Nanoscience and Nanotechnology

Nano is a new buzz word in the scientific community. The word is used a lot more in society
and in products such as the nano car and iPod nano. Nano has been mentioned in films like
Minority Report and Spiderman. It has been in the news with increasing regularity. But what
exactly is nanoscience and nanotechnology, and why all the hype?

Nanoscience: Nanoscience is the study of phenomena and manipulation of materials at the

Nanoscale. It is an interdisciplinary science involving biology, chemistry, physics, medicine,
materials science and engineering.

Nanotechnology: is the creation of: USEFUL/FUNCTIONAL materials, devices and

systems through control of matter on the nanometer length (nm) scale, and exploitation of
novel phenomena and properties (physical, chemical, biological) at that length scale to satisfy
human needs.

Nanotechnology is now applied widely in the ICT (Information and Communications

Technology) industry in the manufacture of smaller integrated circuits (computer ‘chips’) and
more efficient data storage mechanisms. It is also used in the medical devices industry to
make smaller products. Several commercial examples of nanotechnology are on the market,
and many more promising applications of nanotechnology are being investigated.
Nanotechnology will impact virtually every industry in the future.

The nanometre scale

The nanometre scale is conventionally defined as 1 to 100 nm. One nanometre is one
billionth of a meter (10-9 m). The size range is set normally to be minimum 1nm to avoid
single atoms or very small groups of atoms being designated as nano-objects. Therefore
nanoscience and nanotechnologies deal with at least clusters of atoms of 1nm size.
Nanoscience works on a scale 1000 times smaller than anything that can be seen with an
optical microscope.
Figure 1. The Perception of Length Scale - The nanometer (nm)

Nanomaterial

Materials that have at least one dimension smaller than 100 nanometres are called
nanomaterials. Nanomaterials are categorised according to their dimensions as shown in
Table 1.
Scaling Laws in Miniaturization

Miniaturization is the process of manufacturing ever smaller mechanical, optical and

electronic products and devices. There has been increasing strong market demand for
intelligent, robust, multi-functional, and low-cost industrial products. Miniaturization is the
only viable solution to satisfy such market demand.

Advantages of miniaturization

 Small systems tend to move or stop more quickly due to low mechanical inertia. It is
thus ideal for precision movements and for rapid actuation.
 Miniaturized systems encounter less thermal distortion and mechanical vibration
due to low mass.
 Miniaturized devices are particularly suited for biomedical and aerospace applications
due to their minute sizes and weight.
 Small systems have higher dimensional stability at high temperature due to low
thermal expansion.
 Smaller size of the systems means less space requirements. This allows the packaging
of more functional components in a single device.
 Less material requirements mean low cost of production and transportation.
 Ready mass production in batches.

Scaling Laws

The scaling laws are proportionality relations of any parameter associated with an object (or
system) with its length scale. In complex systems scaling laws become relevant for
understanding the interplay among various physical phenomena and geometric characteristics.
Sometimes, relatively simple scaling laws, applicable to very complex systems, can provide
clues to some fundamental aspects of the system. Thus, scaling laws are not only important
for designing microsized systems but also very useful in understanding the basic physical
principles involved in many complex phenomena.

There are primarily two types of scaling laws.

1. Scaling in Geometry: Scaling of physical size of objects

2. Scaling of Phenomenological Behavior: Scaling of both size and material
characterizations
Scaling in Geometry

The laws for geometric scaling are simple and well known. The scaling of various geometric
parameters follows the laws given below:

1. Perimeter (P) ∝ l
2. Area (A) ∝ l2
3. Volume (V) ∝ l3
where l is the length scale.

10 time reduction in length leads to 101 = 10 time reduction in perimeter

10 time reduction in length leads to 102 = 100 time reduction in area

10 ime reduction in length leads to 103 = 1000 time reduction in volume

4. The scaling of surface to volume ration (S/V ratio) – is given as fallows

S ∝ l 2 and V ∝ l 3, S /V ∝ l −1, As the size l decreases, its S/V ratio increases.

Scaling of Phenomenological Behavior:

Scaling of Electrical Parameters

Scaling laws have important consequences for electrical systems. The three passive electrical
elements, resistors, capacitors, and inductors, are taken up for determining the scaling effects.

1. Resistance
The resistance of a given conductor of length L, cross-sectional area A,
and specific resistivity ρ is given by
R = Lρ/A = l1 / l2 = l−1
So, for a given material electrical resistance scales as l–1.

2. Capacitance
For a parallel plate capacitor of plate area A, plate gap d, and ε as the permittivity of gap
insulation material the capacitance.
So, for a given material capacitance scales as l–1.

