Physics of Nanomaterials

Module IV

Characterization Techniques of
Nanomaterials
Learning objectives

X-ray diffraction, small angle X-ray scattering, scanning electron microscopy with energy
dispersive spectroscopy, transmission electron microscope, scanning tunneling microscope

Module IV: Characterization Techniques of Nanomaterials 1

Q.1. Explain the XRD method to characterize the nanomaterials
X-RAY DIFFRACTION (XRD)
1. XRD is extensively used to study the crystal structure of solids, defects and stresses. In XRD, a
beam of X-rays, with wavelength ranging from 0.07 to 0.2 nm, is diffracted by the crystalline
specimen according to Bragg’s law:
λ = 2d sin θ
where d is the interplanar distance and λ is the
wavelength of the X-rays.
The intensity of the diffracted beam is measured as a
function of the diffraction angle (2θ) and the
specimen’s orientation.
2. Figure shows schematic representation of XRD
3. The diffraction pattern can be used to identify the
crystalline phases and their structural characteristics.
XRD is non-destructive and does not require detailed
sample preparation.

4. Homogeneous and inhomogeneous strains in

materials can be measured as X-ray intensity and is
dependent on the Bragg angle.
5. Homogeneous or uniform elastic strain shifts the
diffraction peak positions, without change in peak
profile.
6. A shift in the X-ray peak positions indicates a change
in d-spacing caused by a change in lattice constants.
7. Inhomogeneous strains vary from crystallite to
crystallite or even within a single crystallite. Since
XRD gives averaged information from all such
crystallite volumes, it leads to broadening of the
diffraction peaks, which increases with increase in sin
θ.
8. Peak broadening can also be due to the fine crystallite size, which is independent of sin θ.
9. The contribution of crystallite size and lattice strain to peak broadening can be independently
determined by peak profile analysis.
10. Due to lower energy of the X-ray beam used, the X-ray diffraction intensities are low, particularly
in case of low atomic number materials and hence, detection of phases with small volume
fractions is difficult with XRD.
Q.2. What is SAXS? Explain SAXS method to characterize the materials?
Q.3. Distinguish between XRD and SAXS
SMALL ANGLE X-RAY SCATTERING (SAXS)

Small-angle X-ray scattering (SAXS)

1. SAXS is a small-angle scattering (SAS) technique where the elastic scattering of X-
rays (wavelength 0.1 ... 0.2 nm) by a sample which has inhomogeneities in the nm-range, is
recorded at very low angles (typically 0.1 - 10°). This angular range contains information about
the shape and size of macromolecules, characteristic distances of partially ordered materials, pore

Module IV: Characterization Techniques of Nanomaterials 2

 sizes, and other data. SAXS is capable of delivering structural information of macromolecules
between 5 and 25 nm, of repeat distances in partially ordered systems of up to 150 nm.
2. SAXS to a family of X-ray scattering techniques that are used in the characterization of materials.
In the case of biological macromoleculessuch as proteins, the advantage of SAXS
over crystallography is that a crystalline sample is not needed.

1. SAXS is another powerful tool for characterizing nanostructured materials. Strong diffraction
peaks result from constructive interference of X-rays scattered from ordered arrays of atoms and
molecules.
2. A variety of information can be obtained from the angular distribution of scattered intensity at
low angles.
3. Fluctuations in electron density over lengths in the order of l0 nm or larger are sufficient to
produce appreciable scattered X-ray intensities at angles of 2θ < 5°. These variations can be due
to differences in density or composition, or both, and do not need to be periodic.
4. The amount and angular distribution of scattered intensity provides information about the size of
very small particles or their surface area per unit volume, regardless of whether the sample or
particles are crystalline or amorphous.
5. Since SAXS is very effective in measuring inhomogeneity in the region of 1–100 nm, it has been
widely used in the characterization of nanocrystals.
6. SAXS has also been widely used for the determination of size and ordering of mesoporous
materials synthesized by organic-templated condensation.
7. The apparatus for measuring the distribution of small angle scattering generally employs
transmission geometry using a fine monochromatic radiation beam.
8. SAXS has been employed to characterize a wide spectrum of materials including biological
structures, metallic and non-metallic specimens, composites and mesoporous materials. Small
angle X-ray scattering (SAXS) is a useful analytic technique for the study of aggregated
nanopowders, such as fumed silica and titania.
9. If a wide enough range of scattering angles is observed, the SAXS analysis results in a number of
average features of such systems, including the primary particle size (radius of gyration), primary
particle surface area, concentration, mass fractal dimension of the aggregates, aggregate size and
degree of aggregation. The size distribution of sub-nanoclusters, which cannot be easily estimated
using TEM, can successfully be analysed using SAXS.

