NPTEL Chemical Engineering Interfacial Engineering

Module 2: Lecture 4

Characterization of Solid Surfaces

Dr. Pallab Ghosh

Associate Professor
Department of Chemical Engineering
IIT Guwahati, Guwahati781039
India

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Table of Contents
Section/Subsection
2.4.1 Introduction
2.4.2 Microscopy of surfaces

Page No.
3
313

2.4.2.1 Fluorescence microscopy

2.4.2.2 Confocal microscopy

2.4.2.3 Electron microscopy

2.4.2.4 Scanning probe microscopy

713

2.4.2.4.1 Scanning tunneling microscopy (STM)

2.4.2.4.2 Atomic force microscopy (AFM)

10

2.4.3 Spectroscopy of surfaces

1318

2.4.3.1 Auger electron spectroscopy (AES)

14

2.4.3.2 X-ray photoelectron spectroscopy (XPS)

15

2.4.3.3 Secondary ion mass spectrometry (SIMS)

16

2.4.3.4 Attenuated total reflectance spectroscopy (ATR)

17

2.4.3.5 Total internal reflectance fluoroscopy (TIRF)

18

Exercise

19

Suggested reading

20

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2.4.1 Introduction
A number of microscopic and spectroscopic methods are available which provide
information about the structure of a solid surface and its composition. In this lecture, we
will discuss some of these methods.

2.4.2 Microscopy of surfaces

The optical data are usually in the form of an instantaneously obtained twodimensional map of a patch of the surface. Conventional optical microscopy can
resolve feature down to about 0.5 m.
When light from various feature points in the object are reconstituted in the image,
the image points are not new points, but small disks called Airy disks which contain
diffraction patterns. When the diffraction patterns surrounding the neighboring image
feature points start to overlap, these points are not resolvable.
The minimum object distance d between resolvable points depends on the size of
the Airy disks, which depends on the wavelength of light in the medium between the
object and the objective lens , and the fraction of the light emanating from an
object point captured by the objective lens of the microscope.
This depends on the ratio of the lens diameter to the distance between the object and
the lens. The resolution d for the case of reflected light (non-luminous objects) is
given by,

2n sin

(2.4.1)

where 0 is the wavelength of light in vacuo, n is the refractive index of the medium
and is the polar angle subtended by the lens (see Fig. 2.4.1).

Fig. 2.4.1 Optical microscopy.

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The quantity n sin is called numerical aperture. Since the maximum possible value
of is 2 , sin 1 . For air n 1 , the upper limit of numerical aperture for a dry
objective is practically less than unity.
If the gap between the object and the lens is filled with oil which has n 1 , the
aperture can be increased. The usual oil for oil immersion objective has n 1.515 ,
which renders an upper limit for the aperture of about 1.4.
The resolution (minimum value of d ) of an optical microscope is thus roughly half
the wavelength of the light for a dry objective, and one-third the wavelength of the
light for an oil immersion objective.

2.4.2.1 Fluorescence microscopy

Various methods of surface staining or marking may be used to enhance contrast
between the features of the surface. One of the most powerful methods is the use of
fluorescent markers.
Fluorescence microscopy is very powerful for the examination of biological surface
since fluorophors can be designed to attach to certain surface chemical
functionalities. The fluorophor absorbs photon energy of a particular wavelength and
very quickly (in nanoseconds) re-emits light of a slightly longer wavelength.
The difference between the excitation and the re-emission wavelengths is called
Stokes shift. It is the basis for spectrally separating the incoming and outgoing
radiation.
A strong illumination source is required because the number of fluorophors present is
small, and their quantum efficieny is low. The fluorescence microscopy of a
patterened surface is shown in Fig. 2.4.2.

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Fig. 2.4.2 Fluorescence microscope image of a patterned biosurface.

