S CANNING T UNNELLING M ICROSCOPE
NAUMAN MITHANI Student ID: 301016320
Performed: 10th November 2009 Submitted: 24th November 2009
ABSTRACT
The surface analytical instrument of Scanning Tunnelling Microscope (STM) was employed to measure certain
physical dimensions of a gold-coated, single-period holographic grating with sinusoidal spacing. The average distance
between two grooves was calculated to be 1,639 ± 155 (!9.4%) Å from which the sample was determined to bear 610
± 57 (!9.4%) grooves/mm; the thickness of the sample was determined to be 451 ± 1 (!1.6%) nm. The relative error
margins pertaining to the final values presented are low and thus the experimental results may be considered
satisfactory and valid.
PURPOSE:
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An introduction to scanning tunnelling microscopy as an analytical tool in surface science: analysis of a
holographic gold grating to determine its physical dimensions.
1. INTRODUCTION
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The underlying principle:
A “Scanning Tunnelling Microscope” functions principally by utilising the phenomenon of quantum mechanical
tunnelling. In over-simplified terms, this is the ‘appearance’ or ‘occurrence’ of electrons from one metal to another
when the two metals are a few atomic diameters apart (the metals are separated by an electric insulator e.g. air or
vacuum) [ref. 1, 4].
Simplified reasoning: Metals have a low electrical resistance due to the small energy gaps between valence
molecular orbitals and the conduction band of the unoccupied states (a continuous distribution of electronic levels
for the transportation of electrons) [ref. 1].
As per quantum mechanics, an electron bears the properties and behaviour of both, a particle and a wave. It may
be considered to behave as a ‘soft’ cloud rather than a ‘hard’ particle that is rebounding off the boundary of the barrier
between two metals. The size of the cloud is related to the wavelength of the electrons (on the order of Ångstroms). If
the barrier is large (in terms of energy required) or thick then the electron is repelled off the boundary of the barrier;
however, if it is sufficiently thin then the electron cloud may cross over through the barrier and appear on the other
side (the other metal). This is the phenomenon of quantum mechanical tunnelling; the electron does not possess
sufficient (kinetic) energy to travel over the barrier.
Figure 1: An illustration of the energy barrier and tunnelling.
The (spatial variations of the) electron density of the highest occupied levels of the conduction band are measured
by the STM. These electrons, which are closest to the Fermi level, have the lowest barrier and can undergo tunnelling
to the unoccupied states. Gold’s conduction band is comprised of the 6s5d (6s15d10) valence orbitals. In other words,
the STM images the spatial modulation in the electron density associated with these band states [ref. 1].
Figure 2: An illustration of the energy levels of the 6s and 5d orbitals of Au.
Overview of the STM’s function
In a conventional STM, a voltage (called the bias voltage) is applied between the tip of the metal probe and the
sample in question; this leads to the flow of the tunnelling current. It is the direct or indirect control and monitoring
of this tunnelling current that allows for the reading/imaging of the sample surface. NOTE: If the probe (tip) has been
sharpened to only one atom then an STM can be used to obtain atomic resolution readings/imaging.
Figure 3: An illustration of a one atom tip.
The probe of the STM is maintained at a separation distance of 4 to 7Å, which is the median equilibrium position
between the ranges of attractive (3 to 10Å) and repulsive interactions (less than 3Å) [ref. 3].
Figure 4: This graph shows the plot of the current flowing through the
battery as a function of the separation of the metals. [a] shows an exponential
increase in current as the metals get closer; [b] in the absence of quantum
mechanical tunnelling, no current flows until the metals touch.
Modes of operation of the STM
The STM may be operated in one of two modes: “constant current” OR “constant height”. The mode used in the
experiment was the constant current mode - the probe scans the surface with a fixed/constant tunnelling current. This
constant current is maintained by continuous changes in the feedback voltage which adjust the height of the probe
corresponding to the changes in the topography of the sample. Thus a profile of the surface height, z(x,y)
corresponding to a constant current is obtained as the probe moves across the x-y plane of the sample [ref. 3, 4]. The
results of each run is presented as an image.