3. Inductance
With N as the number of coils per unit length with a coil area A and L as the length of the
inductor, the inductance L is given by
L = μN2A/L = l2 × l1−1 = l1
where μ is the permeability of the material between the coils. Hence, the inductance scales as
l1. In an electrical circuit combinations of these basic units govern the characteristics of a
system. For example, the time constant of a circuit is dependent on the product RC and
governs the behavior when the voltage varies. To understand how it will scale the following
expression helps:

RC = [R] × [C] = l−1 × l1 = l°, So time constant is independent of scaling.

4. Electric Power Loss:

, where V is the applied voltage ∝ l 0

5. Electric field energy density:

where the dielectric permittivity ε ∝ l 0 and the electric field E∝ l −1.

Scaling in Electrostatic Forces

In Fig.2 the electric potential energy induced in the parallel plates is:

Figure 2. Parallel plate capacitor and graph describing paschen’s effect.

Breakdown voltage - The voltage required to initiate discharge.

From paschen’s effect, For d > 10µm , V ∝ l1

A factor of 10 decreases in linear dimension will decrease the potential energy by a factor of
1000.

Scaling in Heat Transfer

Scaling in Heat Conduction

1. Scaling of Heat Flux:

Heat conduction in solid is governed by the Fourier law,

, where qx: heat flux along the x axis; k: thermal conductivity of the solid;
T(x,y,z,t): temperature field.

Rate of heat conduction:

That is, reduction in size leads to the decrease of total heat flow.

2. Scaling in Submicrometer Regime:

In the submicrometer regime, the thermal conductivity is given by,

, where c, V, and λ are specific heat, molecular velocity, and average mean
free path, respectively.

, i.e a reduction in size of 10 would lead to a reduction of total heat flow

by 100.
Why does size matter?

At the nanometre scale, the properties of matter, such as energy, change. This is a direct
consequence of the small size of nanomaterials, physically explained as quantum effects. The
consequence is that a material (e.g., a metal) at the nanoscale exhibit unexpected chemical
and physical properties that are very different from the properties of bulk materials.
Properties like electrical conductivity, colour, strength and weight change when the nanoscale
level is reached. The same metal can become a semiconductor or an insulator at the nanoscale
level.

For instance, 1) bulk silver is non-toxic, whereas silver nanoparticles are capable of
killing viruses upon contact. 2) The optical properties of gold behave differently at the
Nanoscale compared to the macroscale. While gold at the macroscale is a yellow
color, gold at the Nanoscale can appear red.

Figure 3. (a) Gold as a bulk material and nanomaterial.

Why do properties of materials change at nano scale?

1. Due to the smallness of nanomaterials, their mass is extremely small and gravitational
forces become negligible. Instead electromagnetic forces are dominant in determining
the behaviour of atoms and molecules.
2. Quantum confinement: In a nanomaterial, such as a metal, electrons are confined in
space rather than free to move in the bulk of the material.
3. Quantisation of energy: Electrons can only exist at discrete energy levels. Quantum
dots are nanomaterials that display the effect of quantisation of energy.
4. Random molecular motion becomes more important
 5. Nanomaterials have an increased surface-to-volume ratio compared to bulk materials.
This has important consequences for all those processes that occur at a material
surface, such as catalysis and detection.

Figure 4. Schematic drawing showing how surface-to-volume increases as size is decreased.

How would the total surface area increase if a cube of 1 m3 were progressively cut into
smaller and smaller cubes, until it is formed of 1nm3 cubes?
Fabrication methods

Methods for fabricating nanomaterials can be generally subdivided into two groups:

1. top-down approach and

2. bottom-up approach

Top down approach refers to slicing or successive cutting of a bulk material to get nano sized
particle.

Example: Milling, Lithography etc.

Figure 5. Top-down approach

Bottom up approach refers to the build up of a nano material from the bottom: atom by atom,
molecule by molecule or cluster by cluster.

Example: Sputtering, physical vapor deposition etc.

Figure 6. Top-down approach

Top down approach

Numerous top-down fabrication methods used in nanotechnologies are derived from the
fabrication methods used in the semiconductor industry to fabricate the various elements of
computer chips (integrated circuits).

Milling or Ball Milling

Milling is a method of production of nano materials, where we ground the bulk material using
metal ball. This process is used in producing metallic and ceramic nano materials.

Figure 7. Schematic drawing ball Milling.

Lithography

Lithography comes from two Greek words, “lithos” which means stone and graphein which
means write i.e “writing a pattern on stone” It is one of the technique is used to pattern the
surface by removing some part of it. Transfer of design on to substrate to produce required
pattern on a substrate. Here pattern is produced on semiconductor substrate using suitable
high energy radiation.

