Materials Science and Engineering

Institute of Space Technology

By: Dr. Sajid U. Khan

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Reference Text-books

1) Introduction to Nanotechnology
• Robert Preidt, Laura Costlow, April Peter

2) Introduction to NanoScience
• S.M. Lindsay

3) Nanotechnology- Basic Science and emerging technologies

• Mick Wilson, Kamali Kannangara, Geoff Smith, Michelle Simmons, Brkhard Raguse

4) Nanotechnology- Technology Revolution of 21st Century

• Robert Preidt, Laura Costlow, April Peter

5) Advanced Nanotechnology
• S.K. Prasad

6) Nanotechnology- An Introduction to Nanostructuring Techniques

• Michael Köhler, Wolfgang Fritzsche

7) Any text book on Nanomaterials/Nanotechnology

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o Do come to the class at given time
5 Minutes Late = Absent

o Do ask questions at the end of topic/lectures

o OHTs, pop-up quizzes will be conducted on their given
date/times
o Assignments submitted after due time/date will not be
considered
o Lecture Notes@Topics and your personal notes
o Reference books, Internet
o Feed back……Improvement

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Rules regarding assignments

 -Do give references to the material (books,

publication, internet etc)…this help you prepare for
thesis writing

 -Must be written in your own words

 -Every assignment should be unique

 -Two similar assignment will be refused

 -“No Copy-Paste” from internet

 - Last but not the least should be submitted on due

date

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o Introduction to the realm of
nanotechnology/materials
o Quantum Physics OR Quantum Mechanics
o Fabrication Methods in Nanotechnology
o Characterization Methods in Nanotechnology
o Applications
o Dangers of Nanotechnology
o Ethics in Nanotechnologys

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What is the Big Deal About Nanoscience?
“Isn’t it just a bunch of really small things?”
It is, in fact, a bunch of small things. But it is a whole
lot more. What makes the science at the nanoscale
special is that at such a small scale, while all
physical laws affect the behavior of matter,
different laws dominate over those that we
experience in our everyday lives.
For example, the element gold (Au) as we are used
to seeing it has a nice yellowish-brown color to
it—the color we know as “gold.” However, if you
had only 100 gold atoms arranged in a cube, this
block of gold would look very different—its color
would be much more red. Color is just one
property (optical) that is different at the nanoscale.
Other properties, such a flexibility/strength
(mechanical) and conductivity (electrical) are often
very different at the nanoscale as well.
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 What’s interesting about the nanoscale?
 Nanosized particles exhibit different properties than larger
particles of the same substance
 As we study phenomena at this scale we…
 Learn more about the nature of matter
 Develop new theories
 Discover new questions and answers in many areas,
including health care, energy, and technology
 Figure out how to make new products and technologies
that can improve people’s lives

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Small size ─ can put a lot of Nano-things per area
or per volume
• High surface to volume ratio ─ unique
environment of surface atoms
• Surface forces dominate over bulk forces─ for
example, gravity is not important!
• Importance of quantum mechanical effects

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 Exotic behavior of materials at smaller scale

 Exploit new domains in Physics

 New doors open

 New opportunities (new products, new

materials, etc) become accessible

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• Technologically, more powerful computers, new device
structures. Moore’s Law.

• Scientifically, fundamental interest in properties of nm

sized structures. Multi-disciplinary.

•Properties (optical, electrical, magnetic, mechanical) of

structures depend on their size (due to quantum effects).

•By patterning at the nm scale, we can tailor these properties

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The word nano is derived from the Greek word
nannos, which roughly translated means “little
man” or “dwarf.”
In today’s English usage, Nano is a technical
term for measurement meaning 1 billionth of
something. It is usually compounded with the
word meter and as a nanometer, is a measure of
distance of 1 billionth of a meter—
approximately the distance occupied by 5 to 10
atoms stacked in a straight line.

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 Just about making things incrementally smaller?

Just about a simple shift in the most convenient unit of measure?

No, as a Nano scientist/teacher, I DO see something very unique about

Nano:

Nano is about boundaries where BEHAVIOR radically changes:

When the BEHAVIOR OF THE OBJECTS SUDDENLY CHANGES

Or when OUR BEHAVIOR MUST CHANGE to make those things

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Two of the reasons:

1. Ratio of surface area-to-volume of structure increases

(most atoms are at or near the surface, which make them
more weakly bonded and more reactive)

2. Quantum mechanical effects are important

(size of structure is on same scale as the wavelengths of
electrons, resulting in changes in electronic and optical
properties)

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There are big changes in OBJECT BEHAVIOR below ~
10 nanometers:
Newton is out the window. Quantum Mechanics is in.

Hard sensible objects are replaced by squishy electron waves / clouds

And to make things < 100 nanometers WE MUST

BEHAVE differently:

Light will not focus this small

Light image based fabrication ceases to work

Need something new (“Nanotechnology”) - Still being defined!!!

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 The study of objects and phenomena at a very
small scale, roughly 1 to 100 nanometers (nm)
 10 hydrogen atoms lined up measure about 1 nm
 The diameter of a human hair is approx. 10-100 μm
 An emerging, interdisciplinary science involving
 Physics
 Chemistry
 Biology
 Engineering
 Materials Science
 Computer Science

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 Nano (materials)
 nanoscale science (effects)
 nanoscale technology
(fabrication)
 molecular nanotechnology
(chemistry)

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Nano-Technology

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Research and technology development at the atomic,
molecular or macromolecular levels, in the length scale of
approximately 100 nanometer range,

to provide a fundamental understanding of phenomena and

materials at this scale

and to create and use structures, devices and systems that

have novel properties and functions because of their small
and/or intermediate size.

Nanotechnology research and development includes

manipulation under control of the nanoscale structures and
their integration into larger material components, systems
and architectures.
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We will NOT focus narrowly on only certain types of objects

We will NOT get hung up on just one unit of measurement

We will instead search for radical changes in behavior

Behavior of the objects themselves

The changes in our behavior required for their

fabrication

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 5th century BC
 Greek - Democritus of Abdera
“Father of modern science“
- Are we smarter?

