig. 4 A set of shadow images of an amorphous carbon film illustrates the use of shadow images to correct the astigmatism of the
probe-forming lens, to find the coma-free optical axis, and to determine the defocus value of the electron beam.
interpretable image of the crystal lattices in the under-focus

electron Ronchigrams should be significantly enlarged.
Therefore, high-resolution information of local regions can
be extracted from the point projection microscopy images.
The resolution obtainable in this projection microscopy
mode should be comparable to that of the scanned STEM
images.
STEM imaging: convergent beam

electron diffraction and bright-field
and dark-field high-resolution imaging
When an objective aperture is used to limit the large-angle
rays entering the objective lens, convergent beam electron
diffraction (CBED) patterns are formed on the detector
plane. If the specimen is a thin crystal oriented along a
principal zone-axis, instead of shadow images or electron
Ronchigrams as discussed above, a CBED pattern consisting
of sets of convergent beam discs is obtained as schematically

illustrated in Figs 6a (side view) and 6b (top view). Each
diffraction disc subtends the same semi-angle a, which is
determined by the angular size of the objective aperture, at
the specimen. If a > yB (yB is the Bragg diffraction angle of
the diffracting planes), then the convergent beam diffraction
discs overlap as shown in Fig. 6c. For thin, perfect crystals,
the electron intensity within non-overlapping regions (e.g.
the region indicated by numeral 1 in Fig. 6b) is independent
of the probe position and the aberrations of the probeforming lens [4,5]. The electron intensity within regions
where discs do overlap depends on the probe position, the
lens aberrations and the defocus values of the objective lens.
The intensity modulations in regions of overlapping discs are
caused by coherent interference of high-energy electrons
that have different incidence-beam directions (different
incident wave vector Ki) but that are scattered into the same
direction (the same final wave vector Kf) by the crystal.
Fig. 5 Electron Ronchigrams of a GaAs crystal at under-focus (a), near-focus (b) and over-focus (c). Under-focus electron Ronchigram of a
GaAs crystal oriented along the [011] zone axis shows 2-D lattice fringes (d). Electron Ronchigrams of (a)(d) were obtained (recorded on a
tape) on the VG HB-5 STEM shown in Fig. 2. For comparison, image (e) shows an electron Ronchigram of a silicon crystal obtained (recorded
on a CCD camera) on the JEOL 2010F TEM/STEM.
The formation of interference fringes in the overlapping

regions is purely caused by the coherent nature of the
convergent electron nanoprobe.
If a detector is used to collect the signal in the diffraction
plane, then a STEM image is formed when the electron
nanoprobe is scanned across the specimen. Depending on
the detector configuration and positioning, various forms of
STEM images can be generated; the image interpretation,
the achievable resolution and the contrast mechanisms of the
acquired STEM image are determined by the shape and
the size of the detector. In STEM imaging, in addition to
the probe size, detector function is the other most important
variable.
For a fixed probe position X at the sample, the intensity
distribution of the transmitted electrons on the diffraction
observation screen is given by I(K, X) |C(K, X)|2. The
observed image intensity, I(X), as a function of the beam
position X, is given by:
I X
DKjCK, Xj2 dK
where D(K) is the transmission function of the detector.

The detector function, D(K), plays the most important role
in determining the nature of STEM imaging. For example, if
D(K) 1 for all scattering angles, the STEM image is formed
by collecting all the high-energy electrons penetrating
through a thin specimen. If the backscattering and the
electron absorption effects by the sample are negligible,
then, the image intensity I(X) should not vary with the
beam position X at all because of the conservation of
the total number of the high-energy electrons. Therefore,
no contrast will be observed in the STEM image, and
no information about the specimen can be inferred. When
the specimen becomes thicker, however, the absorption
and backscattering of high-energy electrons become appreciable so that an absorption contrast should be observable.
(The imaging theory of backscattered electrons may be
applicable here.)
On the other hand, If D(K) d(K) or d(K G) where G
is a reciprocal lattice vector, then eq. (7) reduces to: I(X)
|C(0, X)|2 or |C(G, X)|2. This is the same form as for BF or
DF TEM imaging with parallel illumination. If a very small
Fig. 6 Schematic diagrams show the formation of convergent electron beam diffraction patterns with overlapping disks: (a) side view and (b)
top view. The numerals in (b) indicates the number of overlapping diffraction discs in that region of the diffraction plane. Coherent
convergent electron beam diffraction pattern from a GaAs crystal oriented along the [011] zone axis (c) shows the overlapping discs. Brightfield STEM image of a TiO2 nanoparticle (d) shows 2-D lattice fringes and the corresponding diffractogram is shown in the inset.
detector is positioned at any point in the overlapping regions

of the diffraction discs, lattice fringes should be obtained by
scanning the electron probe across the specimen. Twodimensional lattice fringes can be obtained by positioning
the STEM detector at a point where three or more nonsystematic diffraction discs overlap. These multiple-beam
interference regions are labeled as numeral 3 (three-beam
interference) and numeral 4 (four-beam interference) in
Fig. 6b. High-resolution BF STEM images can, therefore, be
interpreted exactly as those of HRTEM images. Figure 6d
shows such a BF STEM lattice image of a titania nanoparticle;
the inset in Fig. 6d is the corresponding diffractogram of
the high-resolution BF STEM image. Nanoparticles of
titania are used in many commercial applications, including
industrial catalysts, paints, coatings and fillings in fibers.
High-resolution dark-field STEM images can be easily
obtained by moving the detector to a point outside the
directly transmitted disc. For example, a 2-D DF STEM lattice
image can be obtained by shifting the STEM detector to

position D, which is labeled in Fig. 6b. DF STEM
imaging technique is useful for identifying small particles
in supported metal catalysts, defects in extended crystals and
different phases in polycrystalline nanophase materials.
Similar to the tilted dark-field imaging in HRTEM,
DF STEM technique can provide higher image resolution
under optimum conditions [4,5].
The contrast of high-resolution STEM images varies with
the displacement of the STEM detector. The movement of
the STEM detector corresponds to beam tilt in TEM. In
STEM, however, the relative shift of the BF detector is easily
accomplished by deflecting the whole diffraction pattern
with the use of scanning coils. Unlike beam tilt in TEM, the
movement of scanning coils does not perturb the optical
alignment of the STEM microscope. Thus, the contrast of
specific features of a sample can be conveniently enhanced
or reduced by shifting the position of the STEM detector
without the complication of misaligning or realigning

the microscope. This method is useful for imaging highly
inhomogeneous samples, especially for identifying small
particles or for imaging inter-phase interfaces with enhanced
chemical sensitivity. The disadvantage of both the BF and
DF STEM imaging modes is that most of the transmitted
electrons are not utilized.
STEM imaging: large-angle bright-field

and ADF imaging
The phase contrast of BF STEM images rapidly decreases
with the increase of the detector size. By applying the
Principle of Reciprocity [1], we can deduce that the increase
of the detector size in STEM is equivalent to the increase in
the illumination convergence angle in TEM. The use of large
convergence angles of illumination in TEM pushes the first
crossover of the contrast transfer function to higher values
and causes a rapid damping of high frequency oscillations.
Interpretable image resolution can be improved at the
expense of image contrast.
If the STEM detector is increased to just coincide with the
disc of the directly transmitted electrons, i.e. D(K) A(K),
imaging theory suggests that, with a phase object approximation, the image intensity can be approximated by the
method of Cowley [24]:
IBF X 1 21 cossfX * jt Xj2
where sf(X) is the projected potential along the beam

direction and s is the interaction constant. In a weak phase
object approximation cos(sf(X)) 1 0.5(sf(X))2, thus:

IBF X 1 sfX2 * jt Xj2
This is a form of incoherent imaging: the phase contrast is

washed out and the image resolution is determined by the
probe current distribution inside the sample.
For dynamical diffraction in crystalline materials, the
above consideration is not valid and complicated calculations
need to be considered. Note that eq. (9) suggests that with
the increase of the detector size, the STEM image, within the
weak phase object approximation, changes from coherent
imaging to completely incoherent imaging. Furthermore,
the image formed by a large angle BF (LABF) detector, as
represented by eq. (9), is not a linear image anymore with
respect to the specimen potential. The image resolution
achievable in LABF images should be at least double that
of the point-detector BF STEM image or, by the Principle of
Reciprocity, that of the HRTEM image.
In practice, the relative size of the STEM detector can be
continuously varied by changing the strength of the postspecimen or projector lenses (see Fig. 7). If all the directly
transmitted electrons and a large portion of the scattered
electrons are collected to form the STEM image, then, the
dominant phase contrast, usually visible in BF STEM images,
is significantly suppressed [25,84]. The contrast of LABF
Fig. 7 Schematic diagram illustrates the geometric arrangement of

BF, ADF and HAADF detectors. The parameter y represents the
collection (semi-) angle of the BF detector; a1 and a2 are the inner
and outer collection (semi-) angle of the ADF detector, respectively;
b1 and b2 are the inner and outer collection (semi-) angle of
the HAADF detector, respectively. These collection angles can be
changed by varying the strength of the post-specimen projector
lenses.
images is predominantly due to absorption effect, weak

diffraction effect, plus an electron channeling effect; it is less
sensitive to the change of beam defocus, sample thickness, or
the Fresnel effects at interfaces or surfaces [25]. For crystals
with principal zone-axes aligned in the incident beam
direction, the diffraction and phase contrast are significantly
reduced in LABF images; but the image resolution is
improved [25].
To understand the contrast characteristics and the
resolution of LABF STEM images, we can rewrite eq. (7) as:
Z
IX DLABF K DADF KjCK, Xj2 dK
ILABF X IADF X
10
The diffraction plane is divided into two complementary

parts: a bright field detector and the corresponding ADF
detector (see Fig. 7). If we assume that the specimen is thin
enough so electron backscattering and absorption is negligible, then:
ILABF X IADF X 1
and ILABF X 1 IADF X

11
Therefore, the LABF image is complementary to the

corresponding ADF image obtained with an inner collection
angle as large as that of the LABF detector. LABF images can

be interpreted in the same way as the corresponding ADF
images: improvement in image resolution, increased atomic
number sensitivity and less dependence on sample thickness. For thin specimens, the contrast of the LABF image
could be lower than that of the corresponding ADF image
since most of the directly transmitted electrons do not carry
specimen information. In practice, this large background
signal, however, can be easily subtracted by adjusting the
brightness and contrast controls of the STEM detector.
By collecting electrons scattered outside the central beam
in the diffraction pattern (see Fig. 7), an ADF image of the
sample is formed. In fact, atomic resolution imaging was
first achieved in STEM by using an ADF detector to collect
all the electrons scattered by heavy atoms supported on an
ultra-thin, light-element substrate [95]. ADF images of thin
crystals of Ti2Nb10O29, giving an image resolution much
better than that of the corresponding BF STEM images,
were obtained by Professor Cowley in the early 1980s [11].
For various reasons, this powerful high-resolution imaging
mode, however, was not pursued aggressively by the
research group at Arizona State University until the late
1980s [20,84].
The ADF imaging mode, however, has its drawbacks.
Because of the low collection angle of the ADF detector,
strong dynamical diffraction effects from crystalline materials obscure its compositional sensitivity; this is especially
severe if one wants to detect small metal particles in
supported metal catalysts. The contrast of ADF images of
supported metal catalysts critically depends on the size of the
inner collection angle, a1 (see Fig. 7), of the ADF detector.
For imaging metal particles supported on a thick substrate,
the contrast of the metal particles can change from dark, to
almost none, then to bright with the increase of the inner
collection angle of the ADF detector [20]. This angularfiltering effect is more useful if an annular ring detector is
used, which will be discussed later.
STEM imaging: HAADF imaging or

Z-contrast microscopy
The diffraction effects in ADF images of crystalline materials
can be greatly suppressed by increasing the inner collection
angle of the ADF detector beyond the Bragg reflections so
that only high-angle scattered electrons contribute to the
collected signal (see Fig. 7) [96]. This imaging mode is called
HAADF or Z-contrast microscopy. The inner collection angle,
b1, is the most critical parameter in determining the nature
of the HAADF images; the outer collection angle, b2, is
generally made large enough to collect more high-angle
scattered signals.
In HAADF imaging, the diffraction and phase contrast is
significantly suppressed and the compositional sensitivity is
recovered; but, the signal strength is greatly reduced. The
development of HAADF imaging technique has proved very
successful for characterizing small particles and supported
metal catalysts with sub-nanometer or atomic resolution

and high compositional sensitivity [8385,90]. Small metal
or alloy nanoparticles in high surface-area supports can be
easily revealed in HAADF images. Figure 8a, for example,
shows a high-resolution HAADF image of a g-alumina
supported PdCu alloy catalyst, clearly revealing the size
and spatial distribution of the PdCu nanoparticles. In this
particular industrial catalyst, the alloy nanoparticles as small
as 0.5 nm in diameter can be revealed in the HAADF images
with high contrast and visibility, thus making it possible to
reliably extract information on the size and spatial distribution of subnanometer nanoparticles in commercial catalysts.
Both the size and spatial distributions of metal particles in
supported metal catalysts are important parameters that
determine the activity, selectivity and stability of commercial
catalysts. This type of information cannot be obtained from
any other characterization technique.
Figures 8b and 8c show high-resolution HAADF images
of a Au/TiO2 catalyst precursor material, clearly revealing
clusters of Au-containing species anchored onto the titania
surface. Individual Au atoms as well as Au clusters and
nanoparticles are revealed in the same image; the revelation
of the co-existence of both individual Au atoms/ions and
clusters/patches of Au-containing species on the titania
surface is valuable for understanding the interaction
between the Au compounds and the surface sites or defects
present on the TiO2 nanoparticle support. Oxygen vacancies
on the titania surface are believed to be the anchor sites for
the precursor molecules and may act as the nucleation
centers during the catalyst reduction process [97]. This type
of atomic scale insight into the catalyst precursor material
and how it interacts with the support surface is critical to
developing nanostructured industrial catalysts with desired
performances.
The high atomic-number sensitivity of HAADF images can
be utilized to differentiate clusters or nanoparticles in mixed
metal or alloy catalysts. For example, Fig. 9a shows a HAADF
image of a model catalyst consisting of mixed Pt and Pd
nanoparticles, clearly revealing the Pt nanoparticles with a
much higher intensity. The quantitative interpretation of the
image contrast, however, is not straightforward. Figure 9b
shows intensity line scans across a Pd and a Pt particle of
similar size. The ratio of the peak intensity of the Pt particle
to that of the Pd particle is 1.8far smaller than the ratio
of (ZPt/ZPd)2 2.9if we assume that the same number of
atoms along the beam direction for both the Pt and Pd
nanoparticles is measured. The difference between the
measured and the expected values could originate from
the different shapes of the particles or could be due to intermixing of Pt and Pd in the particles. Even if the nanoparticles
have exactly the same size and shape, the effect of electron
channeling can modify the intensity ratio between the
two particles if they are not oriented along exactly the
same direction with respect to the electron beam. The effect
of electron channeling and poor signal-to-noise ratio
makes it difficult to extract quantitative information on the
Fig. 8 HAADF image of a Pd-Cu/g-alumina alloy nanocatalyst shows the size and spatial distribution of the PdCu alloy nanoparticles as well
as the pore structure and morphology of the g-alumina support (a). HAADF image of a 5wt%Au/TiO2 catalyst precursor material shows the
presence of Au clusters and nanoparticles (b) as well as individual Au atoms (c) anchored onto the titania surface.
composition of mixed metal or alloy nanoparticles, especially

