Unit I: Introduction

Introduction to Nanotechnology:

Nanotechnology, shortened to "nanotech", is the study of the controlling

of matter on an atomic and molecular scale.

Generally nanotechnology deals with structures of the size 100 nanometers

or smaller in at least one dimension, and involves developing materials or
devices within that size.

Nanotechnology is very diverse, ranging from extensions of conventional

device physics to completely new approaches based upon molecular self-
assembly, from developing new materials with dimensions on the nanoscale
to investigating whether we can directly control matter on the atomic scale.

One nanometer (nm) is one billionth, or 10−9, of a meter. By comparison,

typical carbon-carbon bond lengths, or the spacing between these atoms in a
molecule, are in the range 0.12–0.15 nm, and a DNA double-helix has a
diameter around 2 nm. On the other hand, the smallest cellular life-forms,
the bacteria of the genus Mycoplasma, are around 200 nm in length.

To put that scale in another context, the comparative size of a nanometer to

a meter is the same as that of a marble to the size of the earth.

Two main approaches are used in nanotechnology. In the "bottom-up"

approach, materials and devices are built from molecular components which
assemble themselves chemically by principles of molecular recognition. In
the "top-down" approach, nano-objects are constructed from larger entities
without atomic-level control.

Nanobiotechnology is the branch of nanotechnology with biological and

biochemical applications or uses. Nanobiotechnology often studies existing
elements of nature in order to fabricate new devices.

This field includes two approaches,

1. One is the application of nano-scaled tools to biological systems and

2. The other is the use of biological systems as templates in the

development of nano-scaled products.
 It is the intersection of organic and inorganic engineering to solve critical
problems in biology.

These problems can be

1. the creation of new drugs,

2. drug delivery vehicles,

3. targeted drug delivery,

4. diagnostics,

5. sensors,

6. assays,

7. fluidic tools and

8. Manufacturing processes for all of the above.

Structure and property relationships:

The two main reasons why materials at the nano scale can have
different properties are

1. increased relative surface area and

2. New quantum effects.

The unique properties of these nanomaterials give them novel electrical,

catalytic, magnetic, mechanical, thermal, or imaging features that are highly
desirable for applications in commercial, medical, military, and
environmental sectors.

Typically stable substances can become highly reactive and unstable when
the particles become infinitesimal due to their extremely high surface to
mass ratio.

A series of quantum confinement effects arises that significantly change the

way the particles behave such as conductivity, specific heat, increases in
energy band gap, and different wave lengths of emitted light.

The phenomenonological effects these nanoparticles have when combined

with existing bulk material is clear. Materials become stronger, more dent
resistant, exert higher ductility, are lighter, and obtain a host of other
material enhancement characteristics.

The size of the nanoparticle grains strongly effect the property changes in
the bulk material. For instance, the overlapping of different grain sizes
affects the physical strength of the material.

Also, when the crystallites of a material are reduced to the nanometer scale,
there is an increase in the role of interfacial defects: grain boundaries, triple
junctions, and elastically distorted layers. The long established Hall-Petch
model, which shows the inverse relationship between grain size and material
yield strength, has been proven to hold with nanoparticles as well

A study of nanocrystalline Fe powder revealed that when grain size was

decreased from 33nm to 8nm, hardness increased and fracture stress and
elongation to failure decreased. These results can be connected to the
reduction of defects in the material such as micropores and other flaws,
although this has been experimentally and theoretically proven, it is still
difficult to accurately predict the effects that will occur.

It is interesting to note that scientists have been using nanoparticles in tires

for a very long time
and never really understood why the improved effects occurred, besides that
it turned the rubber black.
For years, engineers have been putting carbon black nanoparticles in the
rubber of tires. The results are improved strength and tensile properties,
tear and abrasion resistance, and increased hardness because
of the integration of carbon grains

The material properties of metals can also be improved using techniques of

nanotechnology.
Metals can be modified into nanocrystalline materials that consist of
nanometer-sized grains with a
high density of crystal-lattice defects Interestingly, these metals achieve
extraordinary strength and
hardness and not only maintain, but improve ductility, a unique
characteristic of materials with
improved hardness. Scientists believe that the nanocrystalline grains provide
the strength while the
tensile deformation of the material is kept intact by the embedded larger
grains

Nanofabrication is the design and manufacture of devices with dimensions

measured in nanometers, essentially dealing with dimensions less than
100nm.