 All matter is made up of undividable particles called atoms

 There is a void, which is empty space between atoms
 Atoms are completely solid
 Atoms are homogeneous, with no internal structure
 Atoms vary in

1) Size
2) Shape
3) Weight

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1) chemical elements are made of atoms

2) the atoms of an element are identical in their masses

3) atoms of different elements have different masses

4) atoms only combine in small, whole number ratios

such as 1:1, 1:2, 2:3 and so on

5) atoms can be neither created nor destroyed

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This model was proposed; it is not completely
correct, but it has many features that are
approximately correct

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 Einstein
 Pauli
 Bose
 Heisenberg

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“People tell me about miniaturization, and how far it has progressed
today. They tell me about electric motors that are the size of the nail
on your small finger. And there is a device on the market, they tell
me, by which you can write the Lord's Prayer on the head of a pin.
But that's nothing; that's the most primitive, halting step in the
direction I intend to discuss. It is a staggeringly small world that is
below. In the year 2000, when they look back at this age, they will
wonder why it was not until the year 1960 that anybody began
seriously to move in this direction.

Why cannot we write the entire 24 volumes of the Encyclopedia Brittanica

on the head of a pin?”

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 The term grey goo was coined by
nanotechnology pioneer in this book
 Grey goo alternatively spelled gray
goo is a hypothetical end of the
world scenario involving molecular
nanotechnology in which out-of-
control self replicating robots
consume all matter on Earth while
building more of themselves
 Development of the ability to design
protein molecules will open a path to
the fabrication of devices

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According to Moore’s Law, the number of transistors on a chip roughly
doubles every two years. As a result the scale gets smaller and smaller. For
decades, Intel has met this formidable challenge through investments in
technology and manufacturing resulting in the unparalleled silicon expertise
that has made Moore’s Law a reality.

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Moore's Law won't last forever, though. At
some point, the laws of physics will make it
impossible to keep downsizing
microelectronics at this exponential rate.
Why?
Because eventually, you get down to
manipulating individual molecules, and at that
level, a few atoms out of place could ruin an
entire computer chip. The packed-in transistors
also generate a lot of heat, which could melt the
chip. Engineers are looking to nanoscience for
tools and materials to enable computer chip
manufacturing on an atomic scale.

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 1 meter

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 10 cm

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 1 cm

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The masterpiece of design

100 micrometers

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 10 micrometers

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 1 micrometers

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 100 nm

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 10 nm

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 1 nm

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• Most consider nanotechnology to be technology at sub-
micron scale: 1-100’s of nanometers
• Exact definition of nanotechnology is not clear.

Why is Small Good?

- Faster
- Lighter
- Can get into small spaces
- Cheaper
- More energy efficient
- Different properties for very small structures

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 Neither. Nanotechnology falls in between
these at the mesoscopic scale.

Macro Scale

Mesoscopic Scale
Atomic Scale

Quantum Mechanics
Nanotechnology
Classical Physics

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Albert Einstein Niehls Bohr Max Planck

An understanding of quantum mechanics began in the

early 19th century and had many contributors, including
these well-known physicists.

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It is crucial to realize that the physics on the nanometer
scale tends to become dominated by quantum physics. In
the nano-world one must always be prepared to take
seemingly strange quantum phenomena into account and
hence give up on an entirely classical description.
Although this is not a course in quantum physics it is
nevertheless imperative to get a grasp of the basic ideas
and concepts of quantum physics. Without this it is not
possible to reach a full understanding of the potentials of
nanotechnology. Serious students of nanotechnology are
hereby encouraged to study at least a minimum of
quantum theory

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 We will often refer to something as being “classical” –
that just means it follows Newton’s laws.
 Quantum mechanics is more fundamental than
Newton’s laws
 We shall soon see that for nm-sized objects, the
concepts of “particles” and “waves” become mixed
 Light being an electromagnetic wave has wave-like
properties, as we know, but it also behaves like it is
made of particles in certain situations. The same is true
for what we traditionally think of as particles –
electrons, protons, etc – they sometimes behave like
waves!
 Quantum mechanics is a way of describing this
strange behavior, and is a very powerful tool

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 Quantum mechanics is indeed difficult to grasp
 Our intuition is incorrect and that experiential
knowledge gained from experiment is the only access
we have to reality
 In fact, much of quantum mechanics is so paradoxical
(i.e. self-contradicting) that we can only indicate how
things behave but can't even postulate on a mechanism
for why reality behaves the way that it does.
 So in quantum mechanics we are bound to understand
how matter and energy behave in a probabilistic
manner without the ability to address why it behaves
that way

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 Top down and Bottom up approach
 Carbon nano-tubes (CNTs)
 SWNT, MWNT
 Carbon nano-wires (CNWs)
 Carbon nano-rods (CNRs)
 Solid oxide fuel cells (SOFC)
 AFM/SEM/SPM/STM/XPS/TEM/SIMS

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• Nano-crystalline materials • Nano-photonics
• Nano-particles • Nano-magnetics
• Nano-capsules • Nano-fabrication
• Nano-porous materials • Nano-lithography
• Nano-fibers • Nano-manufacturing
• Nano-springs • Nano-medicine
• Nano-belts • Nano-bio
• Molecular electronics And so on…..
• Quantum dots
• MEMS/NEMS
• Nano-fluidics

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• Information Technology
- Computing, Memory and Data Storage
- Communication
• Materials and Manufacturing
• Health and Medicine
• Energy
• Environment
• Transportation
• Security
• Space exploration
• Other…..
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 Ability to synthesize nanoscale building blocks with
control on size, composition etc.
 Further assembling into larger structures with designed
properties will revolutionize materials manufacturing
 Manufacturing metals, ceramics, polymers, etc. at exact
shapes without machining
- Lighter, stronger and programmable materials
- Lower failure rates and reduced life-cycle costs
- Bio-inspired materials
- Multifunctional Materials
-Self-healing materials
Challenges ahead
- Synthesis and large scale production
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The examination of nature, its models, systems, processes and
elements to emulate or take inspiration from in order to
solve human problems.

Bio-inspiration is a relatively new field of science that is trying

to replicate the phenomena and designs of nature in ways
that are of benefit to man. The manner in which a gecko’s
foot allows it to climb glass, the way in which the wings of a
butterfly sparkle in the sunlight and the complex methods of
flight used by insects have all inspired technologists to
emulate nature.

We basically see something cool and interesting in nature and

try to copy it.

Lets get to some examples

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Gecko’s Sticky Feet

 Geckos are lizards belonging to the

infraorder gekkota
 Can cling to any surface at any orientation
 Can walk on smooth and rough surfaces
 Upside down on a glass surface
 Can walk on dirty or wet surfaces

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For 450 million years, spiders have made silk, protein-
based nanomaterials that self-assemble into fibers and
sheets.

