Surface Characterization by

Spectroscopy and Microscopy

Dr. Nizam M. El-Ashgar

Importance of surface characterization
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Heterogeneous Catalysis.
Semiconductor thin film technology.
Corrosion and adhesion mechanisms
Activity of metal surfaces.
Studies of the behavior and functions of biological
membranes.

Introduction

Definition of Solid Surface:
• The boundary layer between a solid and a vacuum, a gas or a
liquid.
• A part of solid that differs in composition from the average
composition of the bulk of the solid.
Top layer of atoms with a non-uniform composition that varies
from the bulk.
The surface may be several of atomic layers deep.
surface measurements dose not affect the measurement of
average composition of bulk (tiny fraction of the total solid).
Classical Methods:
Provide useful information about the physical nature of surfaces
but less about their chemical nature.
Involve obtaining optical and electron microscopic images of
surfaces and adsorption isotherms, surface areas, surface
roughness, pore sizes and reflectivity.
Spectroscopic Methods: (1950)
Provide information about the chemical nature of surfaces.

Spectroscopic Surface Method
The chemical composition of the solid surface often differs
from the interior or bulk.
Spectroscopic surface methods provide both qualitative and
quantitative chemical information about the composition of
a surface layer of a solid that is a few angstrom units to a
few tens of angstrom units in thickness

General Technique in surface spectroscopy
The solid sample is irradiated with a primary beam made up of
photons, electrons or neutral molecules.

This impact on a solid surface and results in formation of a
secondary beam also consisting of photons, electrons, molecules
or ions form the solid surface.

The type of particles making up the primary beam is not
necessarily the same as the particle of secondary beam.

The secondary beam which results from scattering, sputtering or
emission is studied by a variety of spectroscopic methods.
Most Effective Surface Methods:
Those in which the primary, the secondary beam or both is made up
of either electrons, ions or molecules and not photons to ensure
the measurement be restricted to surface not the bulk.

Examples:
Maximum penetration depth of abeam of 1-keV electrons or ions is
25 Αo. Whereas the penetration depth of a photon beam of the
same energy is about 104 Αo.
Precautions must be taken in case of using two beams of photons
(X-Ray, FL, Raman, IR reflection spectroscopy).
Studying surfaces by these methods is possible but bulk inreferences
must be avoided.
Surface Spectroscopic Methods
Classified according to the nature of the primary and secondary
beams.
Table:

Sampling Surfaces
Three types of sampling methods are employed regardless of the
type of spectroscopic surface method being used.
First method:
Involves focusing the primary beam on a single small area of the
sample and observing the secondary beam.
Second method:
Mapping the surface in which a region of the surface is scanned by
moving the primary beam across the surface in a raster pattern of
measured increments (linear or two dimensional mapping).
Third method:
Depth profiling in which a beam of ions from an ion gun is used to
etch a hole in the surface by sputtering. A finer primary beam is
used to produce a secondary beam from the center of the

Surface Contamination
Contamination of surfaces (by adsorption of some atmospheric
components: water oxygen and CO2) is a problem in analysis.

Even in vacuum these contaminations occurs in a relatively short time.
For example:
At P of 10-6 torr, a clean surface will become covered by a monolayer of gas
molecules in just 3 s.
At P of 10-8 torr coverage occurs in about 1 hr.
At P of 10-10 torr, 10 hr is required.
Provision must often be made to clean the sample surface, in the chamber
used for the irradiating the sample.
Cleaning Methods:
Baking the sample at high temperature, sputtering the sample with a beam of
inert gas ions from an electron gun, mechanical scraping or polishing the
surface with an abrasive, ultrasonic washing with various solvents and
bathing the sample in reducing P to remove oxides.
Other Contaminations:
The primary beam itself can alter the surface as a measurement progresses,
damage occurs that depends on the momentum of the primary beam
particles.

Electron Spectroscopy
XPS, AES and UPS methods are based on analysis of emitted electrons
produced by various incident beams.

The signal from the analyte consists of a beam consists of abeam of
electrons rather than photons.

Determination is of the power of the electrons beam as a function of E (h
ν ) or frequency.

Studying needs high resolution spectral measurements of electrons .

Used to study surfaces.
Types of Electron Spectroscopy:
1- Photoelectron Spectroscopy (XPS) or electron spectroscopy for chemical
analysis (ESCA) :
Sample surface irradiated with monochromatic X-radiation.
2- Auger electron spectroscopy (AES).
Excitation occurs by a beam of electrons.
3- Ultraviolet Photoelectron Spectroscopy (UPS).
A monochromatic beam of UV causes ejection of electrons from the analyte
(not common).

Electron spectroscopy is a powerful tool for the identification of all
the elements in the periodic table except H and He.

The method permits determination of the oxidation state of an
element and the type of species to which it is bonded.

The technique provides useful information about the electronic
structure of molecules.

Applied to gases and solids and to solutions and liquids.

Restricted to surface layer of a few atomic layers thick (20 to 50
Ao) because of poor penetrating power of electrons.

Composition of layers is different from average composition of
entire sample.
Valuable Current Applications:
Qualitative analysis of solid surfaces such as metal alloys,
semiconductors, and heterogeneous catalysis.
Limited applications of quantitative analysis.

X-Ray Photoelectron Spectroscopy

In XPS the kinetic E of emitted electrons is recorded.
The spectrum thus consists of a plot of the number of emitted
electrons or the power of the electron beam as a function of the E
or ν or λ of the emitted electrons .

Principles of XPS:
XPS provides information:
1- About the atomic composition of a sample.
2- about the structure and oxidation state of the compounds.

Physical Bases
Based upon photon in/electron out process.

Photon E (Einstein ): E=hν
where : h - Planck constant ( 6.62 x 10 -34 J s ).
ν - frequency (Hz) of the radiation.

In XPS the photon is absorbed by an atom in a molecule or solid,
leading to ionization and the emission of a core (inner shell)
electron.

But in case of UPS the photon interacts with valence levels
(ionization by lost of one of them)
Process of Photoionization
A + hν
A+* + eWhere A can be an atom, a molecule or an ion and A+* is an
electronically excited cation.
E(A) + h ν = E(A+ ) + E(e-)
Since the electron's energy is present solely as kinetic energy (KE)
this can be rearranged to give the following expression for the KE
of the photoelectron :

KE = h ν – [ E(A+ ) - E(A) ]

The difference in energy between the ionized and neutral atoms, is
generally called the binding energy (BE) of the electron
KE = h ν - BE
Which corrected to:
KE = h ν - BE –W
W is the work function of the spectrometer, which corrects for the
electrostatic environment in which the electron is formed and
measured.
BE of an electron is characteristic of the atom and orbital from which
the electron was emitted.

Experimental Details
The basic requirements:
 a source of fixed-energy radiation (an xray source)
 an electron energy analyzer (which can
disperse the emitted electrons according
to their kinetic energy, and thereby
measure the flux of emitted electrons of a
particular energy)

a high vacuum environment (to enable the
emitted photoelectrons to be analyzed
without interference from gas phase
collisions)

Instrumentation
Expensive: 300,000 – 900,000.