Applications

1. SAXS is used for the determination of the microscale or nanoscale structure of particle systems in
terms of such parameters as averaged particle sizes, shapes, distribution, and surface-to-volume
ratio.
2. The materials can be solid or liquid and they can contain solid, liquid or gaseous domains (so-
called particles) of the same or another material in any combination.
3. Not only particles, but also the structure of ordered systems like lamellae, and fractal-like
materials can be studied. The method is accurate, non-destructive and usually requires only a
minimum of sample preparation.
4. Applications are very broad and include colloidsof all types, metals, cement, oil, polymers,
plastics, proteins, foods and pharmaceuticals and can be found in research as well as in quality
control. The X-ray source can be a laboratory source or synchrotron light which provides a higher
X-ray flux.

Module IV: Characterization Techniques of Nanomaterials 3

SAXS instruments

In an SAXS instrument
a monochromatic beam of X-rays is
brought to a sample from which some
of the X-rays scatter, while most simply
go through the sample without
interacting with it. The scattered X-rays
form a scattering pattern which is then
detected at a detector which is typically
a 2-dimensional flat X-ray detector
situated behind the sample perpendicular to the direction of the primary beam that initially hit the sample.
The scattering pattern contains the information on the structure of the sample. The major problem that
must be overcome in SAXS instrumentation is the separation of the weak scattered intensity from the
strong main beam. The smaller the desired angle, the more difficult this becomes. The problem is
comparable to one encountered when trying to observe a weakly radiant object close to the sun, like the
sun's corona. Only if the moon blocks out the main light source does the corona become visible.
Likewise, in SAXS the non-scattered beam that merely travels through the sample must be
blocked, without blocking the closely adjacent scattered radiation. Most available X-ray sources
produce divergent beams and this compounds the problem. In principle the problem could be overcome
by focusing the beam, but this is not easy when dealing with X-rays and was previously not done except
on synchrotrons where large bent mirrors can be used. This is why most laboratory small angle devices
rely on collimation instead. Laboratory SAXS instruments can be divided into two main groups: point-
collimation and line-collimation instruments:

Q.4.What is main difference between light microscope and electron microscope? What information
one can expect from electron microscope?
A light microscope, which uses glass lenses to focus light, the electron microscope uses electrostatic and
electromagnetic lenses to control the illumination and imaging of the specimen. This imaging can yield
the following information:

1. Topography: The surface features of an object or "how it looks", its texture and direct relation
between these features and materials properties such as hardness, reflectivity, etc.
2. Morphology: The shape and size of the particles making up the object and direct relation
between these structures and materials properties such as ductility, strength, reactivity, etc.
3. Composition: The elements and compounds that the object is composed of and the relative
amounts of them and direct relationship between composition and materials properties such as
melting point, reactivity, hardness, etc.
4. Crystallographic information: How the atoms are arranged in the object and direct relation
between these arrangements and materials properties such as conductivity, electrical properties,
strength, etc.

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Electron Microscopes function exactly as their optical counterparts except that they use a focused beam of
electrons instead of light to "image" the specimen and gain information as to its structure and
composition.
The basic steps involved in the functioning of all the electron microscopes are:
1. A stream of electrons is formed (by the electron source/gun) and accelerated towards the
specimen using a positive electrical potential.
2. This stream is confined and focused using metal apertures and magnetic lenses into a thin,
focused, monochromatic beam.
3. This beam is then focused onto the sample using a magnetic lens.
4. Interactions occur inside the irradiated sample, affecting the electron beam. S. These interactions
and effects are detected and transformed into an image.