Nanofabrication Techniques

Fabricating structures at the nano level can be classified into two main
methods

1. 1.Top-down

2. Bottom-up construction

Top down fabrication:

1. Top down fabrication likened to sculpting from a block of stone.

2. A part of the base material is gradually eroded until the desired shape
is achieved.

3. That is, we start at the top of the blank piece and work our way down
removing material from where it is not required.

4. Nanotechnology techniques for top down fabrication vary but can be

split into mechanical and chemical fabrication techniques.

Top-down approaches

These seek to create smaller devices by using larger ones to direct their
assembly.

• Many technologies that descended from conventional solid-state silicon

methods for fabricating microprocessors are now capable of creating
features smaller than 100 nm, falling under the definition of
nanotechnology.
 • Giant magnetoresistance-based hard drives already on the market fit
this description, as do atomic layer deposition (ALD) techniques.
• Solid-state techniques can also be used to create devices known as
nanoelectromechanical systems or NEMS, which are related to
microelectromechanical systems or MEMS.
• Atomic force microscope tips can be used as a nanoscale "write head"
to deposit a chemical upon a surface in a desired pattern in a process
called dip pen nanolithography. This fits into the larger subfield of
nanolithography.
• Focused ion beams can directly remove material, or even deposit
material when suitable pre-cursor gasses are applied at the same
time. For example, this technique is used routinely to create sub-
100 nm sections of material for analysis in Transmission electron
microscopy.

Bottom up fabrication:

1. Bottom up fabrication can be likened to building a brick house.

2. Instead of placing bricks one at a time to produce a house, the bottom

up fabrication technology places atoms or molecules one at a time to
build the desired nanostructures.

3. Such processes are time consuming and so self-assembly techniques

are employed where the atoms arrange themselves as required.

4. Bottom up approaches seek to arrange smaller components into more

complex assemblies.
Bottom-up approaches

These seek to arrange smaller components into more complex assemblies.

• DNA nanotechnology utilizes the specificity of Watson–Crick

basepairing to construct well-defined structures out of DNA and other
nucleic acids.
• Approaches from the field of "classical" chemical synthesis also aim at
designing molecules with well-defined shape (e.g. bis-peptides).
• More generally, molecular self-assembly seeks to use concepts of
supramolecular chemistry, and molecular recognition in particular, to
cause single-molecule components to automatically arrange
themselves into some useful conformation.

Nanofabrication Techniques

PHOTOLITHOGRAPHY is a technique used to transfer shapes and designs

onto a surface of a photoresist material.
Over the years, this process has been refined and miniaturized;
microlithography is currently used to produce items such as semiconductors
for computers and an array of different biosensors.

Photolithography involves several generalized steps,

1. Cleaning of the substrate,
2. Application of the photoresist material,
3. Soft baking, exposure, developing, and
4. Hard baking.

Each step will be explained briefly below.

1. Cleaning of the Substrate

During substrate preparation, the material onto which the pattern will be
developed is cleaned to remove anything that could interfere with the
lithography process including particulate matter and impurities. After
cleaning, the substrate is dried, usually in an oven, to remove all water

2. Application of the Photoresist Material

There are two types of photoresist materials,

1. Positive and
2. Negative.

Positive photoresists

Become more soluble when they are exposed to UV light So in

photolithography, when the mask is laid down onto the positive photoresist,
the exposed areas (those not covered by the mask) will be removed by the
developing solution leaving only the shape of the mask and the underlying
substrate

Negative photoresist

Materials work in the opposite manner these photoresist materials

polymerize with exposure to UV light, making them less soluble after
exposure. Once the mask has been lifted and the material has been washed
with developing solution, the photoresist covered by the mask is washed
away therefore using a negative photoresist creates the photographic
negative of your mask
Photoresists commonly used in the production of microelectronics include
ethylene glycol, monoethyl ether propylene glycol and methyl ether acetate

Soft Baking

Types of Nanofabrication:

1. Nanolithography refers to the fabrication of nanometer-scale

structures by patterning substrates with at least one lateral dimension
between the size of an individual atom and approximately 100 nm by
employing interaction of beams of photons or particles with materials.