Lithography includes a series of fabrication techniques that share the principle of transferring
an image from a mask to a receiving substrate. A typical lithographic process consists of
three successive steps: (i) coating a substrate (Si wafer or glass) with a sensitive polymer
layer (called resist), (ii) exposing the resist to light, electrons or ion beams, (iii) developing
the resist image with a suitable chemical (developer), which reveals a positive or negative
image on the substrate depending on the type of resist used (i.e. positive tone or negative tone
resist). In conventional microfabrication used in the semiconductor industry, the next step
after lithography is the pattern transfer from the resist to the underlying substrate. This is
achieved through a number of transfer techniques, such as chemical etching and dry plasma
etching.

Classification of lithography

Based on the radiation used (Visible - Laser, UV radiation or X rays) lithography can be
classified as

1. Photolithography
2. Electron beam lithography
3. Ion beam lithography
4. Neutral beam Lithography

1. Photolithography

Photolithography uses light (UV, deep-UV, extreme-UV or X-ray) to expose a layer of

radiation-sensitive polymer (photoresist) through a mask. The mask is a nearly optically flat
glass (or quartz, depending on the light used) plate which contains the desired pattern: opaque
areas (the pattern, made of an absorber metal) on a UV-transparent background. The image
on the mask can be either replicated as it is, placing the mask in physical contact with the
resist (contact mode photolithography) or reduced, usually by a factor of 5 or 10, and
projected to the resist layer through an optical system (projection mode photolithography).

Figure 8. Conventional use of photolithography in the semiconductor industry for fabricating elements
in integrated circuits (e.g. computer chips). A photoresist is deposited on a silicon wafer, exposed to
light through a mask, and the exposed area selectively removed with a developer.
Advantages of lithography:

Uniformity

Reproducibility

Accuracy

Used to produce:

- Mainly in VLSI of circuits, FET, surface gated quantum devices ,

- quantum dots, wires

- Grating, Zone plates

- Electronic and photonic IC

- Broad band communication

Scanning probe lithography:

Scanning probe lithography (SPL) describes a set of nanolithographic methods to pattern

material on the nanoscale using scanning probes.

Based on mechanical interaction, SPL can be classified as fallows

1. Mechanical scratching
2. Pickup and pick down lithography
3. Dip Pen lithography

Mechanical scratching is a nanomachining or nano-scratching top-down approach without

the application of heat. In pickup and pick down lithography, AFM tip is used to pick up the
loosely bound atoms from the surface and placed in desired pattern. Where as in dip pen
lithography AFM tip is used as pen and molecules are used as ink to produce nano patteren.
Bottom-Up Approach

Bottom up approach refers to the build up of a nano material from the bottom: atom by atom,
molecule by molecule or cluster by cluster. In bottom up approach, nanomaterials can be
synthesized in two different phase

1. Gas phase
2. Liquid phase

Gas-phase methods: These include physical vapor deposition and chemical vapour deposition;

Liquid phase: The most established method is sol-gel synthesis and self-assembly.

Keeping in view of our syllabus, only self-assembly is discussed in detail

Self-assembly

The spontaneous arrangement of individual components (atoms or molecules) into an ordered

structure without human/supernatural intervention is known as self-assembly.

Figure 9. Schematic drawing of self assembly of positively and negatively charged

nanoparticles

Molecular self-assembly involves non-covalent or weak covalent interactions (van der Waals,
electrostatic, and hydrophobic interactions, hydrogen and coordination bonds).

Eg: Polymers, DNA, Proteins, Lipids etc self-assembling machines.

Protein is formed by successive addition of hundreds of amino acids.

Self-assembly can be classified as either static or dynamic.

• Static self-assembly involves systems that are at global or local equilibrium and do
not dissipate energy.

• Dynamic self-assembly (D): the interactions responsible for the formation of

structures or patterns between components only occur if the system is dissipating
energy. The patterns formed by competition between reaction and diffusion in
oscillating chemical reactions are simple examples; biological cells are much more
complex ones.

The processes of static and dynamic self-assembly can be further roughly sub-divided into
co-assembly, directed self-assembly and hierarchical self-assembly as shown in Fig. 1.

Figure 10. Graphical rendition of static and dynamic self-assembly and how they relate to co-
assembly, hierarchical assembly and directed assembly.
Co-assembly represents cases in which the simultaneous self-assembly of different building
blocks within the same system
leads to a synergic architecture that could not have been produced by the isolated self-
assembly of either building block.

Hierarchical self-assembly is characterized by the organization of a single building block

over multiple length scales. The original building blocks organize into a ‘first order’
assembly, which becomes the building block for a larger ‘second order’ assembly. This
process can lead to several orders of assembly.

Directed assembly is a case where the self-assembly is directed by external forces that had
been placed by design. This is the typical case for bottom-up-meets-top-down approaches
where a lithographic pattern can be used to direct the self-assembly of colloids from solution
on a substrate.