Report

on

Use of STM in Microscopy and Manipulation

INTRODUCTION

Not long ago it caused a great debate whether we could “see” let alone “manipulate” an
atom. However, this debate was resolved by the invention of the STM (Scanning Tunneling
Microscope) by G. Binnig and W. Rohrer at the IBM Research Laboratory in 1982, as it was used
in viewing surfaces at atomic level. That’s why it was honoured by the Noble Prize in 1986.

The operation of STM is based on the quantum mechanical phenomenon “Tunneling”. It

basically consists of a “tip” which when becomes within 1 nm (10-9 m) from material surface
“sample” voltage is applied between them the electrons can tunnel between the tip and the
sample.

It was later noticed that the tip can cause changes in the material surface due to
interaction between the tip and the sample. The scientists researched these changes in hope to be
able to manipulate the matter at the atomic level. When they succeeded it was the start point of
“Nanotechnology”, now the STM could be used as a “Nano manipulator” and used to build Nano
materials atom by atom, more research brought up the idea of Nano assemblers (very small
manipulating tools) and Nano robots which made “Nanotechnology” one of the most interesting
and promising research fields.

As we said, it all started by the introduction of the STM. In this report we will study the
STM going through three sections:
➢ A brief account on STM and its working principle.
➢ The use of STM in Microscopy.
➢ The use of STM in Manipulation.

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1.0 HOW STM WORKS:

STM is one of the SPM (Scanning Probe Microscope) family which uses probes to see
atoms and molecules at surfaces (It also includes AFM (Atomic Force Microscope), SNOM
(Scanning Near-field Optical Microscope), and MFM (Magnetic Force Microscope) ). Each
member of this family has its working principle, as for STM it is based on the concept
of “quantum tunneling”. STM probes the density of states of a material using tunneling current.

Quantum Tunneling:

Consider a 1-D vacuum barrier

between two electrodes (the tip and the
sampler). Assume the both have the
same work function Ф (work function is
the minimum energy (usually measured
in electron volts) needed to remove
an electron from a solid to a point
immediately outside the solid surface).

Assume Ψ is the wave function,

Ef is Fermi level , E is the energy of the
electron, I is the tunneling current, ρ is
the density of states function, and M is
thetunneling matrix element.

Figure 1. A one dimensional barrier between two

metal electrodes. A bias voltage of V is applied
between the electrodes.

If Ф < E → k is imaginary → Ψ propagates

If Ф> E → k is real → Ψ is attenuated (look Figure 1)
The probability of finding an electron behind the barrier of the width d is

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I is proportional to the probability of finding an electron

I=const.e-22mФђd (*)

A more detailed expression of I was derived by Bardeen

Note: since

(***)

2.0 USE OF STM IN MICROSCOPY:

From (*) it is obvious that the tunneling current (I) is related to distance between tip and
sample (d), that means that we can deduce d from I (measured in nA).

Figure 2. relation between tunneling current (I) and distance (d)

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2.1 Components of STM :

The electronic circuit is shown in Figure 3

Figure 3. Schematic view of an STM

Probe:
It is very important that the tip is
sharp for good accuracy(Look Figure 4);
Tips typically are made out of tungsten,
platinum or a Pt-Ir wire.A sharp tip can be
produced by:
Figure 4. Sharp and blunt tips
• Cutting and grinding
• Electrochemical etching

Amplifier:
It amplifies the tunneling current.

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Feedback (distance control) unit:
Figure 5. Feedback system
To prevent that the surface to crash into
the tip, the distance between the tip and surface
is kept constant during the measurement, The
feedback system determines continuously the
height of the needle by measuring the current
between tip and sample. When this current is to
large or to small the distance has to be adjusted.
The feedback system readjust the distance in such a way that the current gets the right value by
moving the tip up or down(Look Figure 5).
Piezoelectric material:
Piezo-material has the property to expand or shrink a little bit when a voltage is applied
to it. For example the application of 5 V to a 5 mm cube of piezo-material gives an expansion of
about 0.5 nm, it is controlled by feedback unit and the tip is attached to it.

2.2 Modes of operation:

2.2.1 Constant Current Mode

By using the feedback loop the tip is vertically adjusted in such a way that the current
always stays constant. As the current is proportional to the distance to tip, the tip follows a contour
parallel to the surface during scanning. The image of the surface is generated by recording the
vertical position of the tip (Look in Figure 6).

2.2.2 Constant Height Mode

The feedback loop isn’t used, the tip is
at constant height, The image of the surface is
generated by recording the tunneling current. It
is only suitable for smooth surfaces (to avoid
Constant Height Constant Current
tip crash). Mode Mode

Figure 6. Constant Height Mode Vs. Constant

Current Mode

2.2.3 Scanning Tunneling Spectroscopy

From differentiation of (***) we can dedicate that

The density of states can be deduced by changing bias voltage (V) and calculating tunneling
current (I).

2.2.4 Local Work Function Measurement

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If there is an inhomogeneous compound in the surface the work function will be inhomogeneous
as well. This alters the local barrier height. By using the constant height or constant current
modes described above we would get a virtual hole, so we need to measure Ф . From (*) we can
dedicate that

Thus the work function can directly be measured by varying the tip-sample distance.

Figure 7. Examples of surfaces scanned by STM (left: Silicon

carbide , T=300k, middle: Au(111), right: Bucky ball C60 at 5K)

3.0 USE OF STM IN MANIPULATION:

As discussed above, STM is very powerful in studying atomic structure and electronic
properties of surfaces (imaging mode). In these studies, the tip-sample interaction is usually kept
as small as possible so that the investigations don’t cause undesired changes. However, if one
adjusts the parameters to increase the tip-sample interaction in a controlled way, STM can also be
used to fabricate Nano-structures down to the atomic level. Various Nano -structures can be
constructed by different methods, including manipulation of single atoms, scratching, oxidation,
tip-induced chemical reactions, and heating, etc.