in supported metal/alloy catalysts.
Intensity analysis of HAADF images of metal nanoparticles
in supported catalysts has been reported [83]. In practical
industrial catalysts, however, it is difficult to determine the
shapes or shape distributions of the metal nanoparticles
because of the various errors introduced during the analysis
process (e.g. background subtraction, poor signal-to-noise
ratio, etc.) and the effect of electron channeling, especially
for larger particles, on the integrated intensity of individual
nanoparticles cannot be predicted or avoided. It is still an
extremely challenging task to extract statistically meaningful
data on the size distribution of metal or alloy nanoparticles

in industrial heterogeneous catalysts. Quantitative correlation of size distributions of metal nanoparticles in a supported metal catalyst to its performance, which is extremely
important for catalyst optimization processes, is difficult,
if not impossible, to obtain. Quantitative and statistically
meaningful information on the shape distribution of metal
nanoparticles in supported metal catalysts, which can be
important in determining the catalysts selectivity, has not
yet been reported.
When the nanoparticles become much smaller, for
example, clusters of a few to about a hundred atoms, the
Fig. 9 HAADF image of a model catalyst consisting of Pt and Pd

nanoparticles on a carbon support (a) and an intensity linescan
across a Pd and a Pt nanoparticle of similar size (b). Pure Pt
nanoparticles can be easily differentiated from the Pd nanoparticles.
Electron channeling effect complicates quantitative interpretation
of the observed contrast.
effect of electron channeling may not be significant. In this

particular case, the HAADF image intensity may be linearly
dependent on the sample thickness or the total number of
atoms that the electron probe encounters. Thus, it is possible
to determine the 3-D shape of nanoclusters if one can use
the integrated intensity of individual single atoms as an
internal calibration. For example, Fig. 10a shows an atomic
resolution HAADF image of a small Pt cluster. Individual
Pt atoms (indicated by the white arrows) were also revealed
in the image. Figure 10b shows an intensity profile across the
center of the small cluster, revealing that the distance
between the center atomic column and the nearest neighbors is 0.14 nm. Intensity analysis of the individual atomic
columns showed that some atomic columns contain three
Pt atoms along the electron beam direction while others
contain only two Pt atoms. Image instabilities caused by both
external and internal interferences and the sample movement made it difficult to acquire high-quality images with
good signal-to-noise ratio. Environmental control, sample
stability and signal strength are the most challenging issues if
one wants to routinely obtain high-quality, atomic resolution HAADF images of small clusters or nanoparticles and to
perform quantitative intensity analysis of the individual
clusters or nanoparticles.
Fig. 10 Atomic resolution HAADF image of a small Pt cluster and

individual Pt atoms in a model nanocatalyst (a) and the intensity
line scan across the small cluster (b). Using the intensity of the
individual Pt atoms (indicated by the white arrows) as an internal
calibration, the atomic layers (indicated by the numerals) in the
cluster can be deduced.
The use of Cs-correctors has made it possible to significantly improve the resolution of HAADF images and to
greatly increase the effective probe current [73]. Thus, the
location of single dopant atoms or promoter species can now
be observed with clarity, providing structural information
on the relationship between single dopant atoms and the
substrate [90]. Structural promoters of single atoms and
detailed structures of small nanoparticles and quantum dots
can now be investigated with a sub-angstrom resolution
[82,90]. The wide availability of Cs-corrected STEM or TEM/
STEM instruments will undoubtedly enhance our understanding of the structure and physicochemical properties of
small particles and clusters. It is now possible to study the
atomic structure and chemistry of metal or alloy nanoclusters in a dedicated STEM or field emission TEM/STEM
instrument. The direct imaging of the surface arrangement
of different atoms in bimetallic or multimetallic clusters can
provide extremely valuable information for understanding
the performance, especially the selectivity, of nanocluster
catalysts and for synthesizing nanocatalysts with desired
performances.
The nature of the signals collected by the HAADF detector
has been extensively investigated [18,98112]. The contrast
characteristics of incoherent HAADF imaging include:

(i) high atomic-number sensitivityapproaching Z2, (ii) less
dependence on beam defocus and sample thickness,
(iii) absence of proximity effects at interfaces or surfaces
and (iv) higher image resolution. For thin samples, the
image intensity is linearly proportional to the sample
thickness; the electron channeling effect in crystalline
materials, however, significantly modifies this relationship.
The imaging theory of both HRTEM and BF STEM is a
coherent, linear imaging theory: phase contrast and dynamical diffraction effect dominate the image contrast. For ADF
imaging, however, the detector always detects interferences
among the scattered waves and the directly transmitted
beam may not reach the detector; ADF imaging is thus a
non-linear imaging technique. The degree of coherence in
ADF images varies with the size of the inner collection angle.
For a phase object, the inner collection angle modulates a
coherence envelope given by the Airy function that is the
Fourier transform of the corresponding LABF detector.
Within this spatial envelope, the electrons scattered by
the spatially separated scatterers can interfere with each
other. The extent of the lateral envelope is inversely
proportional to the size of the inner collection angle of the
ADF detector. Therefore, increasing the inner collection
angle decreases the spatial extent of the coherence envelope.
When the coherence envelope becomes much narrower
than the distance between the neighboring scatterers, these
scatterers can be treated as independent scattering centers;
the primary electrons are then scattered incoherently.
The strength of the high-angle scattering, which gives the
HAADF imaging signal, depends on several parameters
including (i) large angle elastically scattered electrons,
(ii) phonon scattered electrons and (iii) multiply scattered
electrons. The imaging theory of HAADF microscopy follows
that of incoherent imaging: the high-angle scattered electrons can be treated as being scattered by independent
scattering centers. The lateral coherence of the scattered
electrons is almost completely suppressed because of detector
geometry (averaging effect) and thermal diffuse (phonon)
scattering. The columnar coherence of the scattered electrons is significantly reduced because of phonon scattering
although a small residue of the coherence still exists along
the incident beam direction [103113].
For zone-axis crystals, high-energy electrons may preferentially travel along paths of low-energy potentials in the
sample. This phenomenon is called the electron channeling
in crystalline materials [113]. The propagation of a coherent
convergent electron probe inside a perfect crystal in the
zone-axis channeling condition has been widely investigated
[31,99,113,114]. Remarkable electron focusing effects can
occur under channeling conditions. In fact, the focusing
action of the potential field of a single heavy atom or rows
of atoms extending through a thin crystal can be used to
significantly improve the resolution limits of modern electron microscopes [31]. The imaging properties of atomic
focusers have been investigated and resolutions of better
than 0.05 nm should be achievable in a STEM instrument