2. Self assembly is a bottom up process in which components arrange

themselves into structured units or patterns from a base.

3. Scanning Probe microscopy is used to image surfaces at the

nanometer scale by using a fine probe that is scanned over a surface.
 This gives better resolution as the wavelength of light does not act as
a restraint.

Some important fabrication techniques:

Nanolithography

The technique of nanolithography is the patterning of a thin film where the

line resolution is below 100nm.
There are several primary techniques that are used for patterning in the
nanoscale regime.
1. Electron Beam Lithography
2. X-ray Lithography
3. Extreme Ultraviolet Lithography (EUVL)
4. Light Coupling Nanolithography (LCM)
5. Scanning Probe Microscope Lithography (SPM)
6. Nanoimprint Lithography
7. Dip-Pen nanolithography

Electron Beam Lithography

Electron beam lithography has been used in the production of

semiconductors and the patterning of masks for other types of lithography
(such as X-ray and optical lithography).
In electron beam lithography, the exposed substrate is modified by the
energy from a stream of electrons.

1. It is the practice of scanning a beam of electrons in a patterned

fashion across a surface covered with a resist.
2. The primary advantage of electron beam lithography is that it is one
of the ways to beat the diffraction limit of light.
3. It uses a focused beam of electrons to form the circuit patterns
needed for material deposition on (or removal from) the wafer.
4. It does not use a mask, electron beams are used to directly etch on
the wafer surface.
5. It offers higher patterning resolution than optical lithography because
of the shorter wavelength possessed by the 10-50 keV electrons that it
employs.
Nanosphere Lithography

Nanosphere lithography is similar to other types of lithography. In this type

of lithography, the mask is replaced with a layer of nanospheres. After
exposure and developing, the uncovered resin is washed away leaving
behind nanoscale vertical columns.

Dip Pen Lithography

Dip pen lithography is a type of scanning probe lithography. In this

lithographic technique,
1. The tip of an atomic force microscope (AFM) is used to create micro-
and nanoscaled structures by depositing material onto a substrate.
2. The AFM tip delivers the molecules to the substrate surface using a
solvent meniscus that forms in ambient atmospheres.
3. Structures with features ranging from several hundreds of nanometers
to sub-50 nm can be generated using this technique.

Dip pen lithography is a direct-write method that yields high resolution and
has been used to create microscale and nanoscale patterns with a variety of
‘‘inks’’ (such as biomolecules, organic molecules, polymers, and inorganic
molecules) on a number of substrates.

The technology can now be used to construct protein arrays for proteomics,
pharmaceutical screening processes, and panel immunoassays.

Dip pen lithography involves several steps.

The first is substrate preparation:

1. The substrate is cleaned and rinsed to remove all impurities and
produce a flawless surface.

2. In order to aid in adhesion of the material being deposited, a self-

assembled monolayer may be added to the surface.

3. The AFM tip is then coated with the ‘‘ink’’ to be deposited onto the
substrate. Finally, the tip is used to produce the desired pattern.

Deep X-Ray Lithography

1. In LIGA, a several hundred microns thick radiation sensitive polymer

layer is applied to a substrate (a metallic base plate or a silicon wafer).
 2. This layer is either glued to the substrate or polymerized onto it;
polymethyl methacrylate (PMMA) is an example of a polymer that can
be bonded to the substrate.