2.4.2.2 Confocal microscopy

Confocal microscopy is a variation of the fluorescence microscopy. The present-day
technique is known as laser scanning confocal microscopy. It permits high-resolution
optical sectioning through thick specimens.
This method is extensively used to make three-dimensional scans in solutions, and at
biological interfaces.
The light source is a high-intensity laser point source. The light is reflected off the
dichroic mirror. Then, by means of the objective lens, it is brought to focus on a
sharp diffraction limited spot in the specimen.
The spot then emits fluorescence that passes back up through the objective lens and
an emission filter. It is brought to focus at a particular location where an image of the
original laser point source is formed. This is the confocal plane.
It then moves on to the photodetector, where an image of the illuminated spot is
formed. The image will be formed by fluorescent light emanating not only from the
focal plane of the specimen, but also by the light emanating from planes above and
below it, causing a blurring of the image even when the depth of field is very small.
This problem can be solved by placing a pin-hole aperture in the confocal plane. It
blocks essentially all light coming from above or below the focal place of the
specimen spot.
Since only a single spot is observed, a photomultier tube can be used in synchrony
with the laser to record the photon count from the illuminated spot. Then the spot can
be scanned horizontally to build up the image of the focal plane of the specimen.
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Thereafter, the vertical location of the specimen may be changed, and the scanning
process is repeated to obtain the image of another specimen plane.
Hundreds of vertical sections may be scanned in this way to build up a highresolution three dimensional image of the specimen.

2.4.2.3 Electron microscopy

Electrons have wave-like properties under certain conditions with effective
wavelengths in the nanometer range. This is the motivation for using electron
microscopy to study the topography of a surface.
In transmission electron microscopy (TEM), the image is produced by focusing a
beam of electrons which have passed through and been scattered by a thin specimen.
TEM can resolve features down to ~1 nm. Since the electrons must pass through the
sample, this technique is limited to thin films.
TEM has found wide use in characterizing nanomaterials and in semiconductor
industries.
Fig. 2.4.3 illustrates how TEM can distinguish each metal layer so that the detailed
structure can be known during the processing steps.

Fig. 2.4.3 TEM image of a tungsten via, showing detailed structure of metal
Stack. The sample contains Al, SiO2, Ti, TiN and W (source: H. Zhang, Thin
Solid Films, 320, 77, 1998; reproduced by permission from Elsevier, 1998).
Scanning electron microscopy (SEM) analyzes electrons scattered back from the
surface of the specimen as the impinging beam of electrons is moved across the
surface in a raster pattern. The images produced by a beam hitting the surface at
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oblique angles produce a three-dimensional image. SEM can produce a resolution

of ~10 nm. The SEM image of nanocrystalline palladium supported on
mesoporous carbon is illustrated in Fig. 2.4.4.

Fig. 2.4.4 SEM image of nanocrystalline palladium (< 3 nm) supported on ordered
mesoporous carbon (source: X. Ji, K. T. Lee, R. Holden, L. Zhang, J. Zhang, G. A.
Botton, M. Couillard, and L. F. Nazar, Nature Chemistry, DOI: 10.1038/NCHEM.553;
reproduced by permission from Macmillan Publishers, 2010).
Both TEM and SEM require conductive samples and high-vacuum conditions.
Sometimes, it is difficult to separate the artifacts from true sample features.
Recently, water vapor has been used as gas-ionization detector in environmental
SEM (called E-SEM). Wet and non-conducting samples may be examined under
moderate vacuum.

2.4.2.4 Scanning probe microscopy

One of the most important new developments for probing surface structure is
scanning probe microscopy (SPM). It has found extensive use in nanoscience and
technology.
In this method, a sharp-tipped probe is moved with atomic precision over or near
to a surface allowing surface topography and/or surface forces to be mapped.
The first scanning probe method developed was scanning tunneling microsccopy
(STM). In this method, the basis for measurement is a tunneling electron current
passing between a conducting tip and a conducting or a semi-conducting solid
surface.
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The second method is the atomic force microscopy (AFM). In this method, the
force exerted on or by a cantilever to which a sharp tip is attached is measured
when the probe is in contact, or in the proximity of the surface which is to be
studied.

2.4.2.4.1 Scanning tunneling microscopy (STM)

The idea initially used for STM was based on the concept of field emission
microscopy. It used piezo-electric translators to position a sharp-tipped probe
with precise position (within a few nanometers) over the surface of the
conductive specimen in vacuo. Two such translators were used to position the xy
coordinates of the probe, and a third was used to adjust the vertical position of the
specimen to a position 50 nm away from the probe tip.
The probe was connected to a source of electricity creating a potential difference
great enough (~109 V/cm) to establish a field emission across the gap. As the
emitting probe was rastered across the surface of the specimen, a servo
mechanism adjusted its vertical position to keep the current constant. The
variations in the vertical position were recorded.
In 1981, a variation of this method was developed by Binnig and Rohrer (Nobel
Prize for Physics, 1986). In their method, the device moved an automatically
sharp metal probe tip to within 1 nm of a hard conducting or semi-conducting
specimen surface, and took advantage of the spontaneous tunneling of electrons
across this gap with the imposition of a small bias potential (~13 V).
The tunneling current (~0.0110 nA) occurs when the highest occupied molecular
orbital of the material on one side of the gap overlaps with the lowest unoccupied
orbital of the material on the other side of the gap. The tunneling current for a
given system decreases exponentially with the gap. The STM is schematically
shown in Fig. 2.4.5.