with a probe size of 0.4 nm [32,33,35]. By using carbonnanoshells as the atomic focusers, ultra-high-resolution
images have been obtained and individual tungsten atoms
with a size of 0.06 nm have been observed in diffraction
images by Professor Cowley [35,36,38,39].
The penetration of the incident electrons is different
for probes focused onto atomic columns of different species.
The channeling effect of a convergent probe is important
in interpreting high-resolution HAADF images of crystals
oriented in principal zone-axes. Phonon scattering, plus
the channeling effect, forms the basis of atomic resolution
HAADF imaging of crystalline materials. Because of the
effect of electron channeling and dechanneling on the highangle scattered electrons small perturbations of the potential
field can be manifested in HAADF images. For example, it
is possible to distinguish the location of individual atoms
within, or on the surface of, a substrate. This technique has
been effectively utilized to image the location of individual
Sb dopant atoms within a silicon crystal [115].
In the incoherent imaging limit, the image contrast
becomes a pure number contrast: the total number of
high-angle scattered electrons determines the image intensity at that pixel. Thus, HAADF images can be viewed as the
convolution of the intensity distribution of the incident
probe with appropriate cross-sections for high-angle scattering processes. Since high-angle scattering processes are
highly localized, the resolution of HAADF images is necessarily determined by the size of the incident coherent
electron probe. For crystalline materials, the image resolution may depend on the channeling or atomic focusing
conditions of the specimen.
With coherent, convergent beam illumination, the intensity distribution of the incident probe, I0(X), rather than the
vaguely defined probe size, is usually used to describe the
performance of a STEM instrument. The form of I0(X)
strongly depends on the size of the objective aperture, the
spherical aberration coefficient of the objective lens, the
beam defocus value, the energy of the incident electrons
and the instability of the microscope. The optimum probe
sizes in a STEM instrument depend on the selected imaging
and analytical modes. With the use of smaller objective
apertures, which is usually used for nanodiffraction, the
intensity distribution of the electron probe does not vary
appreciably with the change of beam defocus. On the other
hand, with the use of larger objective apertures, such as
those used in high-resolution STEM imaging, the intensity
distribution within the electron probe becomes increasingly
sensitive to the change of beam defocus. For high-resolution
imaging of zone-axis crystals, it is desirable to use an
objective aperture larger than the optimum aperture and
to work at an under-focus value slightly larger than the
Scherzer focus in order to improve image resolution without
introducing complications in interpreting the image [25].
For imaging small particles, however, the high-resolution
imaging condition may not be desirable since the large
probe tails complicate the measurement of the particle size.

A top-hat or Gaussian probe may be more appropriate for
determining the size distributions of isolated individual
nanoparticles. To determine the shapes and the surface
atomic arrangements of small nanoparticles supported on
high-surface-area supports is still a difficult task. Significant
improvement in image resolution and probe current by
using aberration correctors have made it possible to study
the exact shapes and surface atomic arrangements of small
particles and quantum dots [82]. Electron beam-induced
modifications of the specimen, however, may become an
important issue for determining the true surface structure of
small clusters and nanoparticles.
The high atomic-number sensitivity, the incoherent
imaging characteristics, the higher image resolution achievable and the intuitive relationship to the specimen make
HAADF imaging the most powerful STEM imaging technique for characterizing interfaces and defects, nanoparticles
and nanoparticle systems and other nanoscale systems.
STEM imaging: thin annular detector

and other configured detectors
As shown in Fig. 7, the central beam of the diffraction
pattern can be expanded, by the use of post-specimen or
projector lenses, to overlap the inner edge of the ADF
detector. A thin ring at the outer edge of the directly
transmitted beam, plus a small portion of the scattered
beams, can be collected to form an image of the specimen.
A specially designed thin annular detector (TAD) with only
10% difference between the inner and outer collection
angle can be used to form images that carry unique
information about the specimen [29]. The TAD can be
used to form bright-field (TADBF) or dark-field (TADDF)
images, depending on the size of the inner-collection angle
with respect to the convergence angle of the incidence
probe. By applying the Principal of Reciprocity, this imaging
mode is equivalent to hollow-cone illumination imaging
in TEM. Detailed treatment of the imaging process suggests
that the resolution of TADBF images can be significantly
improved [28,29].
The TAD imaging modes take advantage of selecting the
range of desired frequencies that give higher image resolution and excluding the lower frequencies that contribute to
the background signal. The TAD may also be used to collect
signals of small angle scattering to produce images of
amorphous materials or light element particles. For example,
carbon nanoparticles supported on amorphous silica can be
detected with good contrast [29]. The image contrast due
to strain fields near defects, interfaces and surfaces can be
enhanced in TAD images. Magnetic domains or domain
boundaries may also be revealed in TAD images with high
spatial resolution. The combination of TAD with HAADF
imaging technique can be very effective in examining
both heavy-element and light-element nanoparticles with
atomic-scale resolution.
Other specially configured detectors can be constructed

to increase image resolution, to enhance image contrast or
to extract unique information about certain features of the
specimen. For example, circular detectors splitting into
halves or quadrants have been used to study magnetic fields
or magnetic domain structures of thin films and small
particles [116,117]. Complex configured detectors have
also been explored for increasing image resolution or for
enhancing image contrast. For example, using the opticallens-transfer system shown in Fig. 2, the Cowley group at
Arizona State University explored the possibility of forming
images by excluding all the Bragg diffraction spots from
thin crystals or by using only electrons that are scattered
into certain regions of the diffraction plane. It is, however,
difficult to perform these experiments using physical masks.
The use of high dynamic-range CCD cameras and faster
computers to record the diffraction patterns at each pixel
has made it possible to perform various diffraction-imaging
configurations.
With configured STEM detectors, we can rewrite
eq. (10) as:
Z Ki1
Ii X
Di XjCK, Xj2 dK
12
Ki
XZ
i
Ki1
Di KjCK, Xj2 dK 1
13
Ki
where the summation is over the whole diffraction plane.

The resolution and contrast of the STEM images is then
dependent on the configuration of the configured STEM
detector. By selecting the frequency or the direction of the
wave vector in the diffraction plane, a plethora of imaging
modes can be used to extract complementary or unique
information about the specimen.
By digitally recording the whole diffraction pattern with
energy (E) discrimination for each pixel (probe position X)
on the sample, a 5-D function I(K, X, E) can be generated.
All information about the specimen can be extracted by
off-line processing of these digitally stored, energy-selected
diffraction patterns. By selecting certain portion(s) of the
scattered electrons as an input signal, various types of
images can be formed to give information about the
structure and the chemistry of the sample with atomic
resolution. This process, however, needs a tremendous
amount of computer work, fast image-acquisition systems,
a large collection of data, and a high stability of the
microscope and the specimen. Alternatively, reconstruction
of the wave function in amplitude and phase can be
accomplished by analyzing 4-D functions in the diffraction space. Initial attempts, using the technique of ptychography [118], on super-resolution STEM imaging has been
successful [119,120]. An image resolution better than
0.14 nm has been achieved on an STEM with a nominal
resolution of only 0.42 nm [120].
With the rapid advancement in the image acquisition
systems, faster desk-top computers, specially designed
microscope environments and the use of pulsed electron

beams, we should be able to efficiently use the various
signals available in a STEM instrument with minimum
exposure of delicate specimens to the electron beam. STEM
techniques will become more critical to the fundamental
studies of nanoscale systems and will contribute significantly
to the new era of nanotechnology and nanoscience research.
STEM imaging: secondary and Auger