Components:
1- Source
2- sample holder
3- Analyzer (same function as
monochromator) .
4- detector
5- signal processor and read
out.
Electron spectrometers generally require elaborate vacuum systems to
reduce P in all the components (10-5 – 10-8) torr.
1- Sources
Simplest X-ray sources for XPS are X-ray tubes equipped with Mg or Al
targets and suitable filters.

Mg Kα radiation : hν = 1253.6 eV

Al K α radiation : h ν = 1486.6 eV
The emitted photoelectrons will therefore have kinetic energies in the
range of
ca. 0 - 1250 eV or 0 - 1480 eV
The Kα lines for these two elements have considerably narrower band
width (0.8 – 0.9 eV) than that of higher atomic number targets.
Narrow bands lead to enhanced resolutions.
Relatively sophisticated XPS employ a crystal monochromator to provide
an X-ray beam having a bandwidth of about 0.3 eV.
Monochromators improve S/N ratios.

X-ray Photoelectron Spectrometer

2- Sample Holder:
Solid samples: are mounted in a fixed position as close to photon
or electron source and entrance slit of the spectrometer as
possible.
Sample compartment must be evacuated to a pressure of 10-5 torr or
smaller to avoid attenuation of the electron beam.
Much better vacuums 10-9 to 10-10 are required to avoid
contamination of the sample surface by substances such as O2 or
H2O that react with or are adsorbed on surface.
Gas Samples: Are leaked into sample area through a slit of such a
size as to provide P of 10-2 torr. Higher P lead to excessive
attenuation of the electron beam due to inelastic collisions. If the
sample P is two low weakened signal are obtained.

3- Analyzers:
Most electron spectrometers are of hemispherical type in which the
electron beam is deflected by an electrostatic magnetic field so
electron travel in a curved path.
Radius of curvature depends upon KE of the electron and the
magnitude of the field.
By varying the field electrons of various KE can be focused on the
detector. P maintained at 10-5 or lower.
4- Transducers:
Modern electron spectrometers are based upon solid state, channel
electron multipliers.
Consist of tubes of glass that have been doped with lead or vandium.
When potential of several KV is applied across these materials a
cascade or pulse of 106 – 108 electrons is produced for each
incident electron.
These pulses are then counted electronically.
Two dimensional multichannel electron transducers are offered
All resolution elements are stored simultaneously in a computer for
subsequent display.

Applications of XPS
XPS provides:
- Qualitative and quantitative information about the elemental
composition of matter, particularly solid surface.
- Provides useful structural information.
Qualitative Analysis:
A low resolution, wide-scan XPS (survey spectrum) (next page).
Used to determine the elemental composition of samples.

XPS Spectra

1- Characteristic binding energy associated with each core
atomic orbital i.e. each element will give rise to a
characteristic set of peaks in the photoelectron spectrum at
kinetic energies determined by the photon energy and the
respective binding energies.
2- The presence of peaks at particular energies therefore
indicates the presence of a specific element in the sample
under study.
3- The intensity of the peaks is related to the
concentration of the element within the sampled region.
(quantitative analysis of the surface composition).

- With Mg or Al Kα source, all elements except H and He emit core
electrons having characteristic BE.
Survey spectrum has KE range of 250-1500 eV, which correspond
to BE of about 0-1250 eV.
Every element in the P.T. has one or more E levels that will result
in the appearance of peaks in this region.
The peaks are well resolved and lead to unambiguous
identification provided the element if the element conc. >0.1%.
Sometimes peak overlap is encountered such as O1s/Sb3d or
Al2s, 2p/Cu3s, 3p.
Overlapping problems can be resolved by investigating other
spectral regions for additional peaks.
Peaks from Auger electrons are found in XPS which are readily
identified by comparing spectra produced by two X-ray sources
(Mg and Al, Kα )
Auger peaks remain unchanged while photoelectric peaks are
displaced on the KE scale.

Chemical shifts and oxidation states

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One of the peaks of the survey spectrum is examined under
conditions of high E resolution.
The position of the maximum is found to depend to a small degree
upon the chemical environment of the atom responsible for the
peak.
So depends on: variations in the number of valence electrons and
the type of bonds they form so influence the BE of the core
electrons.
BE increases as the oxidation state becomes more positive.
This chemical shift can be explained by assuming that the
attraction of the nucleus for a core electron is diminished by the
presence of outer electrons.
When one of these electrons removed the effective nuclear charge
sensed for the core electron is increased so BE increases.
Important application: Identification of the oxidation states of the
elements for different kinds of inorganic compounds.

Chemical shifts and structure

The shift in binding E can be rationalized by taking into account the effect
of the various functional groups on the effective nuclear charge
experienced by the 1s core electrons.
As the electron nativity of the attached functional group increases it will
withdraw electron density from carbon so the effective nuclear charge
increases and the BE increases.
XPS provides also the relative number of each type of atoms present in a
compound. Example: The nitrogen 1s spectrum for sodium azide (Na+N3-)
is made up of two peaks having relative areas in the ratio of 2:1
corresponding to the two end nitrogens and the center nitrogen
respectively.
Notes:
The phtoelectrons in XPS are incapable of passing through more than 10-50
A0 of a solid.
Thus the most important applications of electron spectroscopy are for
surfaces.
Examples of uses:
Identification of active sites and poisons on catalytic surfaces.
Determination of surface contaminants on semiconductors.
Analysis of the composition of human skin
Study of oxide surface layers on metal alloys.
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The XPS method has substantial potential in the elucidation of
chemical structure.
Its ability to distinguish among oxidation states of an element.
Quantitative Applications:
For determination of the elemental composition of various inorganic
and organic materials.
Both peak intensities and peak areas have been used as the
analytical parameter as a function with concentration.
Assumption that the surface composition and bulk are the same is
Not always correct.

Chemical Shifts
The exact binding energy of an electron depends not
only upon the level from which photoemission is
occurring, but also upon :
1) The formal oxidation state of the atom.
2) The local chemical and physical environment.
Changes in either (1) or (2) give rise to small shifts in the
peak positions in the spectrum - so-called chemical shifts
Atoms of a higher positive oxidation state exhibit a
higher binding energy due to the extra columbic
interaction between the photo-emitted electron and
the ion core.

Where do Binding Energy Shifts Come From? Or
element or compound identification.

