Surface Sensitivity & Surface Specificity

The problems of sensitivity and detection limits are common to all forms of
spectroscopy. In its simplest form, the question of sensitivity boils down to
whether it is possible to detect the desired signal above the noise level.
In virtually all surface studies (especially those on single crystal substrates)
sensitivity is a major problem. Consider the case of a sample with a surface of
size 1 cm
2
- this will have ca. 10
15
atoms in the surface layer. In order to detect
the presence of impurity atoms present at the 1 % level, a technique must be
sensitive to ca. 10
13
atoms.
Contrast this with a spectroscopic technique used to analyze a 1 cm
3
bulk liquid
sample i.e. a sample of ca. 10
22
molecules. The detection of 10
13
molecules in
this sample would require 1 ppb (one part-per-billion) sensitivity - very few
techniques can provide anything like this level of sensitivity
This is one reason why common spectroscopic techniques such as NMR
(detection limit ca. 10
19
molecules) cannot be used for surface studies, except
on samples with very high surface areas.
Assuming that a technique of sufficient sensitivity can be found, another
major problem that needs to be addressed in surface spectroscopy is
distinguishing between signals from the surface and the bulk of the sample.
In principle, there are two ways around this problem :
To ensure that the surface signal is distinguishable (shifted) from the
comparable bulk signal, and that the detection system has sufficient dynamic
range to detect very small signals in the presence of neighboring large
signals.
To ensure that the bulk signal is small compared to the surface signal i.e. that
the vast majority of detected signal comes from the surface region of the
sample.
It is the latter approach which is used by the majority of surface spectroscopic
techniques - such techniques can then be said to be surface sensitive.
Classification as Scattering Techniques
Microscopy
STM (Scanning Tunneling Microscopy)
AFM (Atomic Force Microscopy)
SEM (Scanning Electron Microscopy)
TEM (Transmission Electron Microscopy)(bulk)
Absorption
NEXAFS (Near Edge X-ray Absorption Fine
Structure)- also called
XANES (X-ray Absorption Near Edge
Spectroscopy)
EXAFS (Extended X-ray Absorption Fine
Structure)(bulk)
Electron Spectroscopies
XPS (X-ray Photoelectron Spectroscopy)
UPS (Ultraviolet Photoelectron
Spectroscopy)
Auger
Diffraction
LEED (Low-Energy Electron Diffraction)
RHEED (Reflection High-Energy Electron
Diffraction)
XRD (X-Ray Diffraction)(bulk)
Desorption
TDS (Thermal Desorption Spectroscopy)
PSD (Photon Stimulated Desorption)
ESD (Electron Stimulated Desorption)
ESDIAD (Electron Stimulated Desorption
Ion Angular Detection)
Vibrational Spectroscopies
IR (Infra Red)
HREELS (High-Resolution Electron Energy
Loss Spectroscopy)
LEED is the principal technique for the determination of
surface structures : it may be used in one of two
ways:
Qualitatively : where the diffraction pattern is recorded
and analysis of the spot positions yields information
on the size, symmetry and rotational alignment of
the adsorbate unit cell with respect to the substrate
unit cell.
Quantitatively : where the intensities of the various
diffracted beams are recorded as a function of the
incident electron beam energy to generate so-called
I-V curves which, by comparison with theoretical
curves, may provide accurate information on atomic
positions.
Low Energy Electron Diffraction
The LEED experiment uses a beam of electrons of a well-defined low energy (typically
in the range 20 - 200 eV) incident normally on the sample. The sample itself must be a
single crystal with a well-ordered surface structure in order to generate a back-
scattered electron diffraction pattern. A typical experimental set-up is shown below.
Only the elastically-scattered electrons contribute to the diffraction pattern: the lower
energy (secondary) electrons are removed by energy-filtering grids placed in front of
the fluorescent screen that is employed to display the pattern.
Basic Theory of LEED
By the principles of wave-particle duality, the beam of electrons may be
equally regarded as a succession of electron waves incident normally
on the sample. These waves will be scattered by regions of high
localised electron density, i.e. the surface atoms, which can therefore
be considered to act as point scatterers.
The wavelength of the electrons is given be the de Broglie relation :
Wavelength, = h / p ( where p - electron momentum )
p = m.v = (2mE
k
)
1/2
= (2m.e.V)