Q.5. Give the principle behind SEM? Explain construction and working of SEM?
Scanning Electron Microscope

A scanning electron microscope (SEM) scans a focused electron beam over a surface to create an
image. The electrons in the beam interact with the sample, producing various signals that can be used to
obtain information about the surface topography and composition.
1. A scanning electron microscope (SEM) is a type of electron microscope that produces images of
a sample by scanning it with a focused beam of electrons.
2. The electrons interact with atoms in the sample, producing various signals that contain
information about the sample's surface topography and composition. The electron beam is
generally scanned in a raster scan pattern (rectangular pattern of image capture and reconstruction
in television), and the beam's position is combined with the detected signal to produce an image.
3. SEM can achieve resolution better than 1 nanometer. Specimens can be observed in high vacuum,
in low vacuum, in wet conditions (in environmental SEM), and at a wide range of cryogenic or
elevated temperatures.
4. The most common SEM mode is detection of secondary electrons emitted by atoms excited by
the electron beam. The number of secondary electrons that can be detected depends, among other
things, on the angle at which beam meets surface of specimen,i.e. on specimen topography.
5. By scanning the sample and collecting the secondary electrons that are emitted using a special
detector, an image displaying the topography of the surface is created.
6. The scanning electron microscope (SEM) is a type of electron microscope capable of producing
high-resolution images of a sample surface. Due to the manner in which the image is created,
SEM images have a characteristic three-dimensional appearance and are useful for judging the
surface structure of the sample.
7. Whole system must be vacuum protected to prevent scattering of the electrons by stray air
molecules and the specimen must absorb or reflect electrons. Samples have to be prepared
carefully to withstand the vacuum inside the microscope.

Principles and capacities

When electron beam incident on sample, inside the samples following interactions takes place.The types
of signals (interactions) produced by an SEM include
a. Secondary electrons (SE),
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 b. Back-scattered electrons (BSE),
c. Characteristic X-rays,
d. Light (cathodoluminescence) (CL),
e. Specimen current and transmitted
electrons.
Secondary electron detectors are standard
equipment in all SEMs,
Back-scattered electrons (BSE) are beam electrons that are reflected from the sample by elastic scattering.
BSE images can provide information about the distribution of different elements in the sample.
Characteristic X-rays are emitted when the electron beam removes an inner shell electron from the
sample, causing a higher-energy electron to fill the shell and release energy. These characteristic X-rays
are used to identify the composition and measure the abundance of elements in the sample.
Construction and working
Detailed explanation of how a typical SEM functions is given in Figure

1. The electron gun produces a stream of monochromatic

electrons.
2. The stream of electrons is condensed by the first
condenser lens. The condenser lens not only forms the
beam but also limits the amount of current in the beam.
The condenser lens together with the condenser aperture
eliminates the high-angle electrons from the beam.
3. The condenser aperture constricts the beam and eliminates
some high-angle electrons.
4. The second condenser lens focusses the electrons into a
thin, tight, coherent beam and is usually controlled by the
fine probe current knob.
5. An objective aperture further eliminates some high-angle
electrons from the beam.
6. A set of coils scan the beam in a grid fashion, the period of
time for which the beam dwells on each point is
determined by the scan speed (usually in the microsecond
range).
7. The final lens, the objective lens, focusses the beam on the
desired part of the specimen.
8. When the beam strikes the sample, it interacts with the
sample and generates radiations, which are detected with
various instruments.
9. Before the beam moves to its next dwell point, these instruments count the number of interactions
and display a pixel on a CRT, the intensity of which is determined by this number (the more the
reactions, the brighter the pixel).