Elemental Shifts

Electronic Effect
Spin-Orbit Splitting or Spin-Orbit Coupling
 Some electronic levels (most obviously 3p and 3d ) give
rise to a closely spaced doublet, Which appear when
spectra expanded.
 Permitted J values = L ± S
 Coupling between L: The Angular Q.N., S: Unpaired
Spin
 The lowest energy final state is the one with maximum J
(more than half full)
 The relative intensities of the two peaks reflects the
degeneracies of the final states (gJ = 2J + 1),
 2D 5/2:
gJ = 2x{5/2}+1 = 6 (lower B.E)
 2D 3/2:
gJ = 2x{3/2}+1 = 4 (higher B.E)
 These two values determines the probability of transition
to such a state during photoionization



The inner core electronic configuration of the initial state of the Pd is:
(1s)2(2s)2(2p)6(3s)2(3p)6(3d)10 ....
with all sub-shells completely full.
The removal of an electron from the 3d sub-shell by photo-ionization
leads to a (3d)9 configuration for the final state - since the d-orbitals (l
= 2) have non-zero orbital angular momentum, there will be coupling
between the unpaired spin and orbital angular momenta.
Spin-orbit coupling is generally treated using one of two models which
correspond to the two limiting ways in which the coupling can occur these being the LS (or Russell-Saunders) coupling approximation and
the j-j coupling approximation.
If we consider the final ionized state of Pd within the Russell-Saunders
coupling approximation, the (3d)9 configuration gives rise to two
states (ignoring any coupling with valence levels) which differ slightly
in energy and in their degeneracy ...
2D 5/2 g J = 2x{5/2}+1 = 6 2D 3/2 g J = 2x{3/2}+1 = 4
These two states arise from the coupling of the L=2 and S=1/2
vectors to give permitted J values of 3/2 and 5/2. The lowest energy
final state is the one with maximum J (since the shell is more than
half full), i.e. J = 5/2, hence this gives rise to the "lower binding
energy" peak. The relative intensities of the two peaks reflects the
degeneracies of the final states (g J = 2J+1), which in turn determines
the probability of transition to such a state during photoionization.

s-Orbital

p-Orbital

d-Orbital

f-Orbital

Chemical Shifts-Electronegativity Effects

Chemical Shifts- Electronegativity Effects

C1s envelope has been resolved into five components
of polystyrene surface exposed to an oxygen plasma.

Applications
of X-ray
Photoelectron
Spectroscopy (XPS)

XPS Analysis of Pigment from Mummy
Artwork

Analysis Carbon Fiber- Polymer Composite
Material by XPS

Analysis of Materials for Solar Energy Collection by
XPS Depth ProfilingThe amorphous SiC/SnO /SnO2 Interface

Polysiloxane Immobilized Ligand
System
O

O
O

CH2

C O C2H5
+ H2N(CH2)2NH2

N

Si

CH2

O

C O C2 H 5

Reflux/
Toluene - C2H5OH

O
O
O
O
O

Si

CH2

C

NH

NH2

CH2

C NH

NH2

N

O

XPS Results
System

Element

Precursor

Core-line

 

%Composition

Product

Core-line

 

%Composition

C

Si

O

N

C1s

Si2p

O1s

N1s

285

102

532

399.5

38.8

17

41.4

2.85

C1s

Si2p

O1s

N1s

285

102

532

399.5

42.4

19.3

28.7

9.6

Conclusion


XPS is a powerful technique for
characterizing solid surfaces.
All types of inorganic solids can be
analyzed.
Elemental (except H, He) and chemical
analyses within a depth of 10 nm.
Quantitative technique.
Extremely useful for surface treatment of
materials.

Auger Electron Spectroscopy AES
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Auger Electron Spectroscopy (Auger spectroscopy or
AES) was developed in the late 1960's.
Deriving its name from the effect first observed by Pierre
Auger, a French Physicist, in the mid-1920's.
It is a surface specific technique utilizing the emission of
low energy electrons in the Auger process
It is one of the most commonly employed surface
analytical techniques for determining the composition of
the surface layers of a sample.

Auger Electron Spectroscopy
Is based upon a two-step process:
First Step: (Ionization)
Involves formation of an electronically excited ion A+* by exposing
the analyte to a beam of electrons or sometimes X-rays.
With X-rays:
A + hν → A+* + eWith an electron beam:
A + e-i → A+* + e’-i + e-A
Where:
e-i represents an incident electron from the source.
e’-i represents the same electron after it has interacted with A and
has thus lost some of its energy.
e-A represents an electron that is ejected from one of the inner
orbitals of A.

Energy levels in an isolated, multi-electron atom

Alternative nomenclature on the left that is used in Auger
spectroscopy.

Electronic Structure - Solid State

In the solid state the core levels of atoms are little perturbed and
essentially remain as discrete, localized (i.e. atomic-like) levels.
The valence orbitals, however, overlap significantly with those of
neighboring atoms generating bands of spatially-delocalized energy levels.
The energy level diagram for the solid is therefore closely resemblant of
that of the corresponding isolated atom, except for the levels closest to the
vacuum level.
The diagram below shows the electronic structure of Na metal:

The Auger Process

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The Auger process is initiated by creation of a core hole - this is
typically carried out by exposing the sample to a beam of high
energy electrons (typically having a primary energy in the range 2 10 keV).
Such electrons have sufficient energy to ionize all levels of the
lighter elements, and higher core levels of the heavier elements.
Ionization is shown to occur by removal of a K-shell
electron, but in practice such a crude method of ionization
will lead to ions with holes in a variety of inner shell levels.
In some studies, the initial ionization process is instead
carried out using soft x-rays ( hν = 1000 - 2000 eV ).
In this case, the acronym XAES is sometimes used.
However, this change in the method of ionization has no
significant effect on the final Auger spectrum.

Relaxation & Auger Emission
Relaxation of the excited ion A+* can occur in either two ways.
2- X-ray Fluorescence:
A+* → A+ + hνf
hνf : Fluorescence photon
The second process recognized as X-ray fluorescence. The energy of
the Fl radiation hνf is independent of the excitation E. So
polychromatic radiation can be used.
2- Auger emission:
A+* → A++ + e-A
e-A : Auger electron
The E given up in relaxation results in the ejection of an electron
(auger electron) with KE, Ek
The energy of the auger electron is independent of the E of the
photon or electron that originally created the vacancy in E level Eb.
So mono-energetic source is not required for excitation.
So it can be distinguished from XPS by this point.

KE of the auger electron is the difference between the E released in
relaxation of the excited ion (Eb- E’b) and the energy required to
remove the second electron from its orbit (E’b).
Ek = (Eb – E’b) –E’b = Eb – 2E’b
Auger emissions are described in terms of the type of orbitals
involved in the production of the electron.
Example:
KLL Auger transition involves an initial removal of a K electron
followed by a transition of an L electron to the K orbital with the
simultaneous ejection of a second L electron.
Other common transitions:
LMM and MNN
XPS Spectra:
Consist of a few characteristic peaks lying in the region of 20 t0 1000
eV.

Auger emission

In previous example, one electron falls from a higher level to fill an
initial core hole in the K-shell.
The energy liberated in this process is simultaneously transferred
to a second electron.
A fraction of this energy is required to overcome the binding energy
of this second electron.
The remainder is retained by this emitted Auger electron as kinetic
energy.
In the Auger process illustrated, the final state is a doubly-ionized
atom with core holes in the L1 and L2,3 shells.
We can make a rough estimate of the KE of the Auger electron from
the binding energies of the various levels involved. In this particular
example,
KE = ( EK - EL1 ) - EL23
Note : the KE of the Auger electron is independent of the
mechanism of initial core hole formation.
The expression for the energy can also be re-written in the
form :
KE = EK - ( EL1 + EL23 )

It should be clear from this expression that the latter two
energy terms could be interchanged without any effect i.e. it is actually impossible to say which electron fills the
initial core hole and which is ejected as an Auger electron
; they are indistinguishable.
An Auger transition is therefore characterized primarily by :
the location of the initial hole

the location of the final two holes

although the existence of different electronic states
(terms) of the final doubly-ionized atom may lead to fine
structure in high resolution spectra.