where
m - mass of electron [ kg ]
v - velocity [ m s
-1
]
E
k
- kinetic energy
e - electronic charge
V - acceleration voltage
General Diffraction Ideas
Bragg Scattering vs. LEED Equation
X-ray Diffraction
Derive LEED equation using Braggs Lawfor X-ray diffraction, where
appropriate angles are substituted and is for the electron wavelength
elec
sin n D =
k
i
k
f
D
Angle
k
i
k
f
xray
2 sin n d =

d
d
Electron
Diffraction
If you consider the backscattering of a wavefront from two adjacent atoms at a well-
defined angle, , to the surface normal, then it is clear that there is a "path difference"
(d) in the distance the radiation has to travel from the scattering centers to a distant
detector (which is effectively at infinity) - this path difference is best illustrated by
considering two "ray paths" such as the right-hand pair of green traces in the above
diagram.
The size of this path difference is a sin and this must be equal to an integral
number of wavelengths for constructive interference to occur when the scattered
beams eventually meet and interfere at the detector i.e.
d = a sin = n.
where :
- wavelength
n - integer (..-1, 0, 1, 2,.. )
For two isolated scattering centers the diffracted intensity varies slowly
between zero (complete destructive interference ; d = (n + ) ) and its
maximum value (complete constructive interference ; d = n.) - with a large
periodic array of scatterers, however, the diffracted intensity is only
significant when the "Bragg condition"
a sin = n.
is satisfied exactly.
As an example we can look at the LEED pattern from an fcc(110) surface. In the
diagram below the surface atomic structure is shown on the left in plan view. The
primary electron beam would then be incident normally on this surface as if fired from
your current viewpoint and the diffracted beams would be scattered from the surface
back towards yourself. The diffraction pattern on the right illustrates how these
diffracted beams would impact upon the fluorescent screen.
The pattern shows the same rectangular symmetry as the substrate
surface but is "stretched" in the opposite sense to the real space
structure due to the reciprocal dependence upon the lattice parameter.
The pattern is also centrosymmetric about the (00) beam - this is the
central spot in the diffraction pattern corresponding to the beam that is
diffracted back exactly normal to the surface (i.e. the n = 0 case in our 1-
D model).
The above illustration of the diffraction pattern shows only the "first-order"
beams i.e. it is representative of the diffraction pattern visible at low
energies when only for n = 1 is the angle of diffraction, , sufficiently
small for the diffracted beam to be incident on the display screen.
The diagram below shows the diffraction pattern that might be expected if the
energy of the incident electrons is doubled - some of the second order spots
are now visible and the pattern as a whole has apparently contracted in
towards the central (00) spot.
LEED Patterns from Cu(110)
In the case of such simple LEED patterns, it is possible to explain the
diffraction pattern in terms of scattering from rows of atoms on the
surface. For example, the rows of atoms running vertically on the screen
would give rise to a set of diffracted beams in the horizontal plane,
perpendicular to the rows, thus leading to the row of spots running in a line
horizontally across the diffraction pattern through the (00) spot.
The further the rows are apart, then the closer in are the diffracted beams
to the central (00) beam. This is, however, a far from satisfactory method
of explaining LEED patterns from surfaces.
A much better method of looking at LEED diffraction patterns involves
using the concept of reciprocal space : more specifically , it can be readily
shown that
" The observed LEED pattern is a (scaled) representation of the
reciprocal net of the pseudo-2D surface structure "
Ewald Sphere Construction in 3-D
The reciprocal space lattice is a set of imaginary points constructed in
such a way that the direction of a vector from one point to another
coincides with the direction of a normal to the real space planes and
the separation of those points (absolute value of the vector) is equal to
the reciprocal of the real interplanar distance.
It is convenient to let the reciprocal lattice vector be 2 times the
reciprocal of the interplanar distance. This convention converts the
units from periods per unit length to radians per unit length. Radians
per centimeter (cm
-1
) are widely used units. It simplifies comparison of
different periodic phenomena. For instance k , the wavevector, has an
absolute value of 2/ If we choose the above convention, we are able
to compare the two values directly. Henceforth this convention will be
used. All it does is expand the size of the reciprocal lattice.
How can one construct a reciprocal lattice from
a direct one?
Pick some point as an origin, then:
a) from this origin, lay out the normal to every
family of parallel planes in the direct lattice;
b) set the length of each normal equal to 2 times
the reciprocal of the interplanar spacing for its
particular set of planes;
c) place a point at the end of each normal.
Real vs. (Reciprocal, Diffraction, or k) Space
k-Space (i.e. spacing of diffraction spots in nm
1
)
Real Space (i.e. spacing of surface atoms in nm)
larger real-space smaller k-space
2
G
a