10. The speed of scanning is such that the entire pattern can be scanned 30 times in a second.

Module IV: Characterization Techniques of Nanomaterials 6

Strengths and limitations of SEM

Strengths
1. Most SEM is comparatively easy to operate
2. Modern SEMs generate data in digital format which are highly portable
3. For many applications data acquisition is rapid
Limitations
1. Samples must be solid and they must fit into the microscope chamber
2. An electrically conductive coating must be applied to electrically insulated samples for study in
conventional SEM

Q.6.What is EDS? Explain the principle behind EDS

Energy-dispersive X-ray spectroscopy (EDS)

1. Sometimes called energy dispersive X-ray analysis (EDXA) or energy dispersive X-ray
microanalysis (EDXMA),
2. Is an analytical technique used for the elemental analysis or chemical characterization of a
sample. It relies on an interaction of some source of X-ray excitation and a sample.
3. Its characterization capabilities are due in large part to the fundamental principle that each
element has a unique atomic structure allowing unique set of peaks on its X-ray emission
spectrum.
4. To stimulate the emission of characteristic X-rays from a specimen, a high-energy beam of
charged particles such as electrons or protons, or a beam of X-rays, is focused into the sample
being studied.
5. At rest, an atom within the sample contains ground state (or unexcited) electrons in discrete
energy levels or electron shells bound to the nucleus.
6. The incident beam may excite an electron in an inner shell, ejecting it from the shell while
creating an electron hole where the electron was.
7. An electron from an outer, higher-energy shell then fills the hole, and the difference in energy
between the higher-energy shell and the lower energy shell may be released in the form of an X-
ray.
8. The number and energy of the X-rays emitted from a specimen can be measured by an energy-
dispersive spectrometer.
9. As the energies of the X-rays are characteristic of the difference in energy between the two shells
and of the atomic structure of the emitting element, EDS allows the elemental composition of the
specimen to be measured.

Four primary components of the EDS setup are

1. the excitation source (electron beam or x-ray beam)

2. the X-ray detector
3. the pulse processor
4. the analyzer.

Electron beam excitation is used in electron

microscopes, scanning electron microscopes (SEM) and scanning
transmission electron microscopes (STEM). X-ray beam
Module IV: Characterization Techniques of Nanomaterials 7
excitation is used in X-ray fluorescence (XRF) spectrometers. A detector is used to convert X-ray energy
into voltage signals; this information is sent to a pulse processor, which measures the signals and passes
them onto an analyzer for data display and analysis. The most common detector now is Si(Li)
detector cooled to cryogenic temperatures with liquid nitrogen; however newer systems are often
equipped with silicon drift detectors (SDD) with Peltier cooling systems.
The excess energy of the electron that migrates to an inner shell to fill the newly created hole can do more
than emit an X-ray. Often, instead of X-ray emission, the excess energy is transferred to a third electron
from a further outer shell, prompting its ejection. This ejected species is called an Auger electron, and the
method for its analysis is known as Auger electron spectroscopy (AES)

Q.7. What is the principle behind TEM? Explain construction and working of TEM

TRANSMISSION ELECTRON MICROSCOPY (TEM)

Transmission electron microscopy can provide microstructural, crystal structure as well as micro-
chemical information with high spatial resolution from each of the microscopic phases individually. TEM
is therefore a very powerful tool for materials characterization. TEM studies not only aid in improved
insight into structure–property correlations, but also in alloy development for improved performance.
1. Transmission electron microscopy (TEM) involves a
high energy electron beam, emitted from an electron
gun, to transmit through a specimen that is in part
transparent to electrons and carries the information
about the inner structure of the specimen.
2. This transmitted electron beam is then reaches the
imaging system of the microscope and the spatial
variation in this information (the "image") is then
magnified by a series of electromagnetic lenses until it
is recorded by hitting a fluorescent screen,
photographic plate, or light sensitive sensor such as a
charge-coupled device (CCD) camera.
3. The image detected by the CCD may be displayed in
real-time on a monitor or computer.
4. TEMs work the same way as SEMs except that the
transmitted part of the electrons is projected onto a
phosphor screen for the user to see.