When describing the transition, the initial hole location is
given first, followed by the locations of the final two holes
in order of decreasing binding energy.

i.e. the transition illustrated is a KL1L2,3 transition .

If we just consider these three electronic levels there are
clearly several possible Auger transitions : specifically,

K L1 L1, K L1 L2,3 , K L2,3 L2,3

In general, since the initial ionization is non-selective and the
initial hole may therefore be in various shells, there will be many
possible Auger transitions for a given element - some weak, some
strong in intensity. AUGER SPECTROSCOPY is based upon the
measurement of the kinetic energies of the emitted electrons.
Each element in a sample being studied will give rise to a
characteristic spectrum of peaks at various kinetic energies.

This is an Auger spectrum of Pd metal - generated using a 2.5 keV
electron beam to produce the initial core vacancies and hence to
stimulate the Auger emission process. The main peaks for
palladium occur between 220 & 340 eV.
The peaks are situated on a high background which arises from
the vast number of so-called secondary electrons generated by a
multitude of inelastic scattering processes.

Auger spectra are also often shown in a differentiated form : the
reasons for this are partly historical, partly because it is possible
to actually measure spectra directly in this form and by doing so
get a better sensitivity for detection. The plot below shows the
same spectrum in such a differentiated form.

Like XPS Auger spectra consist of a few characteristic peaks lying
in the region of 20-1000 eV.
The derivative of the counting rate as a function of the KE of the
electron dN(E)/dE serves as the ordinate.
Derivative spectra are standard for Auger spectroscopy in order to
enhance the small peaks and repress the effect of the large but
slowly changing, scattered electron background radiation.
Well separated peaks obtained (useful for qualitative
identification).

Comparison between XPS and AES
- Auger electron emission and XPS are competitive processes
and their relative rates depend upon atomic number of the
element involved.
Elements of high Z favor XPS (not sensitive for Z < 10).
Elements of low Z favor AE.
Both AES and XPS are complementary, the two techniques
involved in a single instrument.
Auger is of particular strength because of:
1- Its sensitivity to atoms of low Z.
2- Its minimal matrix effects.
3- Its high spatial resolution (detailed exam. Of solid
surfaces). This arises because the primary beam is
electrons ( more tightly focused on surfaces) than X-rays.
Poor information for oxidation state obtained in case of
AES.
Difficulties in quant. analysis in case of AES.

Instrumentation of AES


Is similar to that for XPS except that the source is usually
an electron gun rather than an X-ray tube.
This source consists of a heated tungsten filament (0.1 mm
d) and bent into V-shape tip.
The cathodic filament is maintained at V of 1-50 kV with
respect to the anode contained in the gun.
Wehnelt cylinder surround the filament (-ve).
The Electric Field causes electrons to converge on a tiny
spot called crossover (of diameter d0)
Cathodes contracted from LaB6 rods also used in electron
guns (expensive source and requires better vacuum system
to prevent oxide formation the decrease the efficiency).
Third type: field emission W or C cathode of very sharp tip
(100 nm or less). Held at high potential with intense E.F. at
the tip (> 107 v/cm). Provides a beam of electrons of
crossover diameter of only 10 nm (in case of W = 50 µm
and LaB6 = 10 µm). Disadv: Fragility and requires better
vacuum.


Electron guns produce a beam of electrons with e of 1-10 KeV that
focused on the surface of a sample.
AES is of very high spatial-resolution scanning of solid surfaces.
Normally electron beams with diameter ranging from 500 to 5 µm
are used for this purpose.
Guns producing beams of ≈ µm are called auger microprobes used
to detect and determine the elemental composition of
inhomogeneties

Applications of AES
Qualitative Analysis of Solid Surfaces:
- Auger spectra obtained by bombardment a small area of a surface
( diam 5-500 µm) with a beam of electrons from a gun).
A derivative electron spectrum is obtained with an analyzer.
Advantages:
The low energy auger electrons (20-1000 eV) are able to penetrate
only a few atomic layers (3-20 A) of solid.
Thus electrons penetrate greater dept below sample surface but only
these auger electrons from the first four or five atomic layers
escape to reach the analyzer. (AES reflects the surface comp. of
solids).

Depth Profiling of Surfaces:
- That involves determination of the elemental composition of a
surface as it is being etched away (sputtered) by a beam of argon
ions.
Either XPS or Auger spectroscopy can be used for elemental
detection but AES is the more common.
The microprobe (of d 5 µm) and etching beams are operated
simultaneously.
Intensity of one or more of auger peaks recorded as a function of
time, a depth profile of elemental composition is obtained.
Important for:
Corrosion chemistry, catalyst behavior and properties of
semiconductor junctions.

Line Scanning

Are used to characterize the surface composition of solids as a
function of distance along a straight line of 100 µm or more.
Auger microprobe is used that produces a beam that can be
moved across a surface in a reproducible way.

Secondary ion Mass Spectrometry (SIMS)
SIMS is the most highly developed of the mass spectrometric
surface methods.

Proven useful for determining both atomic and molecular
composition of solid surfaces.
Two types:
1- Secondary-ion mass analyzers.
2- Microprobe analyzers.
Both are based upon bombarding the surface of the sample with a
beam of 5-20 keV ions such as Ar+, Cs+, N2+, or O+2.

The ion beam is formed in an ion gun in which the gaseous atoms or
molecules are ionized by an electron impact source.
The positive ions are then accelerated by applying a high dc
potential.
The impact of these primary ion causes the surface layer of atoms of
the sample to be stripped (sputtered off) largely as neutral atoms.
A small fraction however forms positive or negative secondary ions
that are drawn into a spectrometer for mass analysis.

Secondary mass analyzers:
Serves for general surface analysis and depth profiling.
The primary ion beam diameter ranges from 0.3-5 mm.
Double-focusing, single focusing, time-of-flight and quadruple
spectrometers are used for mass determination.
These spectrometers yield qualitative and quantitative information
about all the isotopes (hydrogen through uranium) present on
surface.
Sensitivities of 10-15 g or better are typical.
Concentration profiles can be obtained with depth resolution of 50 to
100 Ao.

Ion Microprobe Analyzers


Are more sophisticated and more expensive instruments that are
based upon a focused beam of primary ions that has a diameter of
1 to 2 µm.
This beam can be moved across a surface for about 300 µm in
both the x and y directions.
A microscope is provided to permit visual adjustment of the beam
position.
Mass analysis is performed with a double-focusing spectrometer.
The ion microprobe version of SIMS permits detailed studies of
solid surfaces.

Laser-Microprobe Mass Spectrometry

For solid surface studying.

Ionization and volatilization are accomplished with pulsed neodymium-YAG
laser, which after frequency quadrupling, produces a 0.5 µm spot of 266nm radiation.

The power density of the radiation within this spot is 1010 to 1011 W/cm2.

Attenuation of the power of the beam to 1% by means of a 25-step
optical filter.

A second lower power He-Ne laser (λ = 633 nm) is collinear with the
ionization beam (illumination beam) so area chosen visually.
Advantages:

Sensitivity is high (< 10-20).