=
a
Ewald Sphere Construction in 2-D
Ewald Sphere Construction for LEED
The reciprocal net is determined by (defined by) the reciprocal vectors :
a
1
* & a
2
* (for the substrate) and b
1
* & b
2
* (for the adsorbate)
Initially we will consider just the substrate. The reciprocal vectors are
related to the real space unit cell vectors by the scalar product relations:
a
1
. a
2
* = a
1
* . a
2
= 0
and
a
1
. a
1
* = a
2
. a
2
* = 1
a
1
is perpendicular to a
2
* , and a
2
is perpendicular to a
1
*
there is an inverse relationship between the lengths of a
1
and a
1
* (and
a
2
and a
2
* ) of the form :
| a
1
| = 1 / ( | a
1
*| cos A )
where A is the angle between the vectors a
1
and a
1
*.
Note : when A = 0 degrees (cos A = 1) this simplifies to a simple
reciprocal relationship between the lengths a
1
and a
1
*.
Exactly analogous relations hold for the real space and reciprocal
vectors of the adsorbate overlayer structure : b
1
, b
1
* , b
2
and b
2
* .
To a first approximation, the LEED pattern for a given surface structure
may be obtained by superimposing the reciprocal net of the adsorbate
overlayer (generated from b
1
* and b
2
* ) on the reciprocal net of the
substrate (generated from a
1
* and a
2
* )
The diagram below shows an fcc(100) surface (again in plan view)
and its corresponding diffraction pattern (i.e. the reciprocal net) .
We can demonstrate how these reciprocal vectors can be determined by working
through the problem in a parallel fashion for the two vectors :
a
1
* must be perpendicular to
a
2
a
2
* must be
perpendicular to a
1
a
1
* is parallel to a
1
a
2
* is parallel to a
2

The angle, A , between a

1
& a
1
*
is zero
The angle, A ,
between a
2
& a
2
* is
zero
Hence, | a
1
*| = 1 / | a
1
| Hence, | a
2
*| = 1 / | a
2
|

If we let | a
1
| = 1 unit, then |
a
1
*| = 1 unit.
| a
2
| = | a
1
| = 1 unit,
therefore | a
2
*| = 1
unit.
Let us now add in an adsorbate overlayer - a primitive ( 2 x 2 ) structure with the
adsorbed species shown bonded in on-top sites - and apply the same logic as just
used above to determine the reciprocal vectors, b
1
* and b
2
*, for this overlayer.
All we have to do now is to generate the reciprocal net for the adsorbate
using b
1
* and b
2
* (shown in red).
We can demonstrate how these reciprocal vectors can be determined by working
through the problem in a parallel fashion for the two vectors :
b
1
* must be perpendicular to
b
2
b
2
* must be perpendicular to
b
1
b
1
* is parallel to b
1
b
2
* is parallel to b
2