If we figure out how to copy this nano-science feat,

scientists would like to use the material to create an
elevator to space.

Does that sound like a good idea to you?

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Applications?
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Butterfly wing scales in increasing magnitude

Butterfly wings are layers of nanoparticles seperated by

layers of air. The thickness of the layers changes the colors
that we see.

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Butterflies figured out how to
emit light 30 million years ago.

Fluorescent patches on the wings of this

African swallowtail butterflies work in a very
similar way to high emission light emitting
diodes (LEDs).

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“Like Water Off of a Duck’s Back…

Or a Butterfly’s Wing!

This picture shows water

droplets on a wood surface
treated with "Lotus Spray“,
The white bar on this The white bar on this a nanotechnology product
picture of a butterfly wing is nanoscopic view of a modeled after the butterfly
1mm long. butterfly wing is 1 µm. wing and lotus leaf, which
has made the surface
extremely water-repellant
(superhydrophobic).

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Because of the nanostructures on
a butterfly wing or other
hydrophobic surface, a water drop
forms into a ball, rolling from the
surface and taking the dirt with it.
= water
= dirt
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This magnified image shows the
nanostructures on a wing surface. Because of
the waxiness of the surface, the waterdrop
rolls – rather than slides – down the surface
with little friction. The drop collects dirt and
bacteria on its way, and in effect cleans itself.
Nanostructures, (tiny waxy "spikes“), on the
surface prevent a water droplet from reaching
the underlying material. It rolls off the waxy
tips which are very small compared to the
water droplet. The force of the rolling water is
greater than the force of attraction between
the surface and dirt or bacteria which allows
it to be washed away.
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…more materials could be

self-cleaning?

water repellant?

Can you think of some?

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The Namibian Beetle
lives in one of the driest deserts in the
world, the Namib on the southwest coast
of Africa, but obtains all of the water it
needs from ocean fog due to the unique
surface of its back. Microscopic bumps
with hydrophilic (water attracting) tips
and hydrophobic (water repelling) sides
cover its hardened forewings, which it
aims at oncoming fog each morning. Water
droplets materialize out of thin air on its
back, then slide down channels into its
awaiting mouth. Synthetic surfaces
mimicking the beetle’s back have been
created that are several times more
effective than existing fog-catching nets,
and could be used to generate clean
freshwater supplies in arid regions,
refugee camps, and at the tops of
skyscrapers, requiring no pumping.

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The nanostructure of
toucan beaks inspires automotive
panels that could protect
passengers in crashes.

 And inspires construction of

ultralight aircraft components.
 Do it yourself: Study the science
behind it

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Hippo’s Nanopowers?
Hippo sweat is
-a sunscreen,
-hydrophilic
-and antibacterial.

It sounds like promising nanoscience. But, personally, I’m

having a little trouble getting excited about smearing
something called hipposudoric acid on my body!

Can you think of interesting ways to use this

nanoscience or to make it sound more appealing?
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We’ve looked at ways scientists are attempting to mimic the
wonders of nanoscience in nature:
•sticky “feet”
•strong spider silk
•self-cleaning light reflecting butterfly wings
•optical nanoscience

•water collecting beetle backs

•tough and light toucan beaks

•and the list could go on and on.

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 The objective – Research proposal (Novelty)
 Brain storming – Thought process
 References (Proper) – Books, Journals etc
 What about literature survey?
 Figures and Figures captions (Numbering)
 Research proposal
 Materials, Methods, applications

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Programmable Nanomaterials
Our tissues and organs form through a process of self-
assembly in which nanoscale molecules come together
with cells to form specialized structures and scaffolds
that guide tissue and organ development. Materials in
Nature are also typically multi-functional – they
provide mechanical support, bind growth factors, and
support cell adhesion – and they exhibit dynamic
behavior that enables them to adjust their structure and
functions in response to physical cues. This contrasts
with man-made materials, which are often designed to
exhibit only a single or narrow range of functions and
which are not responsive to changes in their
environment. The Programmable Nanomaterials are
designing materials from the nano to the macro scales
that mimic the multifunctionality and responsiveness
of natural materials, particularly for regenerative
medicine and drug delivery.

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 Abrasives (using nanoparticles)
 Lubricants
 Composites (high strength, light weight)
 Catalysts
 Insulators
 Membranes technology
 Coatings and paints (nanoparticles)

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 In-situ (Latin)
 situated in the original, natural, or existing place or
position
 Ex-situ
 Opposite of above
 In-vivo
 In vivo for "within the living" is experimentation using a
whole, living organism
 In-vitro
 In vitro means within glass refers to studies in
experimental biology that are conducted using
components of an organism that have been isolated from
their usual biological context

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Energy Production
-Clean, less expensive by novel nanomaterials and
processes
-Fuel cells, Li-ion batteries, solar cells

• Energy Utilization
-High efficiency and durable home and industrial
lighting
-Reduce total electricity consumption
• Materials of construction - sensing changing conditions
in response
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A fuel cell is a device that generates electricity
by a chemical reaction. Every fuel cell has two
electrodes, one positive and one negative,
called the anode and cathode respectively. The
reactions that produce electricity take place at
the electrodes.
Every fuel cell also has an electrolyte, which
carries electrically charged particles from one
electrode to the other, and a catalyst, which
speeds the reactions at the electrodes
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Quite simply, a fuel cell is a device that converts chemical energy into
electrical energy, water, and heat through electrochemical reactions.
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 Anode
 Negative post of the fuel cell.
 Conducts the electrons that are freed from the hydrogen molecules so
that they can be used in an external circuit.
 Cathode
 Positive post of the fuel cell
 Etched channels distribute oxygen to the surface of the catalyst.
 Conducts electrons back from the external circuit to the catalyst
 Recombine with the hydrogen ions and oxygen to form water.
 Electrolyte
 Proton exchange membrane.
 Specially treated material, only conducts positively charged ions.
 Membrane blocks electrons.
 Catalyst
 Special material that facilitates reaction of oxygen and hydrogen
 Usually platinum powder very thinly coated onto carbon paper or cloth.
 Rough & porous maximizes surface area exposed to hydrogen or oxygen

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 Anode side:
2H2  4H+ + 4e-
 Cathode side:
O2 + 4H+ + 4e-  2H2O
 Net reaction:
2H2 + O2  2H2O
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 Pressurized hydrogen gas (H2) enters cell on anode
side.
 Gas is forced through catalyst by pressure.
 When H2 molecule makes contacts with platinum catalyst, it
splits into two H+ ions and two electrons (e-).
 Electrons are conducted through the anode
 Make their way through the external circuit (doing useful work
such as turning a motor) and return to the cathode side of the
fuel cell.
 On the cathode side, oxygen gas (O2) is forced through
the catalyst
 Forms two oxygen atoms, each with a strong negative charge.
 Negative charge attracts the two H+ ions through the
membrane,
 Combine with an oxygen atom and two electrons from the
external circuit to form a water molecule (H2O).