Applicable to both inorganic and organic (including biological) samples.

Resolution is about 1 µm.

Produces data at rapid rate.
Applications:
Determination of Na/K conc. ratios in frog nerve fiber.
Determination of calcium distribution in retinas.
Classification of asbestos and coal mine dusts.
Determination of Fluorine distributions in dental hard tissue.
Analysis of amino acids.
Study of polymer surfaces.

Electron microprobe
Electron microprobe analysis (EMPA) is a non-destructive method for determining the
chemical composition of tiny amounts of solid materials.

X-ray emission is stimulated on the surface of the sample by a narrow focused
beam of electrons.

The resulting X-ray emission is detected and analyzed with either a wavelength
or an energy dispersive spectrometer.
Instrumentation
The instrument employs three integrated beams of radiation (electron, light and Xray) and < 10 an system is required and λ or E-dispersive X-ray spectrometer.

An electron source, commonly a W-filament cathode referred to as a "gun."

A series of electromagnetic lenses located in the column of the instrument,
used to condense and focus the electron beam (0.1- 1 µm OD) emanating from
the source; this comprises the electron optics and operates in an analogous
way to light optics.

A sample chamber, with movable sample stage (X-Y-Z), that is under a vacuum
to prevent gas and vapor molecules from interfering with the electron beam on
its way to the sample; a light microscope allows for direct optical observation of
the sample.

X-ray produced by the electron beam are collimated.

A variety of detectors arranged around the sample chamber that are used to
collect x-rays and electrons emitted from the sample.


Electrons are produced by heating a filament similar to the
filament in a light bulb (A).
These electrons are then formed into a beam by
accelerating them down a column at very high voltages,
typically 15 to 20 thousand volts.
The electrons pass through lenses that condense the beam
(B), remove aberrations (C) and focus the beam (D).
When the electrons arrive at the sample (E) the beam is
focused into a spot much smaller than 0.001 millimeter in
diameter.
Upon entering the sample, the electrons interact with the
atoms in the sample in what is called the
interaction volume, causing X-rays to be produced.
Each element produces X-rays with characteristic energies.
These X-rays can then be counted by reflecting them
through a crystal (F) and sending them on to a detector
(G).
By counting the X-rays generated by each element in the
sample and comparing that number to the number of X-ray
generated by a standard of known composition, it is
possible to determine the chemical composition of a spot
one one-thousandth of a millimeter in diameter with great
accuracy.

Applications
Provides a wealth information about the physical and chemical nature
of surfaces (Quantitative and Qualitative analysis).

Phase studies in metallurgy and ceramics.

Investigation of grain boundaries in alloys.

Measurement of diffusion rates of impurities in semiconductors.

Determination of occluded species in crystals.

Study of the active sites of heterogeneous catalysts.

Scanning Electron Microscopy
Great importance of studying of physical nature of solid
surfaces in many fields (chemistry, material science, geology
and biology).
Classical methods:
Is the optical microscopy, but of limitted resolution because of
diffraction effects to about the wavelength of light.
Higher resolution techniques (Three types)
1- Scanning electron microscopy (SEM).
2- Scanning tunneling microscopy (STM).
3- Atomic force microscopy (AFM).
Basics:
The surface of the solid is swipt in a raster pattern with finely
focused beam of electrons or with a suitable probe.
The raster is a scanning pattern similar to cathode-ray tube in
TV:

Raster (Scanning pattern)
1- Swept across a surface in a straight line (X-direction).
2- Returned to its starting position.
3- Shifted downward (y direction) by a standard increment.
4- Repeating the process until a desired area of the surface has been
scanned.
5- During scanning process a signal is received above the surface (Z
direction) and stored in a computer system which converted to an
image.

Why Study Surfaces?

Surface – the interface between two of
matter’s common phases:





Solid-gas (we will primarily focus on this)
Solid-liquid
Solid-solid
Liquid-gas
Liquid-liquid
The majority of present studies are applied to
this type of system, and the techniques
available are extremely powerful

The properties of surfaces often control
chemical reactions

Microscopy

Why is microscopy useful?
the analytical chemist?



What can it tell

Sample topography
Structural stress/strain
Electromagnetic properties
Chemical composition

Plus - a range of spectroscopic techniques,
from IR to X-ray wavelengths/energies,
have been combined with microscopy to
create some of the most powerful
analytical tools available…

Imaging Resolution and Magnification
Some typical values for microscopic
methods:
Magnificati
Method

Resolution

Human Eye

0.1-0.2 mm

on
(x)
-

Optical
Microscopy
Electron
Microscopy
Probe
Microscopy

0.1-0.2 um

~1200

30-50 Å

10-75,000

<1 Å

> 500,000

Optical Microscopy - History

An ancient technique – the lens has been around for
thousands of years. Chinese tapestries dating from 1000
B.C. depict eyeglasses.
In 1000 A.D., an Arabian mathematician (Al Hasan) made
the first theoretical study of the lens.
Copernicus (1542 A.D.) made the first definitive use of a
telescope.
As glass polishing skills developed, microscopes became
possible. John and Zaccharias Jannsen (Holland) made the
first commercial and first compound microscopes.
Then came lens grinding, Galileo, the biologists, and many
great discoveries….

Modern Optical Microscopy in Chemistry

As optical microscopy
developed, the compound
microscope was applied to the
study of chemical crystals.
The polarizing microscope
(1880): can see boundaries
between materials with
different refractive indices,
while also detecting isotropic
and anisotropic materials.

http://www.microscopyu.com/articles/polarized/polarizedintro.html

Optical Microscope Design

Microscope design has not
changed much in 300
years
• But the lenses are
more perfect – free of
aberrations
Objective lenses are
characterized NA (numerical
apertures)
• The numerical aperture of a
microscope objective is a
measure of its ability to
gather light and resolve fine
specimen detail at a fixed
object distance
• Large NA = finer detail =
better light gathering

Diagram from Wikipedia (public domain)

http://www.microscopyu.com/articles/polarized/polarizedintro.html

Electron Microscopy (EM)
Scanning electron microscopy (SEM) – an electron beam is scanned
in a raster pattern with a beam of energetic electrons and
“reflected” effects are monitored.
Several types of signals are produced from a surface in this process
including:
1- Backscattered electrons.
2- Secondary electrons.
(Serve the basis of scanning electron microscopy)
3- Auger electrons.
4- X-ray fluorescence photons (used in electron microprobe analysis).
5- Other photons of various energies.
All of these signals have been used for surface studies

Ice crystals
optical

SEM

Electron Microscopy: Resolution

Why can an electron microscope resolve things that are
impossible to discern with optical microscopy?
Example – calculate the wavelength of electrons accelerated by
a 10 kV potential:
1
2

mv 2 = eV

2eV
v=
m

λ=

h
m
h
λ=
=
m 2eV
2meV
6.63 ×10 −34 J s

Note: Resolution
is limited by lens
aberrations!

2(9.11×10-31 kg )(1.60 ×10-19 C)(10 4 V)

λ = 1.23 ×10 −11 m = 0.0123 nm
= 0.123 x 10-3 µm. So EM can see >10000x more detail than visible
light!