The angle, B , between b

1
& b
1
*
is zero
The angle, B , between b
2
&
b
2
* is zero
Hence, | b
1
*| = 1 / | b
1
| Hence, | b
2
*| = 1 / | b
2
|

| b
1
| = 2| a
1
| = 2 units;
| b
1
*| = unit.
b
2
| = 2| a
2
| = 2 units;
| b
2
*| = unit.
Lets look at the c( 2 x 2 ) structure on the same fcc(100) surface.
The diagram below shows both a real space c( 2 x 2 ) structure and
the corresponding diffraction pattern:
In many respects the analysis is very similar to that for the p( 2 x 2 ) structure, except
that:
| b
1
| = | b
2
| = 2 units
consequently
| b
1
*| = | b
2
*| = 1/ 2 units.
The vectors for the adsorbate overlayer are rotated with respect to those of the
substrate by 45. Note that the c( 2 x 2 ) diffraction pattern can also be obtained from
the pattern for the primitive structure by "missing out every alternate adsorbate-derived
diffraction spot". This is a common feature of diffraction patterns arising from centered
structures.
k-Space: Square Lattice Reconstructions
Real space
LEED
LEED: Si(111)7x7
35 eV 65 eV
Larger D spacings give closer
LEED spots (smaller ).
Higher energy electrons give
closer spots.
Bulk 1x
spacing
Surface 7x
spacing
sin n D =
Real Space:
Si surface atoms
7bulk spacing
Reflection High Energy Electron Diffraction (RHEED)
Low Energy Electron Diffraction (LEED) utilizes the
inherent surface sensitivity associated with low energy
electrons in order to sample the surface structure. As the
primary electron energy is increased not only does the
surface specificity decrease but two other effects are
particularly noticeable:

forward scattering becomes much more important (as

opposed to the backward scattering observed in LEED)
the scattering angle (measured from the incident beam
direction) tends towards 180 degrees for back-scattering
and 0 degrees for forward scattering.
In order to extract surface structural information from the diffraction of high
energy electrons, therefore, the technique has to be adapted and the
easiest way of doing this is to use a reflection geometry in which the
electron beam is incident at a very grazing angle - it is then known as
Reflection High Energy Electron Diffraction (RHEED).
The diagram above shows the basic set-up for a RHEED experiment, with
the sample viewed edge-on. In practice the display screen is usually a
phosphor coating on the inside of a vacuum window (viewport) and the
diffraction pattern can be viewed and recorded from the atmospheric side
of the window.
The small scattering angles involved are compensated for by using
relatively large sample/screen distances.
The sample can be rotated about its normal axis so that the electron beam
is incident along specific crystallographic directions on the surface.
In order to understand the diffraction process we need to consider how the
electron beam can interact with the regular array of surface atoms in this
experimental geometry. It is worth noting, however, that the use of glancing
incidence ensures that, despite the high energy of the electrons, the
component of the electron momentum perpendicular to the surface is
small. Under these conditions an electron may travel a substantial distance
through the solid (in accord with the much longer mean free path of such
high energy electrons) without penetrating far into the solid. The technique,
consequently, remains surface sensitive.
What, if any, advantages does RHEED offer over
LEED ?
In terms of the quality of the diffraction pattern absolutely none ! - moreover,
diffraction patterns have to be observed for at least two sample alignments
with respect to the incident beam in order to determine the surface unit cell.
However , ....
The geometry of the experiment allows much better access to the sample
during observation of the diffraction pattern. This is particularly important if it
is desired to make observations of the surface structure during growth of a
surface film by evaporation from sources located normal to the sample
surface or simultaneous with other measurements (e.g. AES, XPS).
Experiments have shown that it is possible to monitor the atomic layer-by-
atomic layer growth of epitaxial films by monitoring oscillations in the
intensity of the diffracted beams in the RHEED pattern.
By using RHEED it is therefore possible to measure, and hence also to
control, atomic layer growth rates in Molecular Beam Epitaxy (MBE) growth
of electronic device structures - this is by far and away the most important
application of the technique.