A benefit of this mode is it can be employed to analyse surfaces which are not relatively flat, as the height of the
various features can be correlated to the changes in the feedback voltage [ref. 3, 4]. The constant current mode is,
however, slower of the two since more time is needed for the internal mechanism of the STM to adjust for the changes
in height than the voltage response in ‘constant height mode’ . This gives rise to other risks: there is greater chance of
image distortion due to piezoelectric creeps, hysteresis, thermal drifts and skipping of the probe tip due to physical
disturbances (akin to the skipping of a phonograph’s tip) [ref. 4]. A comparative advantage is the non-requirement of the
determination of the square root of the work function in order to calibrate z in ‘constant height mode’ [ref. 4].
Choice of the sample and sample material:
The metal, gold (Au), is exceedingly inert at r.t.p. and hence is highly suited. The sample analysed is a gold coated
single period holographic grating with sinusoidal spacing.
2. EXPERIMENTAL PROCEDURE
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The experimental procedure was conducted according to the steps outlined in the burleigh manual [ref. 1] with
alterations stated in the Chem 366 lab manual [ref. 2]. A partial diagram of a conventional apparatus is shown below:
Figure 5: The ISTM head and its components: the tip, fixed in a tip carriage, which is magnetically held in place by the tip mount;
the SEM sample holder, which is plugged into the sample carriage and held magnetically in place on the same mount.
Relevant experimental parameters are provided below:
bias voltage: 1.02 ± 0.01 (! 0.98%) V
tunnelling current: 8.2 ± 0.3 (! 3.6%) nA
3. DATA ANALYSIS
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♦ 3.1: Calculation of uncertainties
if y = f (x1 , x2 , ..., xn )
and the only operators between x and y are ' ! ' and/or ' ÷ ' {eq. 1}
2 2 2
# "x & # "x & # "x &
"y = y % 1 ( + % 2 ( + ... + % n (
$ x1 ' $ x2 ' $ xn '
otherwise :
2 2 2
$ "y ' $ "y ' $ "y ' {eq. 2}
!y = & # !x1 ) + & # !x2 ) + ... + & # !xn )
% "x1 ( % "x2 ( % "xn (
!if y = f ( x )
i.e. when the output is dependant on a single variable
then
"y "x {eq. 3}
=
y x
In the case of an average, where each entry (component) has an associated uncertainty
weight, w ! 1 " i2 ( )
and
n
# (x i / " i2 )
x= i=1
,
n
{eq. 4}
# (1 / " 2
i )
i=1
the uncertainty in the weighted average would, therefore, be:-
1
"x = {eq. 5}
#( )
n
1 " i2
i=1
♦ 3.2: Lines/mm & depth of grooves
• Scanning area: 76,000 × 76,000 Å
x (Å) Δx (Å) = xi - xi-1 z (Å)
peak 1 2,926 - 4,362
peak 2 19,019 16,093 5,806
peak 3 35,112 16,093 -
peak 4 53,400 18,288 6,372
peak 5 68,029 14,629 6,874
peak 6 82,659 14,630 7,126
average irrelevant 15,363 ± 1,078 (! 6.8%) 6,108 ± 983 (! 16.1%)
Table 1: Data from the STM scan of an area of the sample of 76,000 × 76,000 Å scanning range. x (Å) represents the distance of the
surface feature (peak) from the starting point of the scan, Δx (Å) represents the distance between the two surface features, z (Å)
represents the height of the surface feature. Peak 3 is greyed since it was not explicitly visible. The uncertainties in the averages are
standard deviations.
NOTE: The numbers derived here from the output at the scanning range of 76,000 × 76,000 Å serve also as the most
reliable data since it is at this scanning range that presence, absence, distance and height of the features are best
resolved. Therefore, these numbers are used as reference for comparison with other data obtained under other
scanning ranges.