Electron Microscopy: Resolution

What about relativistic corrections? The electrons in an EM
can in some cases be moving pretty close to the speed of
light.
Example – what is the wavelength for a 100 kV potential?

Using the
relativistically
corrected form of the
previous equation:

λ=

λ=

h
m
h
=
m 2eV
2meV (1 + 2eV
)
mc 2
6.63 ×10 −34 J s

2(9.11×10 kg )(1.60 ×10 C)(10 V)(1 +
-31

-19

4

(1.60×10 -19 C)(10 4 V )
2 ( 9.11×10 -31 kg) ( 3×108 m / s ) 2

λ = 3.7 ×10 −3 nm

At high potentials, EM can see atomic dimensions

)

Electron Microscopy: Sample-Beam Interactions

Sample-beam interactions
control how both SEM and TEM
(i.e. STEM) operate:
• Formation of images
• Spectroscopic/diffractometric
analysis
There are lots (actually eight)
types of sample-beam
interactions (which can be
confusing and hard to
remember!)
It helps to classify these 8 types into two classes of sample-beam
interactions:
• bulk specimen interactions (bounce off sample – “reflected”)
• thin specimen interactions (travel through sample-“transmitted”)

SEM: Sample-Beam Interactions
Backscattered Electrons (~30 keV)

Caused by an incident electron colliding
with an atom in the specimen which is
almost normal to the incident electron’s
path. The electron is then scattered
"backward" 180 degrees.
Backscattered electron intensity varies
directly with the specimen's atomic
number. This differing production rates
causes higher atomic number elements to
appear “brighter” than lower atomic
number elements. This creates contrast in
the image of the specimen based on
different average atomic numbers.
Backscattered electrons can come from a
wide area around the beam impact point
(see pg. 552 of Skoog) – this also limits
the resolution of a SEM (along with
abberations in the EM lenses)

SEM: Sample-Beam Interactions+
Secondary Electrons (~5 eV)

Caused by an incident electron passing
"near" an atom in the specimen, close
enough to impart some of its energy to a
lower energy electron (usually in the Kshell). This causes a slight energy loss, a
change in the path of the incident electron
and ionization of the electron in the
specimen atom. The ionized electron then
leaves the atom with a very small kinetic
energy (~5 eV). One incident electron can
produce several secondary electrons.
Production of secondary electrons is closely
linked to sample topography. Their low
energy (~5 eV) means that only electrons
very near to the surface (<10 nm) are
detected. They also don’t suffer from the
backscattered electron lateral resolution
problem depicted in Fig. 21-16 of Skoog.
Changes in topography in the sample that
are larger than this sampling depth can
change the yield of secondary electrons via
indirect effects (called collection
efficiencies).

SEM: Sample-Beam Interactions
Auger Electrons (10 eV – 2 keV)

Caused by relaxation of an ionized atom
after a secondary electron is produced.
The lower (usually K-shell) electron that
was emitted from the atom during the
secondary electron process has left a
vacancy. A higher energy electron from
the same atom can drop to a lower energy,
filling the vacancy. This leaves extra
energy in the atom which can be corrected
by emitting a weakly-bound outer electron;
an Auger electron.
Auger electrons have a characteristic
energy, which is unique and depends on
the emitting element. Auger electrons
have relatively low energy and are only
emitted from the bulk specimen from a
depth of several angstroms.

SEM: Sample-Beam Interactions
X-ray Emission

Caused by relaxation of an ionized atom
after a secondary electron is produced.
Since a lower (usually K-shell) electron
was emitted from the atom during the
secondary electron process an inner
(lower energy) shell now has a vacancy.
A higher energy electron can "fall" into
the lower energy shell, filling the
vacancy. As the electron "falls" it emits
energy in the form of X-rays to balance
the total energy of the atom.
X-rays emitted from the atom will have a
characteristic energy which is unique to
the element from which it originated.
X-ray (elemental) mapping of sample
surfaces is a common applications and a
very powerful analytical approach.

SEM: Sample-Beam Interactions – X-rays

SEM: Sample-Beam Interactions
Cathodoluminescence (CL)

Caused by electron hole pairs, which are
created by the electron beam in certain
kinds of materials. When the pairs
recombine, cathodoluminescence (CL) can
result. CL is the emission of UV-Visible-IR
light by the recombination effect. CL is
usually very weak and covers a wide range
of wavelengths, and requires high beam
currents, lowering resolution and
challenging detector systems!

CL signals typically result from small
impurities in an otherwise homogeneous
material, or lattice defects in a crystal.

CL can be used effectively for some
analytical problems. Some “random”
examples:
• Differentiation of anatase and rutile
• Studying ferroelectric domains in
sodium niobate
• Location of subsurface crazing in
ceramics
• Forensic analysis of glasses

TEM: Sample-Beam Interactions (Thin Sample)

Unscattered Electrons

Incident electrons which are
transmitted through the thin
specimen without any interaction
occurring inside the specimen.
Used to image - the transmission
of unscattered electrons is
inversely proportional to the
specimen thickness. Areas of the
specimen that are thicker will have
fewer transmitted unscattered
electrons and so will appear
darker, conversely the thinner
areas will have more transmitted
and thus will appear lighter.

TEM: Sample-Beam Interactions (Thin Sample)
Elastically-Scattered Electrons

Incident electrons that are scattered
(deflected from their original path) by
atoms in the specimen in an elastic
fashion (without loss of energy). These
scattered electrons are then transmitted
through the remaining portions of the
specimen.

Electrons follow Bragg's Law and are
diffracted. All incident electrons have
the same energy (and wavelength) and
enter the specimen normal to its
surface. So all incident electrons that
are scattered by the same atomic
spacing will be scattered by the same
angle. These "similar angle" scattered
electrons can be collated using magnetic
lenses to form a pattern of spots; each
spot corresponding to a specific atomic
spacing, This pattern can then yield
information about the orientation,
atomic arrangements and phases
present in the area being examined.

TEM: Sample-Beam Interactions (Thin Sample)
Inelastically-Scattered Electrons
Incident electrons that interact with sample
atoms inelastically (losing energy during
the interaction). These scattered electrons
are then transmitted through the rest of
the sample.
Inelastically scattered electrons have two
uses:
1. Electron Energy Loss Spectroscopy (EELS):
The amount of inelastic loss of energy by
the incident electrons can be used to study
the sample. These energy losses are
unique to the bonding state of each
element and can be used to extract both
compositional and bonding (i.e. oxidation
state) information on the sample region
being examined.
2. Kakuchi bands: Bands of alternating light
and dark lines caused by inelastic
scattering, which are related to interatomic
spacing in the sample. These bands can be
either measured (their width is inversely
proportional to atomic spacing) or used to
help study the elasticity-scattered electron
pattern

Electron Microscopy: Basic Design

Basic layout of an electron microscope:
Electron
gun
(1-30 keV)

Computer

Magnetic
lenses and
scanning
coils

Detectors
electrons
photons

Sample
electrons
Detectors

Electron Source (Gun)
Thermionic electron gun – how it works:

Positive electrical potential applied to the
anode
The filament (cathode) is heated until a
stream of electrons is produced
The electrons are then accelerated by the
positive potential down the column (can be
up to 30 kV)
A negative electrical potential (~500 V) is
applied to the Wehnelt cap
Electrons are forced toward the column axis
by the Wehnelt cap
Electrons collect in the space between the
filament tip and Wehnelt cap (a space
charge or “pool”)
Those electrons at the bottom of the space
charge (nearest to the anode) can exit the
gun area through the small (<1 mm) hole
in the Wehnelt cap
These electrons then move down the
column towards the EM lens and scanning
systems

The results:
- Electrons are emitted from
a nearly perfect point
source (the space
charge)
- The electrons all have
similar energies
(monchromatic)
- The electrons will travel
parallel to the column
axis

Electron Optics: Focusing and Scanning

Apertures – usually made of platinum foil, with circular holes of 2
to 100 µm.
The magnetic condenser and objective lens serve to reduce the
image to final spot size on sample (5-200 µm).
The condenser lens system (one or more lenses) to accelerate
electrons to reach the objective lens.
The objective lens is responsible for the size of electron beam
impinging on surface of sample.
The individual lens is cylindrically symmetrical and of 10-15 cm in
height.

Magnetic lenses: Circular electro-magnets capable of
projecting a precise circular magnetic field in a specified
region. The field acts like an optical lens, having the same
attributes (focal length, angle of divergence...etc.) and
errors (spherical aberration, chromatic aberration....etc.).
They are used to focus and steer electrons in an EM (SEM
and STEM).
Goal – a focused, monochromatic (I.e. same
energy/wavelength) electron beam!

Scanning with SEM

Accomplished by the two pairs of electromagnetic coils within the objective
lens.

One pair deflects the beam in the X direction across the sample.

The other pair deflects it in the y direction.

By applying an electrical signal to one pair of the scan coils and varying
the electrical signal (x coils) as a function of time, the electron beam is
moved in a straight line across the sample and then returned to its original
position.

After completion of the line scan, the other set of coils (y coil in this case)
is used to deflect the beam slightly and the deflection of the beam using
the x coils is repeated.
By rapidly moving the beam the entire sample surface can irradiated with the
electron beam.
The signals to the scan coils can be either analog or digital (reproducible
movement and location of the electron beam)
The output signal from the sample can be encoded and stored in the digital
form along with digital representations of the x and y positions of the
beam.
The signals are also used to drive the horizontal and vertical scans of a
cathode-ray tube (CRT).

The image of the sample
Produced by using the output of a detector to control the intensity
of the spot on CRT.
This method of scanning produces a map of the sample in which
there is one-to-one correlation between the signal produced at a
particular location on the sample surface and corresponding point
on the CRT display.
Magnification (M) achievable in the SEM image is given by
M = W/w
Where W is the width of the CRT display and w is the width of the
signal line scan across the sample.
W is constant so magnification is achieved by decreasing w.
So focusing the electron beam to infinity small point could provide
infinite magnification.
But variety of factors limit M to a range of 10X to 100,000X.

Sample and sample Holder
Sample chambers are designed for rapid changing of samples.

Large capacity vacuum pumps are used to hasten the switch from
ambient P to 10-4 torr or less.

Sample holder is capable of holding samples many cm on an
edge.

It can be moved in the x, y and z directions and can rotated about
each axis.
Samples that conduct electricity are easiest to study, because the
unimpeded flow of electrons to ground minimizes artifacts
associated with buildup of charge.
It also conduct heat which minimizes the likelihood of their thermal
degradation.
(biological and most minerals samples do not conduct.
A variety of techniques have been developed for obtaining SEM
images of non conducting samples.
Most common approaches involve coating the surface of the sample
with thin metallic film produced by sputtering or by vacuum
evaporation

Transducers
scintillation devices: most common type:
The detector consists of a doped glass or plastic target that emits a cascade of
visible photons when struck by an electron.
The photons are conducted by a pipe to a photomultiplier tube that is housed
outside the high-vacuum region of the instrument.
Gains 105-106.
Semiconductor transducers:
(flat wafers of semiconductor material) are also used in electron microscopy.
When high E electron strikes the detector, electron-hole pairs are produced
that result in increased conductivity.
Current gains are 103-104
The device is small enough so that it can be placed immediately adjacent to
the sample (leads to high collection efficiency).
Easy to use and are less expensive than scintillation transducers.
X-rays produced:
Usually detected and measured with E-dispersive systems.

Applications
-

-

Provides morphologic and topographic information about the
surfaces of solids that usually necessary in understanding the
behavior of surfaces.
First step in the study of the surface properties of a solid.

Electron Microscopy: Overall Design
TEM design is similar – however,
nowadays, TEM systems
usually include a “cryo-stage”
for keeping samples extremely
cold during analysis

Transmission Electron Microscopy: Applications

Morphology
• The size, shape and arrangement of the particles which make
up the specimen as well as their relationship to each other on
the scale of atomic diameters.
Crystallographic Information
• The arrangement of atoms in the specimen and their degree of
order, detection of atomic-scale defects in areas a few
nanometers in diameter
• We will discuss this topic further during the crystallography
lecture
Compositional Information
• The elements and compounds the sample is composed of and
their relative ratios, in areas a few nanometers in diameter

Scanning Probe Microscopy (SPM)

SPM, also known as profilimetry
Are capable of resolving details of surfaces down to the atomic
level.

Types:
1- The scanning tunnelling microscope: (primary use is
measuring surface topography of samples).
Unlike Optical and electron micropropes SPM reveal details not
on the lateral x and y of a sample but also on the z axis
which is perpendicular to the surface.
Resolution:
SPMs is ≈ 20 a in the x and y direction bu for ideal samples
best resolution is 1 A. R in z direction is better than 1 A.
SEMs is about 50 A.

The scanning tunneling microscope
Capable of resolving features on an atomic scale on the surface of
conducting solid surface.
Main disadvantages:
The requirement that the surface being examined must conduct
electricity.
Principles:
The surface of the sample is scanned in a raster pattern by a very
fine metallic tip.
The tip is maintained at a constant distance d above the surface
throughout the scan.
The up and down motion of the tip then reflects the topology of the
surface.
In order to maintain the tip at constant distance from the sample
surface, a tunneling current between the tip and the sample is
monitored and held at a constant level.
The TC is generated by the voltage V that is applied between the tip
and sample.

A TC that passes through a medium that contains no electrons:
Examples of such media:
Vacuum, nonpolar liquid, or even an aqueous electrolyte solution.
Mechanism of current flow through an insulating medium:
Rationalized by quantum mechanics but will not be dealt here.
Tunneling currents become significant when conductors are within a
few nanometers of one another and when one of conductors is the
form of a sharp tip.
Scanning Tunneling current It is given approximately by:

It = Ve-cd
Where V is the bias voltage between the conductors, C is a constant
that is characteristic of conductor composition
D is the capacity between the lowest atom on the tip and the highest
atom on the sample.
In the tunneling microscope current is held constant by a feedback
mechanism tht moves the tip up and down so d remains constant.
Controlled by a piezoelectric transducer.