3. A mask is placed over the polymer layer and the mask pattern is then
transferred onto the polymer layer using deep X-ray exposure with
wavelengths from 0.2 to 0.6 nm (using Synchtron radiation)

Mechanism:

1. Having short wavelengths (below 1 nm), X-rays overcome the

diffraction limits of optical lithography, allowing smaller feature sizes.
2. If the X-ray source isn't collimated, as with a synchrotron radiation,
collimating mirrors or diffractive lenses are used in the place of the
refractive lenses used in optics.
3. The X-rays illuminate a mask placed in proximity of a resist-coated
wafer.
4. The X-rays are broadband, typically from a compact synchrotron
radiation source, allowing rapid exposure.
5. The mask consists of an X-ray absorber, typically of gold or
compounds of tantalum or tungsten, on a membrane that is
transparent to X-rays, typically of silicon carbide or diamond.
6. The pattern on the mask is written by direct-write electron beam
lithography onto a resist that is developed by conventional
semiconductor processes.
7. The membrane can be stretched for overlay accuracy.

Another manifestation of the photoelectron effect is exposure to X-ray

generated electrons from thick gold films used for making daughter masks.
Simulations suggest that photoelectron generation from the gold substrate
may affect dissolution rates.
 Ion Beam Lithography:

This is a variation of the electron beam lithography technique, using a

focused ion beam (FIB) instead of an electron beam, which scans across
the substrate surface and exposes the sensitive coating.

A grid of pixels is superimposed on the substrate surface, each pixel

having a unique address. The pattern data is transferred to the controlling
computer, which then directs the electron beam to realize the pattern on
the substrate pixel by pixel.

The advantages of ion beam lithography include

 1. computer controlled beam

2. minimized back scattering

3. no necessity for mask

4. minimized diffraction effects

5. higher resolution

6. accurate surface feature registration

7. ion sensitive resists are better responsive

Quantum dot

A quantum dot is a semiconductor whose excitons are confined in all three

spatial dimensions. As a result, they have properties that are between those
of bulk semiconductors and those of discrete molecules.

Quantum dots are semiconductors whose conducting characteristics are

closely related to the size and shape of the individual crystal. Generally, the
smaller the size of the crystal, the larger the band gap, the greater the
difference in energy between the highest valence band and the lowest
conduction band becomes, therefore more energy is needed to excite the
dot, and concurrently, more energy is released when the crystal returns to
its resting state.

The main advantages in using quantum dots is that because of the high level
of control possible over the size of the crystals produced, it is possible to
have very precise control over the conductive properties of the material.

There are several ways to confine excitons in semiconductors, resulting in

different methods to produce quantum dots. In general, quantum wires,
wells and dots are grown by advanced epitaxial techniques in nanocrystals
produced by chemical methods or by ion implantation, or in nanodevices
made by state-of-the-art lithographic techniques.

Applications

1. In modern biological analysis, various kinds of organic dyes are used.

However, with each passing year, more flexibility is being required of
these dyes, and the traditional dyes are often unable to meet the
expectations. To this end, quantum dots have quickly filled in the role,
being found to be superior to traditional organic dyes on several
counts, one of the most immediately obvious being brightness (owing
to the high quantum yield) as well as their stability (allowing much
less photobleaching). It has been estimated that quantum dots are 20
times brighter and 100 times more stable than traditional fluorescent
reporters. For single-particle tracking, the irregular blinking of
quantum dots is a minor drawback.
2. The usage of quantum dots for highly sensitive cellular imaging has
seen major advances over the past decade. The improved
photostability of quantum dots, for example, allows the acquisition of
many consecutive focal-plane images that can be reconstructed into a
high-resolution three-dimensional image.
3. Another application that takes advantage of the extraordinary
photostability of quantum dot probes is the real-time tracking of
molecules and cells over extended periods of time. Researchers were
able to observe quantum dots in lymph nodes of mice for more than 4
months.
4. Semiconductor quantum dots have also been employed for in vitro
imaging of pre-labeled cells. The ability to image single-cell migration
in real time is expected to be important to several research areas such
as embryogenesis, cancer metastasis, stem-cell therapeutics, and
lymphocyte immunology.
 5. Scientists have proven that quantum dots are dramatically better than
existing methods for delivering a gene-silencing tool, known as siRNA,
into cells.
6. First attempts have been made to use quantum dots for tumor
targeting under in vivo conditions. There exist two basic targeting
schemes: active targeting and passive targeting.
7. In the case of active targeting, quantum dots are functionalized with
tumor-specific binding sites to selectively bind to tumor cells.
8. One of the remaining issues with quantum dot probes is there in vivo
toxicity. For example, CdSe nanocrystals are highly toxic to cultured
cells under UV illumination.
9. Another potential cutting-edge application of quantum dots is being
researched, with quantum dots acting as the inorganic fluorophore for
intra-operative detection of tumors using fluorescence spectroscopy.