• Scanning area: 50,000 × 50,000 Å
x (Å) Δx (Å) = xi - xi-1 z (Å)
peak 1 2,220 4,133
peak 2 38,850 36,630 5,189
average irrelevant 18,315* 4,661 ± 528 (! 11.3%)
Table 2: Data from the STM scan of an area of the sample of 50,000 × 50,000 Å scanning range. x (Å) represents the distance of the
surface feature (peak) from the starting point of the scan, Δx (Å) is the distance between the two surface features, z (Å) represents
the height of the surface feature. * It is known from the output at 76,000 × 76,000 Å that the region of 2,220 < x (Å) < 38,850
covers three peaks but only two have shown up " average Δx has been calculated as follows: average Δx = (38,850 - 2,220)/2.
• Scanning area: 30,000 × 30,000 Å
x (Å) Δx (Å) = xi - xi-1 z (Å)
peak 1 725 4,550
peak 2 16,670 15,945 4,601
peak 3 34,428 17,758 4,424
average irrelevant 16,851 ± 906 (! 5.4%) 4,525 ± 74 (! 1.6%)
Table 3: Data from the STM scan of an area of the sample of 30,000 × 30,000 Å scanning range. x (Å) represents the distance of the
surface feature (peak) from the starting point of the scan, Δx (Å) represents the distance between the two surface features, z (Å)
represents the height of the surface feature. The uncertainties in the averages are standard deviations.
• Scanning area: 20,000 × 20,000 Å
x (Å) Δx (Å) = xi - xi-1 z (Å)
peak 1 1,449 3,052
peak 2 16,187 14,738 3,895
average irrelevant 14,738 3,473 ± 421 (! 12.1%)
Table 4: Data from the STM scan of an area of the sample of 20,000 × 20,000 Å scanning range. x (Å) represents the distance of the
surface feature (peak) from the starting point of the scan, Δx (Å) represents the distance between the two surface features, z (Å)
represents the height of the surface feature. Peak 3 is greyed since it was not explicitly visible. The uncertainties in the averages are
standard deviations.
NOTE: The outputs under the scanning ranges of 10,000 × 10,000 Å and 5,000 × 5,000 Å are ignored since distinct
features are no longer discernible. Each peak region under scan shows topographic details, not distinct peaks and
grooves.
• Overall summary
scanning range (Å) average Δx (Å) average z (Å)
76,000 × 76,000 15,363 ± 1078 (! 6.8%) 6,108 ± 983 (! 16.1%)
50,000 × 50,000 18,315 4,661 ± 528 (! 11.3%)
30,000 × 30,000 16,851 ± 906 (! 5.4%) 4,525 ± 74 (! 1.6%)
20,000 × 20,000 14,738 3,473 ± 421 (! 12.1%)
overall 16,385 ± 1,550 (! 9.4%) 4,505 ± 76 (! 1.6%)
Table 5: Tabulated overall of overall averages. Since some the Δx values do not have an associated uncertainty, a regular average and
standard deviation is cited; a weighted average is used for z.
• z (Å) may interpreted alternatively as the depth of the grooves that were created in the surface rather than the
height of the peaks.
overall distance between grooves: Δx = 16,385 Å/grooves (± 9.4%) ! 1.6385 × 10 -3 mm /grooves
" grooves OR lines/mm: 1/(1.6385 × 10-3 mm/grooves) = 610 grooves/mm ± 9.4%
610 ± 57 (!9.4%) grooves/mm.