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2.4.5 Schematic of scanning tunneling microscopy.

Tips for STM scanning are typically made of tungsten wire electrochemically
etched into a sharp uniforrm shape. Often a subsequent chemical etching with
hydrofluoric acid is employed to remove or clean up oxide layers that quickly
form.
STM is limited to conducting or semi-conducting samples. For such samples, its
extraordinary resolution has permitted the investigation of the atomic structure of
the surfaces of such materials, and the manner in which such structure differs
from that in the bulk as a result of the asymmetry of inter-atomic forces acting
upon them. Therefore, this method has limited applications in biology.
STM has been used to analyze LangmuirBlodgett layers. STM can also be used
to manipulate atoms on surfaces. STM is generally applied in ambient air, but it
can be applied in vacuo or under liquids as well. An application is illustrated in
Fig. 2.4.6.

1.6 nm

1.6 nm

1.6 nm

1.6 nm

Fig. 2.4.6 A time-lapsed series of STM images of a disordered glassy set of

terphenyltetracarboxylic acid molecules on graphite. The sequence shows the
movement of a tiling defect across the surface (highlighted in blue) (source: L.
Bartels, Nature Chemistry, DOI: 10.1038/nchem.517; reproduced by permission
from Macmillan Publishers, 2010).
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2.4.2.4.2 Atomic force microscopy (AFM)

Atomic force microscopy is another form of scanning probe microscopy. It is a
very versatile method of characterization of solid surfaces and biointerfaces.
This method was developed in 1986. The microscope has three main parts:
cantilever, sample stage and optical deflection system consisting of a laser diode
and photodetector. The laser beam is reflected off the back side of the cantilever.
A four quadrant photodetector gives the opportunity to measure both normal
bending (ab) and torsion (cd) of the cantilever, corresponding to normal and
lateral forces (see Fig. 2.4.7).
The cantilever is usually microfabricated from silicon or silicon nitride. The
typical dimensions are 100300 m in length, 1030 m in width and 0.53 m
in thickness. The spring constant lies between 0.01 and 100 N/m.
The position of the sample is usually controlled by piezoelectric ceramics, which
move the sample relative to the cantilever in three dimensions. Alternatively, the
cantilever may be mounted on a piezoelectric actuator in order to scan the tip
instead of the sample. The bending of the cantilever, which is a measure of the
tipsample interaction, or loading force, is often determined by an optical
deflection system.

Fig. 2.4.7 Schematic of atomic force microscope.

Forces between 107 and 1015 N can be measured with the AFM.
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In the contact mode of operation, the tip and sample are placed in contact, and
the tip is simply dragged across the surface resulting in a topographical image of
the surface. The scanning is usually done under feedback control where the
sample is moved toward or away from the cantilever during the scan so that the
bending of the cantilever, normal to the surface, remains constant in order to
maintain constant force.
The up and down motion of the sample is therefore a record of the sample
topography. However, the dragging motion of the tip, combined with adhesive
and lateral forces, can cause substantial damage to both the tip and the sample. To
alleviate this problem, a tapping or intermittent-contact mode of operation is
used.
This is accomplished by first oscillating the cantilever at or near its resonant
frequency using a piezoelectric actuator. The oscillation amplitude of the
cantilever in air can be greater than 20 nm when the tip is not in contact with the
surface. Moving the oscillating tip toward the surface until it begins to lightly
touch or tap the surface reduces the oscillation amplitude. The reduction in
oscillation amplitude now becomes the feedback control signal which can be used
to measure the surface topography.
The AFM differs from other forms of microscopes in that a controlled force is
applied to the specimen while imaging. On the one hand, the imaging force can
be a limitation if one is seeking to image weakly bound adsorbates or soft
materials.
On the other hand, if the magnitude of the force is measured as a function of the
tipsurface separation, the chemical and physical properties of the surface (e.g.,
surface forces, stiffness/elasticity, and adhesion) can be measured.
The unique capabilities that the AFM brings to the biological community are:
imaging the structure of biomolecules and biosurfaces with (sub)molecular
resolution, imaging under physiological conditions, including in situ dynamic
events of native biomolecules and living cells in real-time, measuring local
charge densities, mechanical properties and intermolecular forces with

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nanometer-scale spatial resolution, and manipulating individual biomolecules on

the nanometer scale. An application is illustrated in Fig. 2.4.8.