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Advantages
 Fuel cells eliminate pollution; the only by-product
is water
 Fuel cells do not need conventional fuels such as
oil
 Fuel cells have a higher efficiency than diesel or
gas engines
 Most fuel cells operate silently, compared to
internal combustion engines
 The maintenance of fuel cells is simple since there
are few moving parts in the system.
 Fuel cells provide high quality DC power
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Disadvantages
 Fuelling fuel cells is still a major problem since the
production, transportation, distribution and
storage of hydrogen is difficult.
 Reforming hydrocarbons via reformer to produce
hydrogen is technically challenging and not clearly
environmentally friendly.
 Fuel cells are in general slightly bigger than
comparable batteries or engines. However, the size
of the units is decreasing.
 Fuel cells are currently very expensive to produce

 Some fuel cells use expensive materials.

 The technology is not yet fully developed and few

products are available.
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 Introduction
Batteries definition:
Two or more electrochemical cells, electrically
interconnected, each of which contains two electrodes and an
electrolyte. The redox (oxidation-reduction) reactions that
occur at these electrodes convert electrochemical energy into
electrical energy.
In everyday usage, 'battery' is also used to refer to a single
cell. The solid-state batteries are the batteries in which the
electrolyte is in solid state, which is responsible for the
conduction of ions from one electrode to other electrode.

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Secondary batteries

In secondary batteries, the electrochemical reaction is reversible

and the original chemical compounds can be reconstituted by
the application of an electrical potential between the electrodes
injecting energy into the cell.

Such cells can be discharged and recharged many times.

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There are two types of lithium-based batteries available.
1. Lithium batteries
2. Lithium-ion batteries
 In lithium batteries, a pure lithium metallic element
is used as anode. These types of batteries are not
rechargeable.
 In lithium-ion batteries, lithium compounds are
used as anode.
 These batteries are known as re-chargeable
batteries. Therefore, Lithium ion batteries are
considered as best than pure Lithium based
batteries.

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Lithium-ion battery (Li-ion Battery)
Li-ion batteries are secondary batteries.

• The battery consists of a anode of Lithium, dissolved as

ions, into a carbon.
• The cathode material is made up from Lithium liberating
compounds, typically the three electro-active oxide materials,

• Lithium Cobalt-oxide (LiCoO2 )

• Lithium Manganese-oxide (LiMn2 O4 )
• Lithium Nickel-oxide (LiNiO2)

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Principle

• During the charge and discharge processes, lithium ions are

inserted or extracted from interstitial space between atomic
layers within the active material of the battery.

• Simply, the Li-ion is transfers between anode and cathode

through lithium electrolyte.
• Since neither the anode nor the cathode materials essentially
change, the operation is safer than that of a Lithium
metal battery.

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Construction.
• The electrolytes are selected in such a way that there
should be an effective transport of Li-ion to the
cathode during discharge.

• The type of conductivity of electrolyte is ionic in

nature rather than electronic

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 Li- ion Electrolyte

Li-Ion battery Principle

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 - Separation of pollutants
- Catalyst support for conversion reactions
- Waste remediation

• Filters and Membranes

- Removal of contaminants from water
- Desalination- removal of salts/minerals from water

• Reducing auto emissions

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• Thermal barrier and wear resistant coatings

• Battery, fuel cell technology

• Improved displays

• Wear-resistant tires
• High temperature sensors for ‘under the hood’ novel
sensors for vehicles

• High strength, light weight composites for increasing fuel

efficiency

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• Improved collection, transmission, protection of information

• Very high sensitivity, low power sensors for detecting

chem/bio/nuclear threats

• Light weight military platforms, without sacrificing

functionality, safety and soldier security
- Reduce fuel needs and logistical requirements

• Reduce carry-on weight of soldier gear

- Increased functionality per unit weight

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• Advanced miniaturization, a key thrust area to enable new science and
exploration missions
- Ultrasmall sensors, power sources, communication, navigation,
and propulsion systems with very low mass, volume and power
consumption are needed

• Revolutions in electronics and computing will allow “thinking” spacecraft

• Nanotechnology presents a whole new spectrum of opportunities to build

device components and systems for entirely new space architectures

- Networks of ultrasmall probes on planetary surfaces

- Micro-rovers that drive, hop, fly, and burrow
- Collection of micro-spacecraft making a variety of measurements

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 New formulations and routes for drug delivery, optimal drug
usage
 More durable, rejection-resistant artificial tissues and organs
 Sensors for early detection and prevention
 Expanding ability to characterize “genetic makeup” will
revolutionize the diagnostics and therapeutics
 Nanodevices can make gene sequencing more efficient
 Effective and less expensive health care using remote and
in-vivo devices

Lol :-D 111

 With nanotechnology everything is possible.

 With nanotechnology, we will be able to

eliminate cancer and diseases and live forever.

 With nanotechnology, we can easily clean up

the pollution and colonize space.

 Nanotechnology is dangerous. A mistake with

nanomachines can destroy the entire planet
and just leave grey goo behind.

Lol :-D 112

o Nano-machines which can build anything you
want starting from atoms.
o Nano-machines which can swim in your
bloodstream and kill viruses and cancer cells.
o Prosperity, pollution-free industry, almost eternal
life, cure for all diseases, cryonics (low T
preservation) ….
o Smart paints for military applications which can
change camouflage on command and even become
invisible.
o Smart walls in which windows and doors can be
moved on command.