Scanning Tunnelling Microscopy (STM)
Rastering

Piezo actuators Z
DC
bias

X

control
electronics

computer

Y

display
tunnel
current
amp

Constant current imaging:
A feedback loop adjusts the separation
between tip and sample to maintain a
constant current. The voltages applied to
the piezo are translated into an image.
Image represents a convolution of
topography and electronic structure

1/8 in

Besocke-beetle style STM head
Slide courtesy of B. Mantooth and the Weiss Group at Penn State

Scanning Tunnelling Microscopy

Tunnelling current is caused by quantum
mechanical phenomena (confinement of an
electron to a “box” with finite walls)
The tunnelling current It is given by:

I t = Ve − Cd


Where:
V is the bias voltage
C is a constant based on the conducting
materials
d is the spacing between the atom at the tip
and the sample atom

Tips are prepared by cutting and
electrochemical etching – atomic scale
can be achieved because the tunnelling
current falls off exponentially with
increasing gap.

R. J. Hamers, “Scanned Probe Microscopies in Chemistry,” J. Phys. Chem., 1996, 100, 13103-13120.

The atomic Force Microscope

Invented in 1986.
The Atomic Force Microscope was developed to overcome a basic drawback
with STM - that it can only image conducting or semiconducting surfaces.
The AFM, however, has the advantage of imaging almost any type of
surface, including polymers, ceramics, composites, glass, and biological
samples.

Permits resolution of individual atoms on both conducting and insulating
surfaces.
Procedure:
A flexible force-sensing cantilever stylus is scanned in rastyer pattern over the
surface of the sample.
The force acting between the cantilever and the sample surface causes minute
deflections of the cantilever which are detected by optical means.
As in STM the motion of the tip or sometimes the sample is achieved with a
piezoelectric tube.
During a scan the force on the tip is held constant by the up and down motion
of the tip, which provides the topographic information.
Advantages:
It is applicable to nonconducting samples.

An atomically sharp tip is scanned over a surface with feedback mechanisms
that enable the piezo-electric scanners to maintain the tip at a constant
force (to obtain height information), or height (to obtain force information)
above the sample surface.

The AFM works by scanning a fine ceramic or semiconductor tip over a
surface much the same way as a phonograph needle scans a record (for
those of you that remember what a record player was!).

The tip is positioned at the end of a cantilever beam shaped.

As the tip is repelled by or attracted to the surface, the cantilever beam
deflects.

A diode laser is focused onto the back of a reflective cantilever.

As the tip scans the surface of the sample, moving up and down with the
contour of the surface, the laser beam is deflected off the attached
cantilever into a dual element photodiode.

The photodetector measures the difference in light intensities between the
upper and lower photodetectors, and then converts to voltage.

Feedback from the photodiode difference signal, through software control
from the computer, enables the tip to maintain either a constant force or
constant height above the sample. In the constant force mode the piezoelectric transducer monitors real time height deviation.

A plot of the laser deflection versus tip position on the sample surface
provides the resolution of the hills and valleys that constitute the
topography of the surface.

The AFM can work with the tip touching the sample (contact mode), or the
tip can tap across the surface (tapping mode) much like the cane of a blind
person.

The output from the photodiode then controls the force applied to tip so
that it remains constant.

The optical control is similar to tunneling-current control system in the
STM.

Measuring forces
Because the atomic force microscope relies on the forces between
the tip and sample, knowing these forces is important for proper
imaging. The force is not measured directly, but calculated by
measuring the deflection of the lever, and knowing the stiffness of
the cantilever. Hook’s law gives F = -kz, where F is the force, k is
the stiffness of the lever, and z is the distance the lever is bent.

AFM Modes of operation

The tip and cantilever



Performance of AFM depends on the physical charcteristics of the
cantilever and tip.
Early: cantilevers were cut from metal foil and tips were made
from crushed diamond particles.
The tip were glued manually to cantilevers.
Currently: this crude method replaced by semiconductor
production methods in which integral cantilever/tip assemblies are
produced by etching single chips of silicon, silicon oxides or silicon
nitride.
Small and delicate cantilever and tip are suggested.
Typically the cantilevers are a few micrometers in width and about
one micrometer in thickness.
The pyramid-or cone-shaped tips are a few micrometers in height
and width at the base.






Invented in 1986
Cantilever
Tip
Surface
Laser
Multi-segment photodetector

Figure 4. Three common types of AFM tip. (a) normal tip 
(3 µm tall); (b) supertip; (c) Ultralever (also 3 µm tall). 

Tapping mode operation
Disadvantages of the contact mode scanning:
The tip is in constant contact (mode) with the surfcae of the sample
and the downward force of the tip may not be low enough to
avoided damage to sample surface and distortion of image as
consequence (specially in soft materials biological samples,
polymers. or semi hard: silicon wafers).
Overcome by: Tapping mode operation:
a process in which the tip contacts the surface for only a brief time
periodically and then removed from the surface.
The cantilever is oscilated at frequency of a few hundred kilohertz.
The oscillation is driven by a constant driving force and the amplitude
is monitored continuously.
The cantilever is positioned so that the tip touches the surface only
at the bottom of each oscillation cycle. (variety materials images
that difficult to image by constant-contact mode).

Contact Mode
• High resolution
• Damage to sample
• Can measure frictional
forces

Non-Contact Mode
• Lower resolution
• No damage to sample

Tapping Mode
• Better resolution
• Minimal damage to
sample

Applications
Seeing surface structures with high resolution.
Examples:
Semiconductor field.
Silicon surfaces and their defects.
Magnetic domains on magnetic materials.
Biotechnology (DNA, chromatin, protein/enzyme interactions,
membrane viruses).
Advantages:
Permits imaging of biological samples under water without distortion

DNA image

2.5 x 2.5 nm simultaneous topographic and friction image of 
highly oriented pyrolytic graphic (HOPG). The bumps 
represent the topographic atomic corrugation, while the 
coloring reflects the lateral forces on the tip. The scan 
direction was right to left

Comparison of AFM and other imaging techniques

1. AFM versus STM:
It's interesting to compare AFM and its precursor -- Scanning Tunneling
Microscope. In some cases, the resolution of STM is better than AFM
because of the exponential dependence of the tunneling current on
distance. The force-distance dependence in AFM is much more complex
when characteristics such as tip shape and contact force are considered.
STM is generally applicable only to conducting samples while AFM is
applied to both conductors and insulators. In terms of versatility, needless
to say, the AFM wins. Furthermore, the AFM offers the advantage that the
writing voltage and tip-to-substrate spacing can be controlled
independently, whereas with STM the two parameters are integrally
linked.
2. AFM versus SEM:
Compared with Scanning Electron Microscope, AFM provides extraordinary
topographic contrast direct height measurements and unobscured views of
surface features (no coating is necessary).
3. AFM versus TEM:
Compared with Transmission Electron Microscopes, three dimensional AFM
images are obtained without expensive sample preparation and yield far
more complete information than the two dimensional profiles available
from cross-sectioned samples.
4. AFM versus Optical Microscope:
Compared with Optical Interferometric Microscope (optical profiles), the AFM
provides unambiguous measurement of step heights, independent of
reflectivity differences between materials.

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