Fig. 2.4.8 Comparison of surface roughness for graphene on SiO2 (a), and on
mica (b) by three-dimensional AFM topographic data (source: C. H. Lui, L. Liu,
K. F. Mak, G. W. Flynn, and T. F. Heinz, Nature, 462, 339, 2009; reproduced by
permission from Macmillan Publishers, 2009).
The various modes of atomic force microscopy and their applications are
illustrated in Table 2.4.1.
Table 2.4.1 Various modes of AFM
Mode

Name

Quantity measured

Contact AFM imaging

AFM/C-AFM

Nanoscale profilometry

LFM/FFM

In-plane lubricity/friction

KPM

Contact potential difference

TIM

Thermal property mapping

Micro thermomechanical analysis

TMA

Thermal expansions/softening

Scanning force microscopy

FS/SFS

Forcedistance profile

Chemical force microscopy

CFM

Bond force mapping

Pulsed-force mode

PFM

Topography, adhesion, stiffness,

Lateral or friction force

microscopy
Kelvin probe force microscopy
Micro thermal imaging
microscopy

mapping
Tapping or intermittent contact
mode

IC-AFM

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Phase detection imaging

Scanning electrochemical

PDI

Module 2: Lecture 4

Material properties by phase

lagging

ECM/SECM

Current cyclic voltammograms

Non-contact mode

NCM

Near field van der Waals forces

Magnetic force microscopy

MFM

Magnetic domain mapping

Electric force microscopy

EFM

Scanning near-field acoustic

SNAM

Dynamic fluid damping

SNTM

Heated thermocouple tip, thermal

microscopy

Coulombic charge domain

mapping

microscopy
Scanning near-field thermal
microscopy
Ultrasonic force microscopy

property mapping
UFM

Material properties by MHz to subGHz sample vibration

2.4.3 Spectroscopy of surfaces

If a surface (typically a metal surface) is irradiated with a probe beam of photons,
electrons, or ions (usually positive ions), one generally finds that photons,
electrons, and ions are produced in various combinations.
In a spectroscopic method, the intensity or efficiency is studied as a function of
the energy of the produced species at constant probe beam energy.
The spectroscopic methods can be divided into two categories: vacuum and nonvacuum techniques.
Examples of the vacuum techniques are Auger electron spectroscopy (AES), Xray photoelectron spectroscopy (XPS), and secondary ion mass spectrometry
(SIMS).
Examples of the non-vacuum techniques are attenuated total reflectance
spectroscopy (ATR), and total internal reflectance fluoroscopy (TIRF).
Many colloidal solid materials change structure irreversibly under high vacuum
(e.g., the hydrocolloids). Therefore, the high-vacuum methods are of little
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importance for such materials, because of the overwhelming influence of water

on the structure of the solidwater interface.

2.4.3.1 Auger electron spectroscopy (AES)

This method is based on the Auger effect (discovered in 1925 by Pierre Auger),
which is based on the analysis of energetic electrons emitted from an excited
atom after a series of internal relaxation events. AES was developed in the 1960s,
when ultra-high vacuum (UHV) technology became commercially available.
In this technique, probe electrons of energy 23 keV are fired at the surface.
When a primary electon displaces an electron from one of the inner shells of a
surface atom, an electron from an outer shell drops down to take its place. When
this happens, all of the excess energy is taken up by another outer shell electron,
which is then emitted from the atom with an energy which is characteristic of the
atom and independent of the energy of the incident beam. This electron is the
Auger electron, and its energy can be used to identify the surface atom.
Suppose that the incident electron with sufficient primary energy, E p , ionizes the
core level, such as a K level. The vacancy thus produced is immediately filled by
another electron from L1 . The energy EK EL1 released from this transition
can be transferred to another electron, as in the L2 level. The Auger electron will
have energy given by,

E EK EL1 EL 2

(2.4.2)

The excitation process is denoted as a KL1L2 Auger transition.

It is obvious that at least two energy states and three electrons must take part in an
Auger process. Therefore, hydrogen and helium atoms cannot give rise to Auger
electrons. Isolated Li atoms having a single electron in the outermost level cannot
give rise to Auger electrons. However, in a solid, the valence electrons are shared
and the Auger transitions of the type KVV occur involving the valence electrons
of the solid.

