Molecular

Nanotechnology

This chapter describes how we ‘see’ atoms using atomic

microscopy. You will find out how we can pick up atoms and
move them around, or spray them onto surfaces to form
nanomaterials.

II.1. Introduction
- Atoms form materials by combining together in ratios of whole
numbers in the different chemical bonds;
- It is a little harder to find out how many actual atoms are in a gram of
an element. For hydrogen, this number is believed to be about
6.02x1023 and is called Avogadro’s number
- One atom of 1H hydrogen weighs 0.166 x 10-23 grams. Therefore,
one mole weighs 0.166x10-23 x 6.02x1023 = 1gram. If we want to
weigh out atoms in quantities, we can weigh them out in grams and
express the quantity of atoms in moles. Thus 1 gram of hydrogen
atoms is weighed out to get 1 mole or 6.02 x1023 atoms.
- Recently tools have been developed that allow us to see atoms. It is
therefore possible in theory to actually measure Avogadro’s number.

II.2. Electron Microscopes

Electron microscopes are instruments that use a beam of highly
energetic electrons to examine very small objects. This
examination gives information on morphology, topography and
crystallography which we need to define.

- Morphology is the shape and size of the particles making up the

object. In nanotechnology there are nanoparticles of different shape
and size, of the order of up to 100 nm, although it is difficult to
determine where microtechnology starts and nanotechnology finishes;
- Topography, on the other hand, is the surface features of an object or
‘how it looks’, including its texture, or hardness;
- Crystallography describes how the atoms are arranged in the object.
They may be ordered in a regular lattice, thereby producing a crystal,
or they may be randomly organised, in which case they are said to be
amorphous. The way in which the atoms are ordered can affect the
properties of a material, such as its conductivity, electrical properties
and strength.

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 The stepwise stages in obtaining an image in a
Transmission Electron Microscope

1. A stream of electrons is formed by an electron source

and accelerated toward the specimen using a
positive electrical potential;
2. The stream is confined and focused using metal
apertures and magnetic lenses into a thin, focused,
monochromatic beam;
3. The beam is focused onto the sample using a
magnetic lens;
4. Interactions occur inside the irradiated sample,
affecting the electron beam;
5. These interactions and effects are detected and
transformed into an image.

II.3. Scanning Electron Microscope (SEM)

- The first scanning electron microscopes (SEMs) were

developed in 1942 and the first commercial instruments
were released around 1965. Its late development
compared with TEM was due to the electronics involved in
‘scanning’ the beam of electrons across the sample.
- The SEM is especially useful because it has a rather large
depth of field, that is, more of the image being magnified is
in focus. The SEM has an extremely wide range of
magnification, producing images in the range of 10 to
100.000 times. The SEM produces a sharp, three
dimensional view of a specimen, and is very helpful in
analysing its shape and structure.

Fig 2.1: Simplified view

of a SEM

In a SEM (fig 2.1), an electron gun emits a beam of electrons, which

passes through a condenser lens and is refined into a thin stream.
From there the objective lens focuses the electron beam onto the
specimen. When the electrons hit the specimen, a series of
interactions deflect secondary particles to a detector, which then
converts the signal to voltage and amplifies it. This voltage is then
applied to a cathode-ray tube and converted to an image.

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II.4. Transmission Electron Microscope (TEM)
Although developed first, the TEM is now preferred to the SEM for most
applications in nanotechnology. Magnifications of 400 000 times can be
easily obtained for many materials and atoms can be imaged at
magnifications greater than 15 million times.
Materials for TEM must be specially prepared to thicknesses that will
allow electrons to be transmitted through the sample, therefore it is often
the key to a good TEM picture

Fig 2.2: Simplified view of

the structure of the TEM

The components of a TEM are outlined in Fig 2.2.

1. There is an electron gun that produces a stream of electrons.

2. This stream is focused to a small, thin, coherent beam by the use of
condenser lenses. The first lens largely determines the ‘spot size’.
The second lens actually changes the size of the spot on the sample.
The size of the beam is restricted by a condenser aperture.
3. The beam strikes the specimen and parts of it are transmitted.
4. This transmitted portion is focused by the objective lens into an image.
5. A selected area aperture enables the user to examine ordered
arrangements of atoms in the sample.
6. The image is passed through lenses and enlarged.
7. The image strikes the phosphor image screen and light is generated,
allowing the user to see the image. The darker areas of the image
represent the areas of the sample through which fewer electrons were
transmitted (they are thicker or denser). The lighter areas of the image
represent those areas of the sample through which more electrons
were transmitted (they are thinner or less dense).

Note:
- Like SEM, when electrons interact with a specimen there are also
emissions related to the spacing of energy levels in the atoms that in
turn allow those atoms to be characterised and quantified. Thus the
chemical composition of the material can also be measured. This can
also be done with spatial resolution, so not only can the sample be seen
in high magnification, but each of the observed substructures can be
chemically characterised. In some instruments, such as a TEM
equipped with an energy dispersive spectrometer (EDS), elemental
analyses can be obtained from areas as small as a few nanometres in
diameter.
- Because of low count rates, these analyses usually have a relative
error between 5% and 10%. On the other hand, very precise accurate
chemical analyses (relative error ~ 0.5%) can be obtained from larger
areas of the solid (0.5–3.0 micrometres in diameter) using an electron
microprobe with wavelength dispersive spectrometers (WDS). Analyses
at a lower precision and accuracy (1–2% relative) may be obtained from
SEMs equipped with EDS.