electron microscopy and scanning
reflection electron microscopy of
surfaces
In a STEM instrument, the specimen is usually placed inside
the pole pieces of a highly excited objective lens. The emitted
secondary electrons first experience a strong magnetic field
before being collected by an SE detector. Owing to the effect
of this magnetic field, an emitted SE spirals in a cyclotron
orbit with a radius R that depends on the energy and the
emission angle of the SE as well as the strength of the magnetic field. After spiraling out of the bores of the objective
lens, secondary electrons are collected by an SE detector
through a transverse electric field. Because of the effect of
the magnetic field on the trajectory of the emitted secondary
electrons, the SE collection efficiency in a STEM instrument is high. The collection efficiency of low-energy
electrons can be further enhanced by the use of electron
parallelizers located inside the bores of the objective lens
[121,122]. The energy distribution of the collected secondary
electrons can be analyzed by an electron spectrometer.
Secondary electron spectroscopy can be used to investigate the energy distribution of secondary electrons from
different materials, to measure the work function of solid
specimens, and to study the charging effects of nonconducting materials.
Sub-nanometer surface details can be observed in
high-resolution SE images [16,17]. This implies that the
generation processes of secondary electrons are localized
to within 1 nm or less. It was first pointed out [17] and
later experimentally proved [123] that the generation of
secondary electrons is directly related to large-angle inelastic
scattering of the high-energy incident electrons. There exist
large momentum transfer mechanisms during the inelastic
scattering processes such as Umklapp (high-momentum,
low-energy transfer processes) or phonon-assisted electron
excitation processes. Inelastic scattering events involving
these processes are highly localized. The resolution obtainable in SE images is currently limited to 0.5 nm.
Small particles are often observed with a bright contrast
in high-resolution SE images; Fig. 11 shows a set of highresolution SE images of metal particles supported on various
oxides, revealing the high-spatial resolution and good image
contrast of small nanoparticles. The particle contrast in SE
images can be parameterized by the ratio of the particle
radius (R) to the average escape-depth (L) of the collected
secondary electrons. If R/L < 1, the brightness of a particle
increases with the size of the particle and the image intensity
has a maximum at the center of the particle. If R/L > 1, the
particle intensity slowly increases with the size of the particle
and the highest image intensity is approximately at a
distance d (R L) from the center of the particle. For
very large particles, the particle contrast evolves into the
edge-brightness contrast commonly observed in SE images.
Although the resolution of SE images is comparable to the
size of the incident probe, it is impossible to extract
information about the shape of nanoparticles with sizes
less than the escape depth of the collected secondary
electrons. Therefore, we cannot extract information about
detailed surface morphology of very small particles. We can
obtain, however, useful information about the relative
locations of nanoparticles with respect to the surface
topography of the supports. Detailed discussions on the
origin of small particle contrast and the resolution achievable
in SE images have been reported previously [124].
The production of Auger electrons is essentially similar to
that of low-energy secondary electrons; the initial excitation
produced by the inelastic scattering of the incident electrons
decays to generate a low-energy electron that can escape
into the vacuum. In contrast to the diffusion of secondary
electrons, Auger electrons must escape from the specimen
surface without losing any energy in order to be registered as
Auger peak signals. The reason that Auger electron spectroscopy is a surface-sensitive technique lies in the intense
inelastic scattering that occurs for electrons in this energy
range; only Auger electrons generated from the outmost
atomic layers of a solid can survive to be ejected and
registered as Auger electrons. Most of the emitted Auger
electrons are produced within a very short distance from
the sample surface, typically 0.33 nm.
In a STEM instrument, Auger electrons, emitted from
either the entrance or the exit surface of a specimen, can
be collected and analyzed by a cylindrical mirror analyzer
(CMA) or a concentric hemispherical analyzer (CHA)
electron spectrometer. Because of the high energy and
high brightness of the incident electrons, the employment
of magnetic parallizers, and the use of thin specimens in a
STEM instrument, high-quality Auger electron spectra can
be acquired with extremely high peak-to-background
ratios [125127]. Figure 12a shows a high-energy resolution
Auger electron spectroscopy (AES) spectrum of clean silver
nanoparticles supported on a small MgO crystal; the silver
MNN doublet is clearly resolved. Figure 12b shows the
corresponding oxygen KLL Auger peak from the same
specimen area. Surface compositional analysis of individual
nanoparticles is essential for understanding the activity and
selectivity of industrial bimetallic or multi-component catalysts used in a variety of chemical processes. The overall
composition of these individual nanoparticles can usually be
obtained by XEDS. It is, however, extremely difficult to
extract information about preferential surface segregation
or aggregation of individual components in nanoparticles
of different sizes. Because of the high-surface sensitivity of
Fig. 11 High-resolution secondary electron images of Ag (a) and Fe (b) nanoparticles on MgO smoke crystals and Ag nanoparticles on
a-alumina powders (c) and Pd nanoparticles on g-alumina crystals (d). Small metal clusters and nanoparticles on oxide supports are clearly
revealed with high resolution and bright contrast.
Auger electrons, it is possible to determine qualitatively

and, in some cases, quantitatively, the surface composition
of nanoparticles consisting of multiple components. Highspatial resolution Auger electron spectra can provide information about the surface enrichment of specific elements and
information about how this enrichment varies with the size
of the nanoparticles.
For electron transparent specimens, typically used in
STEM instruments, an image resolution <1 nm can be
achieved [125127] in scanning Auger microscopy (SAM)
images. Silver nanoparticles <1 nm in diameter and containing as few as 15 silver atoms have been detected [125].
Figures 12c and 12d show, respectively, Ag and O maps of an
Ag/MgO model catalyst, clearly revealing the high-spatial
resolution of Auger elemental maps, obtainable in dedicated STEM instruments. The resolution in SAM images
depends on several sample- and instrument-related effects.
The sample-related effects include: (i) surface topography,

(ii) escape depth of the collected Auger electrons, (iii)
contribution from backscattered electrons and (iv) localization of the Auger electron generation processes. The last
factor sets the ultimate resolution limit that will be achievable in SAM images. Since the primary inelastic scattering
processes involve excitation of inner-shell electrons, the
generation of Auger electrons is highly localized. With thin
specimens and high-energy incident electrons, the contribution from backscattered electrons should be negligible; it
may, however, degrade the image resolution and affect the
image contrast of bulk samples. The instrument-related
effects include: (i) the intensity distribution of high-energy
electron probes, (ii) the collection efficiency of the emitted
Auger electrons and (iii) the instability of the STEM
microscopes. At present, the instrument-related factors set
the limits of obtainable resolution to 1 nm in Auger peak
Fig. 12 Auger electron spectra of (a) Ag MNN and (b) O KLL peaks of an Ag/MgO model catalyst. Auger maps of silver and oxygen are shown
in (c) and (d), respectively. Auger electron spectra and scanning Auger microscopy images were obtained from the UHV STEM-MIDAS
(Microscope for Imaging, Diffraction, and Analysis of Surfaces) housed at Arizona State University.
images of thin specimens. The minimum detectable mass in

high-spatial resolution SAM images is <3 1021 g [125].
Scanning reflection electron microscopy (SREM) is
another technique that can be used to examine surface
details of bulk crystals. In SREM, the electron nanoprobe is
scanned over the surface with a grazing angle and a selected
part of the resulting diffraction pattern [a convergent-beam
high-energy electron diffraction (CBRHEED) pattern] is used
to form an image of the specimen surface [23]. Surface steps,
dislocations and other types of defects on the surfaces of bulk
crystals can be imaged with high contrast and resolution.
CBRHEED, scanning reflection EELS and XEDS techniques
can be used to provide information on the surface structure,
composition and even electronic states of bulk crystals [23].
If a HAADF detector is used, then the resulting highresolution surface image depends strongly on the atomic
number of the elements present on the specimen surface
and the phase contrast and dynamical diffraction effects are
greatly suppressed [23]. Similar to transmission HAADF

imaging, high-resolution detail of atom rows along which
the electrons can be channeled and atomic scale information
on the surface defects should be obtainable.
STEM diffraction: CEND