3.1 Manipulation of Single Atoms:

The first example of Manipulation was

demonstrated by Eigler and Schweizer in 1990 by
writing the “IBM” company logo with Xe atoms on a
Ni(110) surface (the smallest logo) in the world in
1990 and pioneered the new field of manipulation of
single atoms .

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 Figure 8. the smallest logo in the world

Manipulation of single atoms and

molecules with a STM tip generally requires
atomically clean surfaces and an extreme stability
at the tip-sample junction. Therefore, ultra-high-
vacuum (UHV) environments and low substrate
temperatures are favored in most manipulation
experiments. Figure 9 shows some of possible
interactions between molecule/atom and STM tip.

Figure 9. Interactions between molecule/atom

and STM tip

3.1.1 Lateral Manipulation:

A typical Lateral Manipulation
procedure involves three steps: 1) vertically
approaching the tip towards the manipulated
atom to increase the tip-atom interaction, 2)
scanning the tip parallel to the surface where the
atom moves under the influence of the tip, and
3) retracting the tip back to the normal image-
height thereby the atom is left at the final
location on the surface(Look Figure 10).
Figure 10. Lateral Manipulation

Three basic Lateral Manipulation modes, “pushing”, “pulling” and “sliding”, has been
distinguished. In the “pulling” mode, the atom follows the tip due to an attractive tip-atom
interaction. In the “pushing” mode, a repulsive tip-atom interaction drives the atom to move in
front of the tip. In the “sliding” mode, the atom is virtually bound to or trapped under the tip and
it moves smoothly across the surface together with the tip.

The tip is initially located directly above the atom and hence, only a vertical force
component (F┴) exists. The tip-atom distance is carefully chosen so that the attractive interaction
between them is not strong enough to overcome the desorption barrier of the atom. Since the
lateral force component (F║) is negligible at this point the atom will neither transfer to the tip nor
move to the next adsorption site (ad-site) on the surface. When the tip moves parallel to the

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surface it passes over the manipulated atom,
thereby tracing a part of the atomic contour.
This action increases F║ and decreases F┴
(Figure 11). When F║ overcomes the hopping
barrier of the atom, the atom hops to the next
adsite under the tip. This action alerts the STM
feedback system to retract the tip in order to
maintain the current constant causing an abrupt
increase in the tip-height.
Figure 11. (a) The drawing demonstrates the
vertical and parallel force components involved in
LM. (b) STM tip-height manipulation
curvescorrespond to (1) pulling, (2) pushing, and
(3) sliding modes.
.

3.1.2 Vertical Manipulation:

This process involves the transfer of single atoms or molecules between the tip and
substrate and vice versa. The atom/molecule transfer process can be realized by using an electric
field between the tip and sample, by exciting with inelastic tunneling electrons, or by making
mechanical contact between the tip and the atom/molecule. Transfer mechanism can be explained
by using a model of a double potential well.

Figure 12. Vertical manipulation (VM). (a) A

schematic drawing shows the process. (b) The
double-potential well model. The black
(solid),dash and gray curves represent the shape
of potentials (the well shapes are working
assumptions) at an image-height, under an
electric field, and at the tip-atom/molecule
contact, respectively.

00At an imaging distance, the

atom/molecule has two possible stable
positions, one at the surface and one at the
tip apex.Each position is represented by a
potential well, and the two potential wells are more or less equal in shape, separated by a
barrier.If the tip is stopped above the atom at the same distance and an electric field is applied,

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then the shape of the double potential well changes.The barrier between the two wells reduces,

and the potential well at the tip apex has a much lower energy level.The atom now can easily
transfer to the tip.By applying a reverse polarity bias, the minimum potential well can be changed
to the surface side.The atom can then transfer back to the surface.

Figure 13. Example on Manipulation (quantum

corrals)
3.2 Induced Chemical Reaction at Tip:

The finely focused electron beam from STM tip can also be used to induce
local chemical reaction, which provides another method to fabricate various pre-
designed Nano-structures on the surface.

Example: STM tip-induced synthesis steps of a biphenyl molecule (Look Figure

14).

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Figure 14. Schematic illustration of the STM tip-induced synthesis steps of a biphenyl molecule (Ullmann
reaction). (a),

(b) Electron-induced selective abstraction of iodine from iodobenzene. (c) Removal of the iodine atom to a
terrace site by lateral manipulation. (d) Bringing together two phenyls by lateral manipulation. (e)
Electroninduced chemical association of the phenyl couple to biphenyl. (f ) Pulling the synthesizedmolecule
by its front end with the STM tip to confirm the association.

CONCLUSION

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 The STM in spite of its conceptually simple operation principle has
been proved to be an extremely versatile and powerful technique for many
disciplines in condensed matter physics, chemistry, material science, and
biology. In addition, STM can be used as a Nano-tool for Nano-scale
fabrication, manipulation of individual atoms and molecules, and for building
nanometer scale devices one atom/molecule at a time.

REFRENCES

1.http://www.spmlab.science.ru.nl/
2.http://www.fkf.mpg.de/ga/research/stmtutor/stmconc.html
3.http://www.omicron-instruments.com/
4.Nan Yao, Zhong LinWang ,Handbook Of Microscopy For Nanotechnology
5.Saw-Wai Hla, STM Single Atom/Molecule Manipulation and Its Application to
Nanoscience and Technology
6.E. Zupanič, R. Žitko, H.J.P. van Midden, A. Prodan, I. Muševič, Single atom
manipulation and spectroscopy using low – temperature STM

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