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II.5. Scanning Probe Microscopy (SPM) - Atomic Force
Microscope (AFM)
SPM is a term that encompasses a number of microscopies (AFM
& STM). They have a common operation.
The AFM generates a topological image by systematically moving a
sharp tip across a surface. As the tip tracks the surface, the force
between the tip and the surface causes the cantilever to bend. A
device called an optical lever measures the deflection of the cantilever.
The optical lever of most machines consists of a laser beam reflected
from the gold coated back of the cantilever on to a positional sensitive
diode. The positional sensitive diode can measure changes in position
of the incident laser beam as small as 1 nm, thus giving sub-
nanometre resolution.

The AFM normally works in two modes: noncontact and contact modes.
In non-contact mode the attractive van der Waals forces are measured
by oscillating the cantilever with a small amplitude some 5 to 10 nm
from the surface of the sample. Because non-contact mode measures
the weaker attractive forces, the lateral resolution is often said to be
less than that achieved with contact mode. This is not correct, since
non-contact AFM is used to demonstrate true atomic resolution.

In contact mode the repulsive forces are measured as the sample

cantilever pushes into the sample. These are interactions between
the atoms in the tip and the atoms of the material’s surface.
Consequently the tip is in physical contact with the surface during the
analysis and can cause physical damage to soft materials. This does
not work on soft samples because surface atoms are ripped up like
butter on a knife.
However a way around this is a variant of contact mode called
‘tapping mode’. The cantilever is vibrated so that the tip contacts the
surface intermittently. This intermittent contact serves to reduce the
lateral forces incident on the soft sample, reducing possible surface
damage or tip contamination but maintaining resolution.

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II.6. Scanning Tunnelling Microscope (STM)

The scanning tunnelling microscope (STM) was invented in 1981 by

Binnig and Rohrer at IBM Zurich. Five years later they were awarded
the Nobel prize in physics for their invention, along with the discoverers
of the electron microscope. The STM was the first instrument to
generate real-space images of surfaces with atomic resolution.
STM is similar to AFM except it uses a sharpened, conducting tip with a
bias voltage applied between the tip and the sample. When the tip is
brought within about 1 nm of the sample, electrons from the sample
begin to pass through the 1 nm gap into the tip or vice versa, depending
upon the sign of the bias voltage. In other words, this process invokes
the wave properties of an electron to move across an energy barrier at
lower energy than if it were a particle. The process is called tunnelling.
The resulting tunnelling current varies with tip-to-sample spacing, and it
is the signal used to create an STM image. For tunnelling to take place,
both the sample and the tip must be conductors or semiconductors.
Unlike AFMs, STMs in principle cannot image insulating materials.

Much of the other operations are like AFMs:

In constant-height mode, the tip travels in a horizontal plane above the sample
and the tunnelling current varies depending on topography and the local
surface electronic properties of the sample. Similarly, the tunnelling current
measured at each location on the sample surface constitutes the topographic
image.
In constant-current mode, STMs use feedback to keep the tunnelling current
constant by adjusting the height of the scanner at each measurement point.
The motion of the scanner constitutes the data set. If the system keeps the
tunnelling current constant to within a few percent, the tip-to-sample distance
will be constant within a few tenths of a nanometre. The change in voltage
necessary to keep this constant distance is of course also a measure of
topography, but it can mean other things.
Each mode has advantages and disadvantages. Constant-height mode is
faster because the system doesn’t have to move the scanner up and down, but
it provides useful information only for relatively smooth surfaces. Constant-
current mode can measure irregular surfaces with high precision, but the
measurement takes more time.

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II.7. Nanomanipulator
The scanning tunnelling electron microscope has a computer-controlled
probe that skates across the surface, and the mechanical deflections
are transferred to electrical energy. The probe can also be programmed
to push against the surface. When pushing, the charge separating the
flexing tip and its fixed mount creates an electrical current that is
proportional to the pressure exerted on the tip. By transmitting this
current to the proper computer interface a human can actually do the
touching. This instrument is called a nanomanipulator. It can also be
used to build simple objects and may eventually allow the operator to
‘feel’ when they pick up and move atoms.
II.8. Nanotweezers
Two researchers at Harvard University have created a nanoscale
grasping device ideal for measuring and manipulating molecular
structures. The device is used with the scanning-probe microscope and
consists of carbon nanotube (CNT) tips to form tweezer-like structures.
The tweezer structure can be closed with an applied electrical field like
a pair of chopsticks to produce a device that grasps and moves
molecules or atoms.

II.9. Atom manipulator

Single atom manipulation can be achieved with appropriate selection of
the charge (polarity), the magnitude and duration of a voltage pulse
applied between the STM tip and the sample surface.

II.10. Nano dots or quantum dots

Nanodots or quantum dots are small lifted pieces of raised surface up
to several atoms thick that are created by attaching atoms to the SPM
tip so that a strip of atoms are lifted and then deposited again (we will
discuss later).

II.11. Self assembly

Self assembly is the process whereby molecules line up where you
want them to go naturally.

II.12. Dip pen nanolithography (DPN)

Dip pen nanolithography (DPN) is a direct-write technique that is used
to create nanostructures on a substrate of interest by delivering
collections of molecules via a capillary from an AFM tip to a surface.
One of the most important attributes of DPN is that the same device is
used to image and write a pattern. With the aid of software a DPN
nanoplotter is able to write any type of complicated pattern.

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Fig 2.6: Diagram representing DPN technique (a) and pattern formed using DPN (b).

WHAT YOU SHOULD KNOW IN THE CHAPTER

- The different types of microscopes for seeing
atoms, how they operate, and the things they
measure such as topography and roughness (SEM,
TEM, AFM, STM);
- How atoms are manipulated one by one and moved
to form interesting new structures;
- How we can use self-assembly to generate ordered
surfaces and build the support blocks for millions of
nanomachines;
- How prepare the pattern surfaces by Dip Pen
Nanolithography.