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Several transitions (e.g., KL1L1, KL1L2 , LM1M 2 ) can occur with various transition
probabilities. The Auger electron energies are characteristic of the target material
and independent of the incident beam energy.
The general uses of AES are identification of elements on surfaces of materials,
quantitative determination of elements on surfaces, studies on adsorption,
desorption and surface aggregation, and chemical reactivity at a surface.
The main advantages of this technique are its high sensitivity for chemical
analysis in the 0.520 nm region near the surface, a rapid data acquisition speed,
ability to detect all elements above helium, and capability of high-spatial
resolution. The high-spatial resolution is achieved because the specimen is
excited by an electron beam that can be focused into a fine probe.

2.4.3.2 X-ray photoelectron spectroscopy (XPS)

The X-ray photoelectron spectroscopy is closely related to Auger electron
spectroscopy. It is also called electronic spectroscopy for chemical analysis
(ESCA).
This method uses a monochromatic beam of X-rays to dislodge electrons from the
inner shells (K and L) of the surface atoms, and then analyzes the energy of the
emitted electrons (which includes Auger electrons) directly.
It is much more precise than AES, and can be used to detect changes in the
valence states of the adsorbed species. To illustrate, for 1s sulfur electrons, there
is a chemical shift of over 5 V, and the ionization energy increases as the valence
state of sulfur varies from 2 to +6.
It is possible to analyze oxidation and reduction at the surface of solids using
XPS.
The kinetic energy of the emitted photo-electron is determined in the
spectrometer. It is given by,
E h binding energy of electron

(2.4.3)

where is the frequency of the initial X-ray and is the work function of the
spectrometer.

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The binding energy is influenced principally by the nature of the atom from
which it originated, but it is affected also by the valence state of the atom and, to
some extent, by the disposition and polarity of the bonds from the adjacent atoms.
These chemical shifts can also be used to identify more subtle effects in the
adsorbate molecules.
The kinetic energies of the emitted photo-electrons are normally very low.
Therefore, only electrons from the upper 15 nm are able to escape. Thus, this
method is very sensitive to the surface structure.
XPS has been used to characterize polymer surfaces and to determine the
thickness of polymer layers on metals.
Since X-rays are very penetrating, a grazing angle is often used to emphasize the
contribution from the surface atoms.

2.4.3.3 Secondary ion mass spectrometry (SIMS)

The secondary ion mass spectrometry is used for identifying atomic surface
constituents. A primary beam of ions is aimed at the surface and the secondary
particles (which comprise of a different composition and charge) are collected
and focussed in a mass spectrometer. It is identified in the usual way by their
charge/mass ratio.
The primary beam species are ions such as Cs+, O+2, O+, Ar+ and Ga+ with
energies in the range of 130 keV. Therefore, this process is usually much more
energetic than electron bombardment. This results in the sputtering of the surface.
Atoms are gouged out of the surface and some primary ions are incorporated in
the solid. The implantation of primary ions can occur to depths of up to 10 nm.
The secondary beam consists of monoatomic and polyatomic particles of sample
material and resputtered primary ions along with primary electrons and photons
with kinetic energies in the range of zero to several hundred electron volts.
The primary beam can be focussed to less than 1 m in diameter. It can be
scanned across the surface to yield a microanalysis of the surface structure. The
beam can also be trained on a certain area of the sample and will gradually gouge

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out the surface and generate a depth profile of the material in the surface layers.
This process is known as dynamic SIMS.
At the lowest energy level of scanning and microanalysis, the method is called
static SIMS. As little as one millionth of a monolayer can be detected by this
method, which is among the the most sensitive techniques available for analyzing
the surface.
An important drawback of this method is that it destroys the surface it analyzes.