4. DISCUSSION
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(1) Ohmic resistance:
calculation of respective uncertainty:
2 2 2
" !x % " !x % " !x %
V as per eq.1 : !y = y $ 1 ' + $ 2 ' + ... + $ n '
V = IR ! R= # x1 & # x2 & # xn &
I
2 2
where : " !V % " !I %
( !R = R $ +
V = 1.02 ± 0.01V # V '& $# I '&
I = 8.2 ± 0.3 nA
2
" 0.01 % " 0.3 ) 10 %
2 +9
!R = 1.243 ) 10 8 * $ ' +$
!R =
1.02
= 1.243 " 10 8 $ # 1.02 & # 8.2 ) 10 +9 '&
8.2 " 10 #9
!R = 0.004 ) 10 8 ,
" R = (1.243 ± 0.004)×10 8 Ω
If the tip touches the surface then there is no longer a (tunnelling) gap. If the gold layer on the sample is
assumed to be 4,505 Å (450.5 × 10-9 m) thick (and area is ignored) and has a linear sensitivity (ρlinear) of ~1×10-6 Ω/m
then:
R = ρlinear · distance
= 1×10-6 Ω/m · 450.5×10 -9 m
= 4.505 × 10-13 Ω, (~21 orders of magnitude lower)
Naturally, since air, an electric insulator, was the medium in between the tungsten tip and the gold surface, the
tunnelling gap resistance was very high. In other words, the barrier between the two metals was too high for the
electrons to overcome by flowing in the form of a classical current, hence tunnelling occurred. There would be no
appreciable tunnelling once the metals would touch as there would no longer be an insulator barrier and the electrons
would flow like a classical current. The resulting current, I, would be:
V 1.02V
I= ! I= = 2.26 " 1012 A , ~21 orders of magnitude higher than the tunnelling current of 8.2 × 10 -9 A.
R 4.505 " 10 #13 $
(2) Ohmic resistance and temperature:
An increase in temperature (T) translates into an increase in the kinetic energy of the constituent atoms;
consequently, the frequency and amplitude of the random (thermal) vibrational motion and interatomic2 collision
amongst the atoms increases. The atoms may be considered physical obstacles for electron flow, and increased
mobility of the atoms will only impede the electrons more as the probability of an electron encountering an atom is
higher. In other words, R, ρ, and T are directly proportional. If the voltage is constant, a rise in T will cause a rise in R
and thus cause a drop in the current.
In the case of a tunnelling current, it is the wave-like nature of an electron, the lower electric potential of a metal
and the thickness of the separating barrier (or separation distance) that drives a tunnelling current. Since an increase in
T would cause a further increase in the resistance of the barrier (assuming it is not a vacuum) and the metals, it would
favour more electrons towards the tunnelling ‘route’; secondly, a higher T would lend more effective kinetic energy to
the electrons thereby raising the probability of successful tunnelling.
(3) Quantification of the no. of electrons... :
... using the formula:
charge (Q )
cuurent ( I ) =
time ( t )
where :
I = 8.2 nA ! 8.2 " 10 #9 C / s
Qe = charge of an electron = 1.602 " 10 #19 C
I 8.2 " 10 #9 C s
= = 5.118 " 1010 electrons s
Qe 1.602 " 10 #19 C
electron
" no. of electrons flowing per second ≈ 5.1 × 10 10
if the area scanning area of the 76,000 × 76,000 Å (! 7,600 × 7,600 nm) is considered then:
total area scanned = 5.776 × 107 nm2,
area of a gold atom: π·r2,
where:
r(Au) = 0.144 nm
" area = π·(0.144 nm)2 = 0.0651 nm2
5.776 ! 10 7 nm 2
" no. of Au atoms in the specified scanning range: 2
= 8.866 ! 10 8 Au atoms
0.0651 nm Au atom
5.118 ! 1010 electrons
" ratio of electrons:Au atoms: = 57.72 " 58
8.866 ! 10 8 Au atoms
If the tunnelling current and the corresponding ratio of electrons flowing per Au atoms scanned (only ~58) suggest
that the tunnelling process is quite sensitive and undemanding in terms of energy or input requirements.
...
(4) Tunnelling current and tunnelling transmission coefficient, T(E):
T ( E ) ! e" L 2 m# /! 2
where :
L: tunneling gap
m: mass of an electron
#: work function
!: Planck constant
T ( E ) : frequency of tunnelling electrons
if the following values are substituted: ϕ = 5×10 -19 J, m = 9×10 -31 kg and L has units of Å; and the equation is
derived further as per the burleigh manual [ref. 1] then:
T(E) = e-2L
d T (E)
= !2e!2 L
dL
!
