Professional Documents
Culture Documents
1- Heterogeneous Catalysis.
2- Semiconductor thin film technology.
3- Corrosion and adhesion mechanisms
4- Activity of metal surfaces.
5- 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
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+* + e-
Where 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 x-
ray 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
O CH2 C O C2H5
O Si N + H2N(CH2)2NH2
CH2 C O C2 H 5 Reflux/
O
Toluene - C2H5OH
O
O
O CH2 C NH NH2
O Si N
O CH2 C NH NH2
O
XPS Results
System Element C Si O N
C1s Si2p O1s N1s
Precursor Core-line
285 102 532 399.5
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
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= Note: Resolution
m is limited by lens
aberrations!
h m h
λ= =
m 2eV 2meV
6.63 ×10 −34 J s
λ=
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
h m h
previous equation: λ= =
m 2eV 2meV (1 + 2eV
mc 2
)
6.63 ×10 −34 J s
λ=
(1.60×10 -19 C)(10 4 V )
2(9.11×10 kg )(1.60 ×10 C)(10 V)(1 +
-31 -19 4
2 ( 9.11×10 -31 kg) ( 3×108 m / s ) 2
)
λ = 3.7 ×10 −3 nm
Unscattered Electrons
Incident electrons which are
transmitted through the thin
specimen without any interaction
occurring inside the specimen.
Electron
gun Computer
(1-30 keV)
Magnetic
lenses and
scanning Detectors
coils
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 The results:
- Electrons are emitted from
Electrons are forced toward the column axis
a nearly perfect point
by the Wehnelt cap
source (the space
Electrons collect in the space between the charge)
filament tip and Wehnelt cap (a space - The electrons all have
charge or “pool”) similar energies
Those electrons at the bottom of the space (monchromatic)
charge (nearest to the anode) can exit the - The electrons will travel
gun area through the small (<1 mm) hole parallel to the column
in the Wehnelt cap axis
These electrons then move down the
column towards the EM lens and scanning
systems
Electron Optics: Focusing and Scanning
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
amp
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 piezo-
electric 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.
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