As a consequence, the top-down approach for nanocrystal production has

received more attention.

There are two basic disintegration technologies for drug nanocrystals,

namely
(i) pearl/ball milling and
(ii)High pressure homogenization.

In pearl milling,

1. The drug macrosuspension is generally filled into a milling container

containing milling pearls made from materials like glass, zircon oxide,
or special polymers such as hard polystyrene derivatives.
2. The pearls are then moved by a stirrer and in the due process the drug
is ground to nanocrystals due to the impact between the pearls.
3. A general problem of pearl mills is the erosion of material from the
milling pearls leading to product contamination. The erosion mainly
depends on the hardness of the drug and the milling material and the
milling time required, which can be from few hours up to several days.
4. Such problems have been circumvented by the use of pearls made
from polymeric materials that tend to minimize the erosion.
5. The possibility of scaling up with pearl mills does exist;
6. However, there is a limitation on the size of the mill, due to its weight.
Approximately two thirds of the mill volume is occupied by the pearls,
leading to a heavy weight of the machinery, thus limiting the
maximum batch size.
Chemical Vapor Deposition

Chemical vapor deposition allows the user to deposit the CNTs directly onto
a substrate.

Chemical vapor deposition is commonly used in the manufacturing of metals

and ceramics.

This technique can produce CNTs at a continuous rate and is easily scalable
to produce large amounts of CNTs for commercial distribution.
By changing growth conditions such as
1. growth temperature,
2. carbon source,
3. catalyst,
4. catalyst-to-carbon ratio, and
5. Type of substrate, CNTs can grow in a variety of ways, including
randomly oriented and aligned.

There are several ways to perform chemical vapor deposition, including

1. hotwall chemical vapor deposition,

2. cold-wall chemical vapor deposition,
3. high pressure CO conversion (HiPCO) chemical vapor deposition, and
4. laser-assisted chemical vapor deposition;

Both hot-wall and cold-wall chemical vapor deposition are forms of thermal
chemical vapor deposition.

In hot-wall chemical vapor deposition processes, such as thermal

chemical vapor deposition, the process takes place in a high temperature
tube furnace.
1. The substrate that the CNTs will be deposited on is placed inside of the
tube and the entire tube is heated (heating the substrate to the
growth temperature).
2. A hydrocarbon source, such as benzene, xylene, or hexane, is also
introduced into the tube.
3. Once in the tube, it decomposes and deposits onto the substrate.

In cold-wall chemical vapor deposition processes, including plasma-

enhanced chemical vapor deposition,
 1. The temperature of the sample holder is raised and the rest of the
system is left at a lower temperature.

In HiPCO chemical vapor deposition,

2. High pressure carbon monoxide is fed into the system and used as the
carbon source.

Laser-assisted chemical vapor deposition is a technique that is used for

thin film deposition and can be adopted to produce films of CNTs.

3. In laser-assisted chemical vapor deposition, the global energy source

that warms the furnace is replaced by a localized energy source, the
laser.
4. In this method, the source of the energy on the substrate is localized,
so the growth of the CNTs can be limited to the area over which the
laser passes.
5. Laser-assisted chemical vapor deposition is controlled by two
mechanisms:

• Photolytic laser-assisted chemical vapor deposition and

• pyrolytic laser assisted chemical vapor deposition.

Depending on the conditions, such as temperature and position of the laser

beam, both mechanisms can take place simultaneously.

In such cases, one mechanism for CNT deposition may dominate the other.
Only the photolytic process can occur at low temperatures, but at high
temperatures both the photolytic and pyrolytic processes can occur
simultaneously.
Pyrolytic or photolytic reactions are caused by the laser radiation
wavelength, precursor compounds used, and chosen substrate material.