The advantage of STEM is that the electron beam can be
stopped at any point of interest on a sample and diffraction
or spectroscopy can be performed at that point with an
atomic or nanometer scale resolution. As discussed earlier,
CBED patterns can be formed in the observation screen
and the size of the diffraction discs is determined by the
convergence angle of the incident probe (see Fig. 6). These
CBED patterns are, however, different from those obtained
in a TEM. First, the sizes of the electron probes are usually
1 nm in diameter, much smaller than those obtainable
in TEM; thus, the diffraction patterns obtained in STEM are
usually called micro- or nano-diffraction patterns. Second,

the use of a field emission gun warrants the coherent nature
of a convergent nanoprobe: the illuminating aperture is
filled with completely coherent radiation and the final probe
entering the specimen can be treated as perfectly coherent.
In contrast, the illuminating aperture in conventional TEM
is considered incoherently filled and the illumination is
treated as completely incoherent.
CEND is the only technique that gives full diffraction
information about individual nanoparticles. Diffraction
patterns from the various parts of a nanoparticle can be
obtained to provide information about the structure as well
as the morphology of the nanoparticle.
For a perfect, thin crystal (no thickness variation, no
defects, no bending), there are no differences in the
diffraction patterns that are obtained with either a coherent
or an incoherent electron beam provided the diffraction discs
do not overlap (a < yB in Fig. 6a). This is a consequence of
the Bragg law: for each incident direction, only scattering
through mutiples of the Bragg angle is allowed; thus,
electrons with different incident beam directions cannot
interfere with each other although the incident electron
probe is completely coherent. If the crystal is thicker, the
intensity distribution within the diffraction discs may become
non-uniform, with sets of lines, bands or complicated
shapes. This is mostly due to dynamical diffraction effects
giving a variation of the incident and diffracted beam
intensities as a function of the incidence angle. If we ignore
the fine-details, CEND patterns of perfect crystals can be
treated the same way as those generated by an incoherent
electron beam with a nanometer-size probe.
For crystals containing defects (edges and bending,
stacking faults and dislocations, thickness variations, etc.)
elastic scattering from these defects can coherently interfere
with each other or with the Bragg-diffracted electrons.
Diffraction patterns, characteristic of the unique nature of
the defects, can be observed. For thicker or strongly scattering samples, any discontinuity in the sample can have some
observable effect on the CEND patterns. For example, when
a small electron beam scans across a straight edge of a MgO
cube aligned along the [001] zone-axis, first the central
transmitted disc shows strong streaking towards the crystal;
then diffraction spots appear at non-Bragg positions (Fig. 13).
Fine structures in these CEND patterns change rapidly with
the movement of the probe position. The streaking of the

central transmitted spot is attributable to the influence of the
crystal inner potential. The interference among waves
arriving from different incident beam directions gives rise
to perturbations of the Bragg diffraction spots. When only
part of the incident probe is positioned inside the MgO
crystal, electrons with different incident directions interact
with different parts of the crystal. The scattered electrons
interfere with each other to give a diffraction pattern
characteristic of the beam position and that part of the
specimen. Simulations using dynamical electron diffraction
theory show that the intensity distributions in CEND
patterns are sensitive to the surface or the defect structures
of the specimen [128]. A surface channeling effect may
also be responsible for the fine features observed in
CEND patterns from straight edges of small crystals; in this
case, the diffraction pattern can be treated as the combination of transmission and reflection high-energy electron
diffraction.
When the incident probe is positioned near the edge of
a crystal, CEND discs may show annular rings or splitting of
diffracted spots [47], which are clearly shown in Fig. 13.
Internal discontinuities, such as fault planes, out-of-phase
boundaries and thin layer precipitates, may give characteristic structures in their corresponding CEND patterns. For
example, CEND patterns from antiphase domain boundaries in ordered alloys show spot splitting of superlattice
reflections [49]. It is, however, impossible to make accurate
measurements of lattice parameters in CEND patterns
because of the large sizes of the diffraction spots. An error
of 5% or higher than that is common in determining lattice
constants of small particles by the CEND technique, and
much larger errors can frequently occur because of coherent
interference effects.
It is important to correlate the characteristic features of
CEND patterns to particle properties, such as the structure
of the particle, the nature of defects within the particle, or
the shape and size of the particle. A frequently observed
characteristic feature is the splitting of diffraction spots
along certain crystallographic directions of a small
particle. Figure 14 shows a set of CEND patterns that were
obtained from different positions on a small Au cuboctahedral particle, demonstrating the various features of
CEND patterns from nanoparticles. The spot splitting
Fig. 13 CEND patterns from a MgO cube oriented along the [001] zone axis. From left to right: the electron beam was moved toward the
MgO crystal. The spot streaking and splitting are unique characteristics of coherent electron nanodiffraction resulting from the discontinuities
at the specimen surface.
Fig. 14 CEND patterns obtained at different positions of a small Au cuboctahedral nanoparticle. These nanodiffraction patterns contain
information on the 3-D shape of the Au nanoparticle (see text for detailed discussions).
in non-overlapping CEND patterns is attributable to the

coherent nature of electrons diffracting from an abrupt
discontinuity of the scattering potential at particle edges. It is
also observed that the spot splitting is related to the
geometric forms of the diffracting particles; some splitting
occurs in a well-defined crystallographic direction. Depending on the probe position relative to the center of the
particle, annular rings may be observed (see diffraction
pattern 3 in Fig. 14). CEND patterns are sensitive to edges,
thickness variations and facets; the 3-D information of
nanoparticles is reflected in their CEND patterns. Analysis
of CEND patterns at each pixel element of a nanoparticle
should provide detailed information about the 3-D structure
of small clusters and nanoparticles.
Dynamical simulations reveal that for a particle that has
facets smaller than the size of the incident probe, the
incident electrons may interact with several facets of the
small particle [128]. The thickness of the particle may vary
rapidly even within a region of only 1 nm in diameter.
The electron probe effectively interacts with the particle

morphology under illumination. The intensity variations of
the splitting spots are related to the probe positions with
respect to the particle facets and are related to the length of
the facets along the incident beam direction. The direction of
spot streaking or splitting is directly related to specific edges
or facets of a small particle (Fig. 14). Furthermore, the
intensity profiles across the splitting spots vary with the
types of particle wedges. In principle, it is possible to deduce
the 3-D structure of nanoparticles by quantitatively analyzing the intensity distributions of their CEND patterns. Before
this technique can be effectively and reliably utilized to
extract the rich information coded in CEND patterns of
small particles, many experimental difficulties, such as
particle stability, contamination and accurate control of
beam defocus, have to be overcome.
When metal atoms aggregate from the vapor phase or in a
liquid, they usually form a crystal, having shapes of regular
pentagonal bi-prisms or icosahedra. Their internal structure
Fig. 15 CEND patterns obtained from small Ag icosahedral nanoparticles along the 5-fold symmetry axis (a) and the 3-fold symmetry axis (b);
the corresponding simulated patterns are shown in (c) and (d), respectively.
is a complex arrangement of 5 or 20 twinned components.