Lol :-D 113

 Theory
 Fabrication of nanostructures
 Precursor nanomaterials and nanoparticles
 Behavior of precursors/particles size shape

 Processing and Characterization

 E.g. electrodes, environment etc

 Integration of nanodevices
 Nano-manufacturing education

Lol :-D 114

Lol :-D 115
 -Silicon Technology-
Semiconductor grade silicon

Lol :-D 116

 Si accounts for about 26 % of the crust
 After Oxygen the most abundant element on earth crust
 Berzellius came up with some form of it in 1824 (amorphous)
 It was Deville in 1854 who first obtained regular crystalline Si
 High chemical reactivity of Si
 Problem in making it and keeping it clean
 Liquid Si indeed does react with all substances known to man - it
is a universal solvent
 This makes crystal growth from liquid Si somewhat tricky
 Hard to produce Si crystals with very low oxygen concentrations
 No other material with properties so precisely matched to the
needs of the semiconductor industry

Lol :-D 117

 Fortunately, the steel industry needs Si, too
 Si was already used as a crucial alloying component of steel before it
started its career as material of our times.
 Metallurgical grade (MG-Si) and Electronic grade (EG-Si)

 Like for most metals, the reducing agent is carbon in the form of coal or
coke
 The chemical reaction that take place at about 2000 oC is
SiO2 + 2C ⇒ Si + 2CO
 There are plenty of other reactions that may occur too,
 e.g. Si + C ⇒ SiC. This will reduce yield of Si
 your reactor ends up as a piece of junk if you make SiC
 What we have to do now is to purify the
MG-Si - about 109 fold

Lol :-D 118

 This can be done in Three steps:

1. First, Si is converted to SiHCl3 (Trichlorosilane)

via the reaction Si + 3HCl ⇒ SiHCl3 + H2

2. Second, the SiHCl3 is distilled resulting in

extremely pure Trichlorosilane

3. Third, high-purity Si is produced by the

Siemens process or, to use its modern name, by
"Chemical Vapor Deposition" (CVD) process

Lol :-D 119

• An optimized mix of SiHCl3 (Trichlorosilane), H2 and doping gases like
AsH3 (Arsine) or PH3 (Phosphine) are admitted into the reactor.
• If everything is right this will only be the Si - a chemical reaction takes place,
reducing the SiHCl3 to Si and forming HCl

SiHCl3 + H2 ⇒ Si + 3 HCl

• The chemistry is extremely dangerous: AsH3 and PH3 are among the most
poisonous substances known to mankind
• PH3 was actually used as a toxic gas in world war II with disastrous
effects.
•HCl (in gaseous form) is even more dangerous

•Still, it works and abut 10.000 tons of poly-Si are produced at present with
this technology

Lol :-D 120

Lol :-D 121
 We now have hyper-pure poly-Si, already doped to the desired
level, and the next step must be to convert it to a single crystal
 Two methods for single crystal growth
1. Czochralski or CZ method (Crucible grown)
 The Czochralski method, invented by the Polish scientist J. Czochralski
in 1916
 The method of choice for high volume production of Si single crystals
 Exceptional quality

2. Float Zone or FZ method

 This method produces crystals with the highest purity
 But is not easily used at large diameters
 150 mm crystals are already quite difficult to make
 Nobody so far has made a 300 mm crystal this way
 Float zone crystal growth is only used for some special purposes

Lol :-D 122

o A crystal is "pulled" out of a vessel containing liquid Si by dipping
a seed crystal into the liquid
o The pulling rate (usually a few mm/min) and the temperature profile
determines the crystal diameter
o Everything else determines the quality and homogeneity
o segregation coefficient kseg of impurity atoms important factor
o Concentration of impurity atoms in the growing crystal and melt
o Usually lower than 1 because impurity atoms "prefer" to stay in
the melt
o Crystal growing is simultaneously a purification method
o why practically only As, P, and B is used for doping?
o Their segregation coefficient assures homogeneous distribution
during crystal growth

Lol :-D 123

Lol :-D 124
 200 mm Si crystal

Thin Si seed crystal

 Not only have to support

the weight of the crystal but
also the torque needed to
rotate

Lol :-D 125

 FZ silicon is a high-purity alternative to crystals grown by the CZ
process
 Based on the zone-melting principle
 Invented by Henry Theuerer in 1962
 Process takes place under vacuum or in an inert gaseous atmosphere
 Starts with a polycrystalline rod and a monocrystalline seed crystal
 The impurities contained in the feed material prefer to remain in the
melt and thus could be swept to the end
 Near-perfect single crystal
 There is no incorporation of impurities that the melt picks up by
dissolving the crucible material
 Oxygen which can not be avoided in CZ crystal growth
 FZ process is used always when very low oxygen concentrations are
important
 Limitations: Large diameter crystals can not be grown

Lol :-D 126

Lol :-D 127
 It may appear rather trivial now to cut the crystal into slices
 wafer production is even difficult than a single Si crystal
production
 Polished surface flatness about 1 µm for all 10.000 or so produced
daily in one factory
 The number of Si wafers sold in 2001 was about 100.000.000 or
roughly 300.000 a day
 Only tightly controlled processes with plenty of know-how and
expensive equipment will assure these specifications
 less than two nm of "native oxide“ forms rather quickly in air and
protects the wafer from chemical attacks
 The final polishing and cleaning steps are done in a cleanroom
where the wafers are packed for shipping
 Labeling: Doping type, Impurity concentrations, Oxygen and carbon
concentration, dopant used (P, As or B), resistivity etc.

Lol :-D 128

o Microelectronics
o IC industry
o Semiconductor
technology
o Solar Cells
o MEMS
o Thin film technology
o Sensors and actuators
o Microfluidics- lab on a chip
o Other in development
phase
Figure: MEMS based microscopic gear- could be
used for mechanically "locking" your computer;
which might be more secure than just software
protection

Lol :-D 129

 Normal air is full of dirt usually called
particles
 What happens when a particle e.g. pollen,
scrapings from whatever unknown things
falls on a chip
 Anything that can "fall" on a chip is called a
particle
 They may be attracted electrostatically and
that makes it quite difficult to remove them
 Everything that falls on a chip with sizes >
0,1 µm or so will be deadly
 We need a clean room for 2 reasons:
 It provides absolutely clean air usually
through filters in the ceiling
 It immediately removes particles generated
somewhere in the cleanroom by pumping Fig: Pollen on wiring matrix of a
256 k Memory array (1985)

Lol :-D 131

 Personnel Control
 Dress code
 Personal Hygiene
 Gowning
 Environmental Control
 Entrance and exit
 Materials and supplies
 Cleaning and maintenance
 Atmospheric

Lol :-D 132

 A cleanroom is a controlled environment in which the concentration of
airborne particles is controlled to specified limits

A cleanroom is more than a filtration system

 The particles/contaminants are generated by people, process, facilities

and equipment

These contaminants can produce a “killer defect”

 Must be continually removed from the air

The only way to control contamination is to control the total

environment

Air flow rates and direction, pressure, temperature, humidity and

specialized filtration all need to be tightly controlled

Lol :-D 133

 Five basic sources - All can contribute to contamination

 1. Facilities
 Walls, floors and ceilings
 Paint and coatings
 Construction material (dry wall, saw dust etc.)
 Air conditioning debris
 Room air and vapors
 Spills and leaks

Lol :-D 134

2. People
 Skin flakes and oil

 Cosmetics

 Spittle

 Clothing debris (fibers etc.)