Functioning of a TEM
The functioning of a TEM is similar to a slide projector in
some respects. A projector shines (transmits) a beam of light
through the slide; as the light passes through it is affected by
the structures and objects on the slide. This causes only some
part of the light beam to be transmitted through some part of
the slide. This transmitted beam is then projected on the
viewing screen, forming an enlarged image of the slide. A more technical explanation of the working of a
typical TEM is as follows (Fig. ):

Module IV: Characterization Techniques of Nanomaterials 8

 1. The electron gun at the top of the microscope produces a stream of monochromatic electrons.
2. This stream is focussed to a small, thin, coherent beam by the use of condenser lenses 1 and 2.
The first lens determines the spot size, the size of the electron beam that strikes the sample. The
second lens changes the size of the spot from a wide dispersed spot to a pinpoint beam on the
sample.
3. The beam is restricted by the condenser aperture (usually user selectable), knocking out high-
angle electrons (those far from the optic axis, the dotted line down the centre).
4. A part of the beam that strikes the specimen is transmitted.
5. This transmitted portion is focussed by the objective lens into an image.
6. Optional objective and selected area metal apertures can restrict the beam—the objective aperture
enhancing contrast by blocking out high-angle diffracted electrons, and the selected area aperture
enabling the user to examine the periodic diffraction of electrons by ordered arrangements of
atoms in the sample.
7. The image is passed down the column through the intermediate and projector lenses, being
enlarged all the way.
8. When the beams strike the phosphor image screen light is generated, which causes the image to
be visible to the operator. The area through which very few electrons are transmitted look darker
(they are thicker or denser).
9. The lighter areas of the image represent those areas of the sample through which more electrons
were transmitted (they are thinner or less dense).
10. When the electron beam passes through the specimen, its interaction with the electrons present in
the specimen generates a variety of radiation, which can give a lot of information about the
specimen.
11. Elastic scattering gives diffraction patterns and no energy is lost in this process.
12. Inelastic interaction of the electron beam with the electrons at dislocations, grain boundaries, and
second-phase particles, in the sample can lead to changes in the intensity of the transmitted
electrons. Both elastic and inelastic scattering can give immense information about the sample.
Applications

1. Individual wire/rod/tube/particle accurate size and shape

2. Internal structure of (microstructure ) of individual nanowire/rod/particle
3. Comopsition of individual nanowires/rods/particles
4. Topography
5. Composition
6. Crystallinity
7. Defects
8. Morphology
Strengths and limitations of TEM
Strength:
1. The TEM technique is especially powerful in elucidating structural features that range in size
from 100 to 10000 Ao
2. TEM studies allow for phase identification of extremely small particles of materials

Limitations
1. TEMs are large and very expensive
2. TEMs require special housing and maintenance
3. Images are black and white

Q.8. Distinguish between XRD, SEM and TEM

Module IV: Characterization Techniques of Nanomaterials 9

S.No XRD SEM TEM
1 X-Ray diffraction SEM is based on scattered TEM is based on transmitted
electrons electrons
2 Based on Bragg’s SEM focuses on sample’s TEM seeks to see what is
condition surface and composition inside or beyond the surface
3 Average particle size SEM shows the sample bit by TEM shows the sample as a
bit whole
4 Sample size bulk or Sample size bulk or thin film Sample size is less than 100
thin film nm
5 Phase and structure Composition analysis of Composition analysis of
group of grains individual grains
6 Lattice parameter, strain Morphology, Topology Crystallography, defects
7 1-30 KV accelerating voltage 100-300 KV accelerating
voltage

8 E-beam wavelength ~ nm E-beam wavelength ~ pm

9 SEM provides 3D images TEM delivers 2D images

Q.9. What is the principle behind STM? Explain construction and working of STM? OR
What is STM? Explain positive and negative bias? Give different modes of operations of STM

Scanning Tunneling Microscope (STM)

STM is the tunnelling current between a metallic tip and a conducting substrate which are in very close
proximity but not actually in physical contact.