Large metal particles of cuboctahedron, decahedron,
icosahedron and other multiple-twinned structures can be
examined in HRTEM images [129,130]. For particles
with sizes <2 nm in diameter, however, it is difficult to
unambiguously determine their shape by imaging techniques. CEND technique can provide information about the
shape of clean, metallic nanoparticles. For example, a large
portion of clean silver nanoparticles with sizes <3 nm
in diameter was observed to give unique CEND patterns
exhibiting 5-fold-symmetry. Figure 15a shows such a CEND
pattern and Fig. 15c shows a simulated CEND pattern of a
small icosahedron with the incident beam direction along
the 5-fold symmetry axis. The simulated pattern closely
matches the experimental one. Figures 15b and 15d show,
respectively, experimental and simulated CEND patterns of a
small icosahedral Ag nanoparticle oriented along its 3-fold
axis. Although the general features are similar between
the experimental and the simulated CEND patterns, quantitative comparison has not yet been performed. These small
particles are not stable under intense electron beam irradiation and their structure fluctuates rapidly during observation. Detailed quantitative analyses of digitally recorded
CEND patterns will provide information on the shape of,

as well as the defective structure in, small nanoparticles.
Simulations of CEND patterns of various shapes of nanoparticles should provide insight into the nature of CEND
from nanoparticles or other nanosystems.
CEND technique has been applied to the study of defects
[49,50], supported catalysts [55,56,89], structure of carbon
nanotubes [59,60], and biological systems [6365]. The
recent application of using coherent beams of small diameter
for deriving the structure of double-walled carbon nanotubes with high resolution and contrast clearly demonstrated the potential of employing coherent nanoprobes to
extract structural information of periodic or non-periodic
objects [131].
STEM nanospectroscopy:
XEDS and EELS
XEDS is now routinely used, in TEM, SEM or STEM
instruments, to identify unknown phases or to obtain
information on the spatial distribution of certain phases of
interest. In a modern FEG TEM/STEM instrument, XEDS
can be conveniently used to analyze the features revealed
in HAADF images by stopping the incident probe at any

point of interest. With the recent development of image
and spectrum acquisition systems, both qualitative and
quantitative information on the composition of individual
nanocomponents can be obtained. The availability of faster
computers for automation and online data analysis make it
possible to analyze extremely complex nanoscale systems
and to quickly diagnose their basic composition.
One of the most useful techniques for understanding
the behavior of bimetallic nanoparticles and for guiding
the development of industrial bimetallic catalysts is the
composition-size plot method developed by the Lymans
group [132,133]. The composition-size plots can provide the
compositional profiles of the individual bimetallic nanoparticles or clusters; they reveal whether the compositions of
individual nanoparticles vary with their sizes or with their
relative locations with respect to the catalyst support. When
ultramicrotomed samples are used, this method can quantitatively map out how the compositional profiles vary within
the supports, the treatment conditions, or the preparation
procedures. The composition-size plot method can also be
applied to studying the compositional evolution of individual bimetallic nanoparticles during the catalytic reactions.
Figure 16 shows examples of how the composition-size
plots are used to provide information on the nature of
bimetallic catalysts and how the information can be used to
develop new synthesis strategies in order to obtain particular
structures that give desired performances. Figure 16a is a
composition-size plot obtained from a 2wt%Pd1wt%Cu/
g-Al2O3 bimetallic catalyst. Each data point represents the
composition of that individual bimetallic nanoparticle. The
nanoparticles selected for analysis are located at different
regions of the catalyst powders. The plot shows that the
composition of the individual PdCu nanoparticles does not
vary much with the size of the particles; but they do change
significantly with the location of the individual particles.
Further analysis of the corresponding HAADF images
show that the compositional variations of the individual
PdCu nanoparticles revealed in Fig. 16a are related to the
macro- and nano-structure of the g-Al2O3 aggregates/
powders. Therefore, the metal precursor deposition processes have to be modified in order to obtain bimetallic
nanoparticles with a uniform composition throughout the
catalyst powders.
Figure 16b shows another example of studying bimetallic
catalysts. The composition-size plot clearly shows that
the composition of the individual PdNi particles in a
5wt%Pd1wt%Ni/TiO2 bimetallic catalyst changes significantly with the sizes of the individual nanoparticles and also
varies with their relative locations with respect to the
substrate structure: smaller particles contain more Pd and
larger particles contain more Ni. This observation can be
explained if Pd preferentially segregates to the particle
surface or if Pd-rich particles do not sinter as much during
the catalyst preparation processes. By changing the synthesis
procedures, the composition-size profile can be modified.
Fig. 16 Composition-size plots of (a) 2wt%Pd1wt%Cu/g-Al2O3 and

(b) 5wt%Pd1wt%Ni/TiO2 bimetallic catalysts. These compositionsize plots of bimetallic nanoparticles provide critical information
on the synthesisstructureperformance relationships of nanostructured bimetallic or multiphase heterogeneous catalysts.
Comparison of composition-size plots to the catalysts

performance can provide important information on the
synthesisstructureperformance relationships.
In practical applications to developing industrial catalysts,
hundreds of data points in each composition-size plot are
usually needed to provide statistically meaningful data of the
catalyst of interest. In developing industrial catalysts, in
order to optimize the synthesis protocols to make a potential
commercial catalyst tens or even hundreds of catalysts will
have to be tested and analyzed; this is time consuming and
extremely expensive. Automated analyses and faster data
acquisition systems are highly desired for wide applications
of the composition-size plot method for solving challenging
nanoscale materials problems.
A consequence of using small electron probes to achieve
high-spatial resolution is that the X-ray signal originates
from a much smaller volume; thus, a weaker signal is
collected and longer acquisition times are usually needed
to obtain statistically meaningful data points. Specimen-drift
correction, either manually or automatically, is usually
required for obtaining statistically meaningful X-ray signals
when very small particles are analyzed. Nevertheless, XEDS
can detect the presence of just a few atoms if the analyzed

volume is small enough. With the recent development of
Cs-correctors for dedicated STEM instruments, the total probe
current can be significantly increased, thereby providing
higher counts of the collected X-ray signals. Future development that focuses on significantly improving the X-ray
collection efficiency and reduction of beam-induced modifications (e.g. by using pulsed electron beam) can have a
profound impact on the fundamental understanding of
bimetallic nanoparticles or quantum dots.
Elemental maps can provide valuable information on
the 2-D elemental distributions; they are especially useful
for characterizing multiphase materials. Electronspecimen
interaction processes and the effective generation volume
of the X-rays determine the ultimate resolution of X-ray
mapping of nanophase materials. In practice, however,
the extremely low counts of the collected X-ray signal
from small nanoparticles and specimen drifting limit the
achievable resolution in X-ray elemental maps. A statistically

meaningful elemental map requires longer acquisition time
that in turn requires the use of automatic drift correction
or ultra-stable microscopes and samples. Higher-resolution
maps, however, are needed to determine the degree of
surface segregations, which may be accomplished by using
Cs-correctors to reduce the probe size but still having enough
beam current. Automatic specimen-drift correction may also
have to be used to reduce specimen-drifting effect. The
conditions for optimum X-ray mapping include: (i) high
beam current within a small probe size, (ii) high X-ray
collection efficiency and (iii) long acquisition times per pixel
if automatic specimen-drift correction techniques are used.
Figure 17 shows XEDS spectra and the elemental maps of
a 5wt%Pd1wt%Ni/TiO2 catalyst, clearly revealing that the
individual nanoparticles dispersed onto the TiO2 powders
contain both Pd and Ni. The elemental distribution within
each individual PdNi bimetallic nanoparticles, especially
Fig. 17 XEDS spectra from a PdNi alloy nanoparticle (darker line) and from the TiO2 support (lighter line) of a 5wt%Pd3wt%Ni/TiO2
bimetallic catalyst. Elemental maps of Ni, Pd and Ti show the distribution of Pd and Ni across the TiO2 support.
within the small nanoparticles, however, is not revealed in