 Hair

3. Tool Generated
 Friction and wear particles

 Lubricants and emissions

 Vibrations

 Brooms, mops and dusters

Lol :-D 135

4. Fluids
 Particulates floating in air
 Moisture
 Floor finishes or coatings
 Cleaning chemicals
 Plasticizers- clean room gloves
 Deionized water

5. Product generated
 Silicon chips
 Quartz flakes
 Cleanroom debris
 Aluminum particles

Lol :-D 136

 Shower each day before entry
 Control Dandruff
 Do not smoke before entry
 No chewing gum or tobacco
 No Cosmetics should be worn
 Facial hair will need to be covered

Lol :-D 137

 Proper gowning order

 Hair cover
 Coverall
 Shoe covers
 Gloves
 Face mask
 Safety Glasses

Lol :-D 138

 Do Not carry non-cleanroom items into the
cleanroom
 Do not carry cleanroom items out of the
cleanroom
 Do not use pencils or erasers
 Paper should be kept in a plastic sleeve
 Do Not cut the cleanroom wipers
 Clean everything you carry into the cleanroom

Lol :-D 139

 Enter and exit quickly
 Only one person may enter at a time
 Make slow movements inside the clean room
 Pass from the gowning area to the clean area
slowly to reduce migration of particles between
areas
 Leave your stuff at the gowning area or
elsewhere

Lol :-D 140

 Do not take new chemicals into the cleanroom without
permission
 Always read MSDS for every chemical you use
 Large quantities of chemicals must be stored outside
the cleanroom
 Chemicals inside the cleanroom should be properly
stored
 All chemical containers should be clearly labeled with
their contents and Hazard Classification
 Unattended chemicals and experiments should be
labeled with the owners name, immediate contact
number, list of all chemicals involved, and estimated
time of return or completion.

Lol :-D 141

 In case of a small spill
 Inform all users in the cleanroom
 Clearly mark the affected area
 Use appropriate absorbent material to clean up the
spill
 In case of large spill
 Inform all users in the cleanroom
 Clearly mark the affected area and evacuate
 Contact cleanroom staff immediately

Lol :-D 142

 PARTICLES/MINUTE (0.3
PEOPLE ACTIVITY
microns and larger)

Motionless (Standing or Seated) 100,000

Walking about 2 mph 5,000,000

Walking about 3.5 mph 7,000,000

Walking about 5 mph 10,000,000

Horseplay 100,000,000

Lol :-D 143

Lol :-D 144
Lol :-D 145
 Planar technology or layer technology
 Novel techniques with extremely high precision and resolution
have been developed
 Precision has been increased from microns, sub-microns down to
below 20 nm
 Apart from dimensions means of fabrication has also changed
 Though some technological restrictions
 wafer, glass = substrates
 Thick films > 1 μm (practical definition)
 Thin films < 1 μm > 100 nm
 Ultra thin films 1-10 nm
 Continuous layer or structured layer both can be regarded as layer
 Structures that are not connected can also be regarded as a layer

Lol :-D 146

 Several approaches
 Top down approach
 Bottom up approach
 Direct and indirect approaches
 Physical Methods (routes)
 Chemical Methods (routes)

Lol :-D 148

 Photo-litho-graphy: latin: light-stone-writing
 Top-down manufacturing technology
 Great applications in
 Microelectronics (ICs, transistors, etc.)
 Microelectromechanical Systems (MEMS)
 Sensors
 In photolithography, the pattern is created
photographically on a substrate (silicon wafer)

Lol :-D 149

 The steps involved are
 wafer cleaning
 Photoresist application
 +ve photoresist

 -ve photoresist

 Soft baking
 Mask alignment
 Exposure
 Development

Lol :-D 150

  Prepare the substrate (silicon wafer):
 Wash with appropriate solvent to remove any
matter and other impurities
 ethanol, methanol, acetone, *Piranha solution
 Dry in Oven at 80-150°C for some time 5-30 min.
 Place on hotplate and cover with Petri dish
 Remove organic, ionic, and metallic impurities
 Deposit Primer (optional)
 Chemical that coats the substrate and allows for
better adhesion of the resist
*Piranha solution, also known as piranha etch, is a mixture of sulfuric acid (H2SO4)
and hydrogen peroxide (H2O2)

Lol :-D 151

 A layer of SiO2 (silicon dioxide) on the surface of the
wafer is deposited to serve as a barrier
 The thickness of oxide layer is dependent on

 Temperature of the furnace

 Holding time

 Spin on the photoresist on the surface of the wafer

 Standard methods are to use high spin coaters as a function
of rpm and time
 Produces a thin uniform layer of photoresist on the wafer
surface.

Lol :-D 152

 Wafer held onto vacuum
photoresist
chuck dispenser
 Dispense ~5ml of
photoresist
 Slow spin ~ 500 rpm
 Ramp up to ~ 3000 - 5000
rpm
 Quality measures: vacuum chuck
to
 thickness vacuum spindle
 uniformity pump
 particles & defects

Lol :-D 153

 Photoresist is an organic polymer which changes its
chemical structure when exposed to ultraviolet light.
 It contains a light-sensitive substance whose
properties allow image transfer onto a printed circuit
board.
 There are two types of photoresist: positive and
negative
 The resist that becomes more acidic while exposed is
called positive, because the exposed resist is
removed

Lol :-D 154

PHOTORESIST MATERIAL PARAMETERS

A large number of material properties possessed by the

resist play a role in how effectively these functions are
performed which can be grouped into three categories:

(a) Optical properties, including, resolution,

photosensitivity, and index of refraction

b) Mechanical/chemical properties, including:

viscosity, adhesion, etch resistance, thermal stability,
flow characteristics, and sensitivity

c) Processing and safety related properties, including,

cleanliness, metals content, process latitude, and shelf
life.
Lol :-D 155
Positive resists

 Prints a pattern that is the same as the pattern on the

mask
 The resist is exposed to UV light wherever the underlying
material is to be removed
 Exposure to the UV light changes the chemical structure
 Becomes more soluble in the developer
 The exposed resist is then washed away by the developer
solution
 The mask contains an exact copy of the pattern which is
to remain on the wafer.