1. If the tip is biased with respect to

the surface by the application of
Module IV: Characterization Techniques of Nanomaterials 10
 a voltage between them then electrons can tunnel between the two, provided the separation of the
tip and surface is sufficiently small-this gives rise to a tunnelling current.
2. The direction of current flow is determined by the polarity of the bias. If the sample is biased -ve
with respect to the tip, then electrons will flow from the surface to the tip as shown in Fig. (a),
whilst if the sample is biased +ve with respect to the tip, then electrons will flow from the tip to
the surface as shown in Fig. (b).
3. The tunnelling current is therefore a very sensitive function of this separation. Imaging of the
surface topology may then be carried out in one of the two ways:
1. In constant height mode [in which the tunnelling current is monitored as the tip is scanned
parallel to the surface, cf. Fig (a)].
2. In constant current mode [in which the tunnelling current is maintained constant as the tip is
scanned across the surface, cf. Fig. (b)].
4. If the tip is scanned at what is nominally a constant height above the surface, then there is
actually a periodic variation in the separation distance between the tip and the surface atoms. At
one point the tip will be directly above a surface atom and the tunnelling current will be large
whilst at other points the tip will be above hollow sites on the surface and the tunnelling current
will be much smaller [cf. Fig. (a)]. A plot of the tunnelling current vs. tip position therefore
shows a periodic variation which matches that of the surface structure-hence it provides a direct
'image' of the surface (and by the time the data has been processed it may even look like a real
picture of the surface!).

(a) Constant height mode operation of the STM tip, (b) constant current mode operation of the STM tip.

5. In practice, however, the normal way of imaging the surface is to maintain the tunnelling current
constant whilst the tip is scanned across the surface. This is achieved by adjusting the tip's height
above the surface so that the tunnelling current does not vary with the lateral tip position. In this
mode, the tip will move slightly upwards as it passes over a surface atom, and conversely, slightly
in towards the surface as it passes over a hollow, as shown in Fig. (b).
6. The principle of the STM is straightforward.
A sharp metal tip (one electrode of the tunnel junction) is brought close enough (0.3–1
nm) to the surface to be investigated (the second electrode), such that, at a convenient operating
voltage (10 mV–1 V), the tunnelling current varies from 0.2 to 10 nA, which is measurable. The

Module IV: Characterization Techniques of Nanomaterials 11

 tip is scanned over a surface at a distance of 0.3–1 nm, while the tunnelling current between it and
the surface is measured.
7. In STM, a conductive tip placed above the surface of a sample moves on the sample surface with
its height being adjusted continuously to keep the tunnelling current constant. The tip position is
monitored to map the surface topography of the sample.
8. Figure schematically depicts an STM structure. A sharp tip of tungsten or PtIr alloy is mounted
on a three-dimensional positioning stage. The tip movement above the sample surface in three
dimensions is controlled by piezoelectric arrays.
9. The distance between the tip and the sample is around 0.2 and 0.6 nm, which generates a
tunnelling current of about 0.1–l0 nA. The spacial resolution is about 0.01 nm in the x- and y-
directions and about 0.002 nm in the z-direction, which leads to a true atomic resolution in three
dimensions.

Modes of operation
10. STM is commonly operated in two modes. One of them is constant current imaging, in which a
constant current is maintained between the sample and tip. During the movement of the tip over
the sample surface, the vertical position of the tip is changed to maintain a constant separation
between the two. Since the tunnelling current is sensitive to distance, constant current imaging
will provide excellent surface topographic contrast of the surface atom contours.
11. In contrast to the constant current mode, constant tip position results in variationsin tunnelling
current due to changes in tip separation distance brought about by the 3D topographic features of
the surface atoms. In the constant current mode, the contrast is related to electron charge density
profiles, while faster scan rates are possible in the constant height mode.
12. The STM operates in both constant height and constant current modes depending on a parameter
selection in the control panel. In the constant current mode, the feedback gains are set high, the
tunnelling tip closely tracks the sample surface, and the variation in tip height required to
maintain constant tunnelling current is measured by the change in the voltage applied to the piezo
tube. In the constant height mode, the feedback gains are set low, the tip remains at a nearly
constant height as it sweeps over the sample surface, and the tunneling current is imaged.

Module IV: Characterization Techniques of Nanomaterials 12