these elemental maps. Information on the surface segregation of individual PdNi bimetallic nanoparticles, which
is most important for understanding the performance of
bimetallic nanocatalysts, cannot be extracted from Fig. 17.
Electron energy-loss signals carry detailed information
on the composition, chemistry and electronic structure of
nanoparticles with atomic resolution and sensitivity. The
combination of atomic resolution HAADF imaging with
EELS has already proved extremely valuable for extracting
atomic-scale information on the composition and electronic
structure of various materials systems [74,75,7880,8689,
134,135]. The combination of EELS with HAADF in a STEM
instrument significantly extends the usefulness of STEM in
solving challenging nanoscale or atomic scale materials
problems.
It is important to understand the effect of the electronic
structure of the interfacial regions between the metal nanoparticles and the support on the catalytic performances of
supported catalysts. Since catalytic reactions usually involve
bonding and electron transfer processes, the electronic
properties of the metalsupport interfacial regions can play
a critical role in determining surface adsorption and electron
transfer processes. Furthermore, the interfacial regions may
also act as active sites during the catalytic reactions since
these regions may have a structure that represents neither
the metal nanoparticles nor the support. Knowledge of the
atomic and electronic structure of the interfaces can help
us better understand the performance of heterogeneous
catalysts.
Recently, atomic resolution EELS and HAADF techniques
have been applied to the study of nanophase Sn(Sb)O2
catalysts [86], reduction behavior of metal nanoparticles
in alumina-supported Pd catalysts [87] and the alloying
behavior of supported PdCu bimetallic catalysts [88]. These
preliminary investigations already showed that atomic
resolution EELS, together with HAADF imaging technique,
can provide valuable information on the fundamental
understanding of the electronic structure as well as surface
composition of the individual nanoparticles and their interactions with the support.
Figure 18a shows a HAADF image and Fig. 18b shows the
corresponding EELS spectra that were obtained from the
different regions labeled in 18a, respectively. The sample is a
PdNi/TiO2 bimetallic catalyst. The EELS spectra suggest that
the bimetallic particle can be described by the grape model:
a thin skin of pure Pd layer encapsulates a PdNi alloy core.
This type of structure may have profound effect on the
adsorption and catalytic properties of bimetallic catalysts.
The knowledge of preferential surface segregation of individual bimetallic nanoparticles is critical to designing supported bimetallic catalysts and to an understanding of their
performance. Knowing how the preferential surface segregation of individual bimetallic nanoparticles depends on the
particle size, composition and the catalyst preparation
methods, one can make significant progress in tuning the
Fig. 18 HAADF image of a 5wt%Pd1wt%Ni/TiO2 bimetallic catalyst

shows a PdNi alloy nanoparticle in contact with the TiO2 support
(a). (b) EELS spectra, obtained from the corresponding points of
the PdNi alloy nanoparticle shown in (a), show that the Pd is
preferentially segregated to the surface of the alloy nanoparticle.
The spectra also reveal the presence of TiOx species across the surface
of the PdNi alloy nanoparticle.
properties of supported bimetallic catalysts to achieve high

selectivity and activity. The concept of binding-energy
engineering in developing heterogeneous catalysts refers
to tuning the molecular adsorption and dissociation behavior of nanoparticles by controlling their sizes, atomic
structure, shape, surface and bulk composition, and interface
structures.
Figure 18 also shows that strong metal support interactions occurred during the catalyst preparation processes;
TiOx species had migrated to the surfaces of the PdNi alloy
nanoparticle. Detailed analyses of the EELS spectra revealed
that the TiOx species covered the whole surface of this
particular PdNi alloy particle. The coverage of TiOx species
on metal or alloy nanoparticles depend on the precursor
species, catalyst treatment, properties of the particle surface,
and the interfacial properties between the metal/alloy
particles and the support. The metalsupport interaction

profoundly affects the adsorption behavior of the metal or
alloy nanoparticles.
EELS technique can be used to analyze individual atomic
columns or single atoms located either inside or on the
surface of a substrate [74]. With the use of Cs-correctors
to form sub-angstrom probes, it is expected that atomic
resolution EELS can be performed on a wide variety of
materials to provide chemical and electronic structure of the
elements of interest. Further incorporation of monochromators in the field emission TEM/STEM instruments [77]
will significantly enhance the power of atomic resolution
EELS in studying nanoparticles and nanoparticle systems;
and information on the fine electronic structure of nanoparticles and nanoclusters may provide a better understanding of the selectivity of heterogeneous catalysts.
tireless training of the author in mastering the various STEM techniques

and for his encouragement in applying these powerful STEM techniques
to solving challenging industrial problems.
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Published by Oxford University Press

Journal of Electron Microscopy 54(3): 251278 (2005)

Scanning transmission electron microscopy and

Scanning transmission electron microscopy (STEM) techniques can

electron microscopy, STEM, Z-contrast microscopy, nanodiffraction,

Dedicated to the memory of the late Professor John M. Cowley.

STEM the most powerful microscope for characterizing

252 J O U R N A L O F E L E C T R O N M I C R O S C O P Y , Vol. 54, No. 3, 2005

energy analysis of the inelastically scattered electrons, can

acquired to provide multitudinous information on the

J. Liu STEM of nanoparticles and surfaces 253

particles, surfaces and biological systems [48,4266].

further enhance and expand the impact of STEM techniques

254 J O U R N A L O F E L E C T R O N M I C R O S C O P Y , Vol. 54, No. 3, 2005

STEM imaging: shadow image,

scattering angle and l is the wavelength of the incident

where Q(K) is the Fourier transform of the transmission

where K0 is the cut-off wave-vector determined by the

where D is the defocus value of the electron probe and Cs is

where s p/(lE0) is the interaction constant, E0 is the

J. Liu STEM of nanoparticles and surfaces 255

incident electrons are not variables during an experiment;

256 J O U R N A L O F E L E C T R O N M I C R O S C O P Y , Vol. 54, No. 3, 2005

the beam defocus we move the specimen along the optical

Correlation of shadow images, obtained from different

J. Liu STEM of nanoparticles and surfaces 257

interpretable image of the crystal lattices in the under-focus

STEM imaging: convergent beam

of sets of convergent beam discs is obtained as schematically

258 J O U R N A L O F E L E C T R O N M I C R O S C O P Y , Vol. 54, No. 3, 2005

The formation of interference fringes in the overlapping

where D(K) is the transmission function of the detector.

J. Liu STEM of nanoparticles and surfaces 259

detector is positioned at any point in the overlapping regions

image can be obtained by shifting the STEM detector to

260 J O U R N A L O F E L E C T R O N M I C R O S C O P Y , Vol. 54, No. 3, 2005

without the complication of misaligning or realigning

STEM imaging: large-angle bright-field

where sf(X) is the projected potential along the beam

This is a form of incoherent imaging: the phase contrast is

Fig. 7 Schematic diagram illustrates the geometric arrangement of

images is predominantly due to absorption effect, weak

The diffraction plane is divided into two complementary

and ILABF X 1 IADF X

Therefore, the LABF image is complementary to the

J. Liu STEM of nanoparticles and surfaces 261

angle as large as that of the LABF detector. LABF images can

STEM imaging: HAADF imaging or

metal catalysts with sub-nanometer or atomic resolution

262 J O U R N A L O F E L E C T R O N M I C R O S C O P Y , Vol. 54, No. 3, 2005

composition of mixed metal or alloy nanoparticles, especially

data on the size distribution of metal or alloy nanoparticles

J. Liu STEM of nanoparticles and surfaces 263

Fig. 9 HAADF image of a model catalyst consisting of Pt and Pd

effect of electron channeling may not be significant. In this

Fig. 10 Atomic resolution HAADF image of a small Pt cluster and

264 J O U R N A L O F E L E C T R O N M I C R O S C O P Y , Vol. 54, No. 3, 2005

characteristics of incoherent HAADF imaging include:

than 0.05 nm should be achievable in a STEM instrument

J. Liu STEM of nanoparticles and surfaces 265

probe tails complicate the measurement of the particle size.

STEM imaging: thin annular detector

Other specially configured detectors can be constructed