Lol :-D 156

 Positive Lithography: “Whatever shows goes”

Areas exposed to light

Ultraviolet Light become photosoluble.

Chrome island on
glass mask Island
Shadow on
photoresist
Window
photoresist
Exposed area
of photoresist

photoresist
oxide oxide

silicon substrate silicon substrate

Resulting pattern after the

resist is developed.

Lol :-D 157

Negative resists

 Negative resists behave in just the opposite manner

 Exposure to the UV light causes the negative resist to
become polymerized
 More difficult to dissolve.
 Negative resist remains on the surface wherever it is
exposed
 The developer solution removes only the unexposed
portions
 Masks used for negative photoresists contain the
inverse of the pattern

Lol :-D 158

 Negative Lithography
Ultraviolet Light
Chrome island
on glass mask Exposed
area of
photoresist

Shadow on
photoresist

photoresist
oxide
silicon substrate

Window
Resulting pattern photoresist

after the resist is Areas exposed to light

developed become polymerized and
resist the developing
chemical.
oxide

silicon substrate

Lol :-D 159

Lol :-D 160
Lol :-D 161
Lol :-D 162
 Poly(methyl methacrylate) or PMMA
 Polyurethane
 SU-8- Epoxy based polymer
 Used by IBM but now sold to Microchem
 Phenol formaldehyde resin (Novolac)
 Deep ultraviolet resists (DUV)
 Polyhydroxystyrene base resists

Lol :-D 163

 Partial evaporation of photo-
resist solvents
 Improves adhesion
 Improves uniformity
 Improves etch resistance
 Optimizes light absorbance
characteristics of photoresist

Lol :-D 164

 Transfers the mask image to UV Light Source
the resist-coated wafer
 Activates photo-sensitive
components of photoresist Mask
 Three basic types
 Contact
 Proximity
l
 Projection
 Alignment errors (many
different types)

Lol :-D 165

 Soluble areas of photoresist are dissolved by developer
chemical

 Visible patterns appear on wafer

 windows
 islands
 Quality measures:

 line resolution
 uniformity
 particles & defects

Lol :-D 166

**. Etching can be done chemically or with ion bombardment
Lol :-D 167
 Hard Bake

 Higher temperature
 Evaporate remaining
photoresist
 Improve adhesion

Lol :-D 168

Inspection

 Optical or SEM metrology

 Quality issues:
 particles
 defects
 critical dimensions
 linewidth resolution
 overlay accuracy

Lol :-D 169

 Software Mask
 Processing steps in Photolithography
 It needs a lot of process steps - most of them difficult and complex
- to make a chip.
 Even the most simple 5 mask process requires about 100 process
steps.
 A 16 Mbit DRAM needs about 19 masks and 400 process steps.

To give an idea what this contains, here is a list of the ingredients for a
16 Mbit DRAM at the time of its introduction to the market

 57 layers are deposited (such as SiO2 (14 times), Si3N4, Al, ...).
 73 etching steps are necessary (54 with "plasma etching", 19 with
wet chemistry).
 19 lithography steps are required (including deposition of the
resist, exposure, and development).
 12 high temperature processes (including several oxidations)
 37 dedicated cleaning steps are built in; wet chemistry occurs 150
times altogether.
 158 measurements take place to assure that everything happened
as designed.
Lol :-D 171
Soft Lithography is an umbrella term for a set of techniques that rely on
printing and molding to make microstructures and nanostructures. It was
originally developed in order to circumvent the limitations of
photolithography, which has been the basic technology used for making all
microelectronic systems. The invention of photolithography is arguably as
important as that of the wheel, bronze, or movable type in terms of its impact
on society. It is, however, a technology that is specialized for use in
microelectronics.

Lol :-D 172

 Features
+ Parallel technique: large area patterning
+ Applicable to wide range of materials
+ Applicable to non-planar and liquid surfaces
+ Layer-by-layer 3D structuring possible
+ “Bio-compatible”
+ Low capital & operating costs

PDMS stamp fabrication

PDMS: durable, deformable, chemically & thermally stable, permeable to gases &
solvents, transparent

Lol :-D 173

 Why PDMS?
 Good chemical stability

 Does not swell

 Permeable to gases and solvents

 Thermal stability up to 190 oC

 Optically transparent

 Durable and deformable

Lol :-D 174

Lol :-D 175
Application areas
Electronic components BaTiO3 multi-layer capacitors
MEMS devices, microcantilevers Pb(Zr,Ti)O3
Sensors, biosensors SnO2, nanoporous SiO2
Solar cells TiO2 , SiO2
Electroluminescent pixel displays YVO4:Ln3+-phosphors
Data storage Pb(Zr,Ti)O3
RFID tags Multiferroics, magneto-electric composites
(etc.)

Approaches for precursor solutions for micromoulding

1. Colloidal dispersion of NPs (~40 vol% solids or less)

2. Molecular solution of metal ions or complexes (usually ~10% or less)

Challenges of patterning oxides

 Large shrinkage of precursors (20-95%) during drying & solidification
 Obtaining full control over the shape of patterned features
 Prevent grain growth, coarsening, typical for densifying oxides > 90% density

Lol :-D 176

 Micromolding in Capillaries (MIMIC)
 Microtransfer Molding (µTM)
 Solvent Assisted Micromolding in Capillaries
(SAMIM)
 Replica Molding (REM)
 Microcontact Printing (µCP)
 Nano-Imprint Lithography (NIL)
 Embossing
Lol :-D 177
MIMIC µTM

Lol :-D 178

 Network of empty channels

 Low-viscosity liquid

 Spontaneous filling by capillary action

 Evaporation of solvent & gases

 Solidification within the confines

 Thermal or UV curable

Lol :-D 179

Features
 Quasi-serial patterning technique
 No residual layer; no post-etch required
 Pattern formation based on capillary force
 Applicable for ‘open’ patterns only

Washburn equation:

 gD t dL 1
L~ ~
 4h  dt t

 L, t = penetration length, time

 D = capillary diameter
 h, g = viscosity, surface tension precursor
•TiO2(anatase) Sol-gel Patterns