"if dL = 0.1 A
then
d T (E)
d T ( E ) = 0.1# = ! 0.2e!2 L
dL
$ ! 0.2 %T ( E )
As shown, a change of 10% in L (0.1Å) will cause a change of 20% in tunnelling frequency of electrons, T(E), thus a
20% change in the current, I. The technique may therefore be considered quite sensitive since the resultant change in I
is twice the change in L.
(5) Potential environmental interference:
The STM scans were conducted in open air which is acceptable for the level and complexity of the intended work,
since air is a reasonably strong electric insulator.
In other scenarios, where the would be a presence of water, would cause no interference since the distance
between the tip and sample is a on the scale of a few atoms. There is not enough room for multiple water molecules to
come between the tip and sample and act as a conductor and cause the current to leak out into the environment.
The sample, though, ought to be inert to water (and dissolved oxygen). If the sample is not inert to its
environment and e.g. suffers corrosion or adsorption then the STM scanning would be impeded. The surface under
scan would no longer be that of the sample but some other material (e.g. Fe corroding to FeO) with different
properties and arrangement of its crystal lattice structure. Formation of an insulating surface oxide layer or adsorption
of other substances would only serve to cause an unplanned and unaccounted for changes in the sample and
subsequent imaging. Buildup of other substances e.g. surface oxide layer or adsorbates could increase the tunnelling
gap between the tip and the actual metal’s atoms.
If the adsorbed substance is electrically sensitive and a tunnelling current still flows then the tunnelling process
could indeed alter its distribution.
Effectively, environmental interference (unplanned and unaccounted for) could diminish the useful resolution/
imaging of the STM scans or halt the tunnelling process altogether.
(6) Applications of STM:
STM may be used in virtually any surface science research and application e.g. semi-conductors and
microelectronics in physics-based engineering & (surface) catalysis in chemistry research. Through tip-sample
interactions, the STM may be used to manipulate atoms and molecules thus allowing for creation of synthetic
molecular-scale devices and objects.
The STM is unique in the level of resolution it provides and its versatility in analysis: in-situ electrochemical
studies, effects of adsorbates, etc.
It is not possible to directly obtain the same information the STM may provide (or at equal resolution). Several
techniques can provide similar information:
• LEED: Low Energy Electron Diffraction
This and X-ray diffraction techniques require large-scale order, and can only provide averaged information about the
local and defect structure [ref. 4].
• SEM: Scanning Electron Microscopy
Its resolution in not high enough to provide atomic-scale information. Moreover, there are numerous logistical,
experimental and operational constrictions.
• TEM: Transmission Electron Microscopy
In certain situations, it may provide atomic-scale resolution but requires special sample preparation: the sample must
be specially thinned [ref. 4].
5. CONCLUSION
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The gold-coated holographic grating was determined to have 610 ± 57 (!9.4%) grooves/mm, and an average
thickness of 450.5 ± 0.8 (!1.6%) nm. The relatively low error margins in the final values presented suggest that the
values are valid and satisfactory.
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6. REFERENCES:
[ref. 1]: Miller, R.J.D., Mizes, H.A., Samsavar, A.; Instructional Scanning Tunnelling Microscope; Burleigh Instruments;
1992
[ref. 2]: T. Johanssion, J.-C. Brodovitch; Chemistry 366W-3 Physical Chemistry Laboratory; August 2009 edition; pg
III-1 to III-3; SFU Cornerstone, Greater Vancouver, 2009
[ref. 3]: Scanning tunneling microscope; Wikipedia, The Free Encyclopaedia; Nov. 2009 <http://en.wikipedia.org/w/
index.php?title=Scanning_tunneling_microscope&oldid=323647234>
[ref. 4]: Bai C.; Scanning Tunneling Microscopy and Its Application; Springer Series in Surface Sciences; 2nd ed.; Springer;
2000.
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