2.4.3.4 Attenuated total reflectance spectroscopy (ATR)

Only a few spectroscopic techniques can be applied directly to the study of the
solidliquid interfaces.
Due to the small volume of the interfacial region, very few methods have
sufficient sensitivity to provide information about any interface involving
aqueous solutions.
One of the most promising spectroscopic methods is ATR, because it can be
concentrated on the interfacial region alone, and can be arranged to sample that
region several times in a single measurement.
Using a thin glass block, the ATR beam can be bounced several times off the
interface during a single pass. At each encounter, the reflection/penetration
depends on the properties of the interfacial region.
The final beam has a signature which contains information on the adsorbed
material in the interface. The visibile/ultraviolet method has been used to the
study of surfactant, polymer, and protein adsorption at the glassaqueous solution
interface. An application is shown in Fig. 2.4.9.
In the case of visible/UV radiation, the aim is to get the bulk of light absorption
process occurring in the interface. Therefore, most studies have been carried out
at the interface between the glass (or quartz) and the adjoining aqueous solution.
With FTIR, the ATR mode can be used to study the surface near where the
reflection is occurring.
Since water has a strong absorption in the IR region, the IR spectra of aqueous
systems are normally studied in extremely short path-length cells. The ATR
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method is a way of circumventing that problem, especially for suspensions, since

such cells cannot be easily filled or cleaned and would be easily plugged with the
solid.

Fig. 2.4.9 ATR-FTIR spectra of adsorbed mussel adhesive protein on polystyrene

(PS) and poly(octadecyl methacrylate) (POMA) surfaces using ATR-FTIR
spectrometry (source: A. M. Baty, P. A. Suci, B. J. Tyler, and G. G. Geesey, J.
Colloid Interface Sci., 177, 307, 1996; adapted by permission from Elsevier Ltd.,
1996).

2.4.3.5 Total internal reflectance fluoroscopy (TIRF)

This technique is closely related to ATR. However, instead of studying the
absorption due to the evanescent wave, the excitation due to that wave produces a
fluorescent emission which is collected in a monochromator and passed on to a
photomultiplier tube for analysis.
The exciting laser beam is chopped at a characteristic frequency so that the
fluorescent emission is modulated at that frequency. This aids in the detection
process.
After suitable calibration, the TIRF signal can be used to measure the adsorption
of the substrate at the solidliquid interface.

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Exercise
Exercise 2.4.1: Calculate the resolution of an optical microscope if the wavelength of
(reflected) light in vacuo is 600 nm, refractive index of the medium is 1.43 and the
numerical aperture is 0.9. Assume that the object is non-luminous.

Exercise 2.4.2: Answer the following questions clearly.

a. What size range of objects is measurable by optical microscopy?
b. Define resolution. How does it depend on the wavelength of light and numerical
aperture?
c. What are the main advantages of fluoroscence microscopy?
d. What is Stokes shift?
e. What are the advantages of confocal microscopy?
f. Discuss the advantages and disadvantages of SEM and TEM?
g. What is scanning probe microscopy? Give two examples.
h. Explain the principle of scanning tunneling microscopy. Discuss its applications.
i. Explain how atomic force microscopy works. What magnitude of force can it
measure? Mention five modes of operation of atomic force microscopy, and
explain their applications.
j. Mention two examples of vacuum-based and non-vacuum spectroscopic
techniques for characterizing a fluidsolid interface.
k. Explain how Auger electron spectroscopy works. Mention three uses of Auger
electron spectroscopy.
l. What is X-ray photoelectron spectroscopy? What is its difference with Auger
electron spectroscopy?
m. Mention two important applications each of secondary ion mass spectrometry and
attenuated total reflectance spectrometry.

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Suggested reading
Textbooks
A. W. Adamson and A. P. Gast, Physical Chemistry of Surfaces, John Wiley,
New York, 1997, Chapter 8.
J. C. Berg, An Introduction to Interfaces and Colloids: The Bridge to
Nanoscience, World Scientific, Singapore, 2010, Chapter 4.
R. J. Hunter, Foundations of Colloid Science, Oxford University Press, New
York, 2005, Chapter 6.

Reference books
L. L. Schramm, Dictionary of Nanotechnology, Colloid and Interface Science,
Wiley-VCH, Weinheim, 2008 (find the topic by following the alphabetical
arrangement in the book).

Journal articles
A. M. Baty, P. A. Suci, B. J. Tyler, and G. G. Geesey, J. Colloid Interface Sci.,

177, 307 (1996).

C. H. Lui, L. Liu, K. F. Mak, G. W. Flynn, and T. F. Heinz, Nature, 462, 339
(2009).
H. Zhang, Thin Solid Films, 320, 77 (1998).
L. Bartels, Nature Chemistry, DOI: 10.1038/NCHEM.517 (2010).
X. Ji, K. T. Lee, R. Holden, L. Zhang, J. Zhang, G. A. Botton, M. Couillard, and
L. F. Nazar, Nature Chemistry, DOI: 10.1038/NCHEM.553 (2010).

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