Lol :-D 181

Results obtained with Soft-lithographic techniques

LaPO4:Eu fluorescence
nanoparticles (6 nm)
embeded in hybrid
organosilica, patterned with
micromolding in capillaries
(MIMIC) technique

PZT line patters by

Soft Confocal Imprint
lithography (SCIL)
and Nano-transfer
molding (NTM),
having line widths =
3D layer by layer sturctures 380 nm
obtained with with
micromolding in capillaries
(MIMIC) technique for
waveguid applications

Sajid et al ACS App. Mater. & Inter. 2009

Lol
182:-D
Lol :-D 183
Precursor solution requirements

 Low viscosity h
 Typically low solids content, hence large
shrinkage

Lower S/V ratio

Higher S/V ratio

Capillary front dries during penetration

Viscosity rise sets penetration length Low-g surface contaminations prevent
Effect increases with S/V ratio penetration of solution in capillary
Lol :-D 184
MIMIC: No spontaneous penetration of precursors PDMS
Hydrophobic
surface

Material Contact angle (°)

PDMS 110
Oxidised Si
Silicon oxide, plasma-treated <5
Hydrophilic
surface

Hydrophilic stamps by O-plasma treatment

120 100
Contact angle/ 

95
110
100
PDMS 90
85
Polyisoprene
80
90
75
80 70
65
70
60
60 55
50
50
45
40 40
35
30
30
20 25
20
10
15
10
10 100 1000 0 10 20 30 40 50 60 70 80 90 100

(Log) Time/ min Time/ min

 Disadvantage: penetration under stamp; formation of a residual layer

 Stamp with hydrophilic and hydrophobic patches required
Lol :-D 185
TiO2 patterns on Si
Precursor: TiO2 (80 nm, in water), patterns annealed at 600°C

_
5 mm

BaTiO3 on Si Fluorescent LaPO4:Eu NPs embedded in hybrid organosilica

CSD in 2ME; 800°C based on (OR)3Si-C2H4-Si(OR)3 sol-gel precursor

Lol :-D 186

Shrinkage problems occur with increasing object size
Cure: down-scaling feature sizes

Examples of shrinkage in sol-gel TiO2

Isolated objects by MIMIC

Lol :-D 187

Physical drying
Example: TiO2 nanoparticles, 80 nm, 12 vol% in water; thermally treated at 550°C
 PDMS stamp

Physical & chemical drying

Pattern (wet)
Occurs in gelling systems, sol-gel silica, CSD solutions
Si substrate

Si substrate

AFM Sol-gel titania

Si substrate

SEM BaTiO3 Line pattern Martin & Aksay, J. Mater. Res. 2003

AFM Sol-gel organosilica

 Titania line pattern by MIMIC

Lol :-D Organosilica line pattern by mTM 190

 MIMIC & mTM applied to make 2D patterns and 3D structures of
oxides
 Obtaining control over shape of pattern for 3D stacking remains
challenge

 mTM
 Applicable for both connected and isolated patterns
 No Residual layer or very thin
 Pattern shapes different than MIMIC

 MIMIC
 Demanding technique, many parameters to optimize
 Penetration of precursors in PDMS channels problematic
 More hydrophilic stamps required, but residual layer becomes a
problem

 Solid state contents of liquid oxide precursors very low

 Severe shrinkage, applicability limited to objects ~10 mm or
smaller

Lol :-D 191

 Many approaches and names e.g.
 Nano-Imprint Lithography (NIL)
 Embossing (hot embossing or RT)
 Soft-Confocal-Imprint lithography (SCIL)
 Hard Imprint lithography
 Soft-Nano-Imprint lithography
 Somewhat same as conventional Micromolding (CµM)

**Innanofabrication one needs to be tricky and use different

direct and indirect approaches towards the fabrication and
integration

Lol :-D 192

 Nano-Imprint process
Stamp
A stamp is fabricated by electron beam lithography
Polymer
Substrate (EBL) and dry etching

The stamp is pressed into a soft thermoplastic,

thermosetting or UV-curable polymer or other
materials on a substrate combined with heating
or UV radiation
The polymer is cured and the stamp release
from substrate

Residual imprint polymer under stamp

protrusion removed by ‘descum’ process

Imprinted pattern transferred into substrate by

dry etching

Lol :-D 193

 Versatile, cost effective, flexible and high throughput (parallel)
method for fabrication of down to 10 nm structures even over large
areas (wafers)

Applications in:

•Semiconductor memory
•Micro and nano fluidics
•Optical devices e.g. LEDs and lasers
•Life science, e.g. lab-on-a-chip systems, bio sensors
•Radio frequency components
•Renewable energy
•Security (holography, tags, etc.)
•Nanotechnology

Lol :-D 194

Lol :-D 195
Lol :-D 196
Lol :-D 197
 Upgrade Parts Include

 Stamp
 Stamp Holder
 Substrate Holder
 Stamping control

Lol :-D 198

Lol :-D 199
Lol :-D 200
Lol :-D 201
Lol :-D 202
Lol :-D 203
 Contact printing is an efficient method for
pattern transfer
 A conformal contact between the stamp and the
surface of the substrate is the key to its success
 Printing has the advantage of simplicity and
convenience
 Once the stamp is available multiple copies of
the pattern can be produced
 Printing also has the potential to be used for
patterning large areas

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 Microcontact printing is one of the most useful techniques for
generating patterns of functional organic surfaces over large areas
(>cm2)
 The general procedure brings a topographically patterned PDMS
stamp, wetted with a solution of an alkanethiol or other molecules
(phosphonic acids, alkylsiloxanes, isocyanides) that can form SAMs
into contact with the surface of a metal, metal oxide, or
semiconductor for a few seconds
 An ordered monolayer forms rapidly at the points of contact (As
shown in Figure in next slide )
 This procedure works best with alkanethiols and derivatives on
gold, silver, palladium, and platinum
Microcontact printings give lower-resolution features
 This methodology can tailor properties (wettability,
biocompatibility, reactivity) of the surface, by transferring organic
films that are only 1 to 2 nm thick
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 The concept of Microcontact printing use the relief pattern on the
surface of a PDMS stamp to form patterns of SAMs on the surfaces of
substrates by contact. For example, alkylthiol on Au and Ag surfaces.

Simple and suitable for non-planar

substrates!
Xia, Y. N. and Whitesides, G. M. “Soft Lithography”. Annu. Rev. Mater. Sci. 28, 153-184
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(1998)
Making metal electrodes by Microcontact printing

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