Introduction to nanoscience and nanotechnology

Pandit Deendayal Petroleum
University
Introduction to Nanoscience and
Nanotechnology
Dr. Bharat Parekh
School of Technology
Pandit Deendayal Petroleum University
Gandhinagar-382007
Gujarat, India

Plan of the Talk

• Nanoscience-Definition
• Background
• Lesson from Nature
• Building nano structures
• Synthesis of nanomaterials (CdTe)
• Applications in different field
• Nano Industry
• Summary

Introduction
• A biological system can be exceedingly small. Many of
the cells are very tiny, but they are very active; they
manufacture various substances; they walk around;
they wiggle; and they do all kinds of marvelous
things—all on a very small scale. Also, they store
information. Consider the possibility that we too can
make a thing very small that does what we want—that
we can manufacture an object that maneuvers at that
level.
(From the talk “There’s Plenty of Room at the Bottom,” delivered by Richard
P. Feynman at the annual meeting of the American Physical Society at the
California institute of Technology, Pasadena, CA, on December 29, 1959.)

What is Nanoscience?
When people talk about Nanoscience, many start by
describing things
• Physicists and Material Scientists point to things like
new nanocarbon materials:

• They effuse about nanocarbon’s strength and electrical
properties

Graphene Carbon Nanotube C60 Buckminster
Fullerene
"We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience

Biologists counter that nanocarbon is a recent discovery
THEY’VE been studying DNA and RNA for much longer
(And are already using it to transform our world)


And Chemists note THEY’VE synthesized molecules for over a
century
<= First OLED material: tris 8-hydroxyquinoline
aluminum
(OLED = organic light emitting diode)

Commercial OLED material: Polypyrrole

Most heavily investigated molecular electronic switch: Nitro oligo
phenylene ethynylene

All of these things ARE very small
Indeed, they are all about the size of a nanometer:
Nano = 10-9 = 1/ 1,000,000,000 = 1 / Billion A nanometer is
about the size of ten atoms in a row

This leads to ONE commonly used definition of nanoscience:
Nanoscience is study of nanometer size things (?)

Why the question mark? Because what is so special about a
nanometer?
A micrometer is ALSO awfully small:
Micro = 10-6 - 1/1,000,000 = 1 / Million
A micrometer (or "micron") is ~ size of light's wavelength


And microtechnology has been rolling along for half a
century!
Microelectronics = Integrated circuits, PC's, iPods, iPhones . . .

Intel 4004: The original "computer on a chip" - 1971 (Source: UVA Virtual Lab)

Also = MEMS (Micro-electro-mechanical-systems):
Air bag accelerometers, micro-mirror TVs & projectors . . .

(Source: Texas Instruments DLP demo - www.dlp.com/tech/what.aspx)


Indeed, microtechnology has gotten smaller EVERY year

MOORE'S LAW: The (then almost whimsical) 1965 observation by Intel co-
founder Gordon Moore that the transistor count for integrated
circuits seemed to be doubling every 18-24 months

He was really sticking his neck out: IC's had only been invented 7 years before!
(by Moore, his Fairchild/Intel colleagues, and Texas Instrument's Jack Kilby)

But his "law" has since been followed for forty five years:

(Source: www.intel.com/technology/mooreslaw/index.htm)


So is Nanoscience/technology really new & unique?
• Micro is also VERY small
• Micro has been around for a long time
• Micro has steadily shrunk to the point that it is now
almost NANO anyway !
• Leading to a LOT of confusion about the distinction
between Micro & Nano
• Even among scientists!!
• And likelihood that Nanotechnology will be built UPON
Microtechnology
• Either by using certain Microfabrication techniques Or,
literally, by being assembled ATOP Microstructures

Meaning that the NANO "revolution" is just a lot of hype?

Just about making things incrementally smaller?
Just about a simple shift in the most convenient unit of
measure?
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


Boundary :
ELECTRON WAVES Separate NanoSCIENCE from MicroSCIENCE
The discovery that electrons = waves led to QUANTUM MECHANICS
A weird, new, counter intuitive, non-Newtonian way of looking at
the nano world With a particular impact upon our understanding of
electrons: Electrons => Waves

How do you figure out an electron’s wavelength?
electron = h / p
“De Broglie’s Relationship”( = electron wavelength, h = Planck’s
Constant, p = electron’s momentum)
This relationship was based on series of experiments late 1800’s /
early 1900’s
To put the size of an electron’s wavelength in perspective:


Nanometer Scale - Unknown Behavior

• “Magical Point on Length Scale, for this is the point
where the smallest man-made devices meet atoms
and molecules of the natural world.”
– Eugene Wong, Knight Rider Newspapers, Kansas City Star, Monday Nov.
8th, 1999

• Just wait, the next century is going to be incredible.
We are about to be able to build things that work at
the smallest possible length scales, atom by atom .
These little nanothings will revolutionize our
industries and our lives.”
– R. Smalley, Congressional Hearings, Summer 1999.

Size of Things
Millimeters Microns Nanometers

Ball of a ball point pen 0.5
Thickness of paper 0.1 100
Human hair 0.02 - 0.2 20 – 200
Talcum Powder 40
Fiberglass fibers 10
Carbon fiber 5
Human red blood cell 4–6
E-coli bacterium 1
Size of a modern transistor 0.25 250
Size of Smallpox virus 0.2 – 0.3 200 – 300

Electron wavelength: ~10 nm or less
Diameter of Carbon Nanotube 3
Diameter of DNA spiral 2
Diameter of C60 Buckyball 0.7
Diameter of Benzene ring 0.28
Size of one Atom ~0.1


How Big is a Nanometer?
• Consider a human hand

skin

white blood cell DNA atoms
nanoscale

Source: http://www.materialsworld.net/nclt/docs/Introduction%20to%20Nano%201-18-05.pdf

History of Nanomaterials
• 1974 The word Nanotechnology first coined by Nario
Taniguchi, Univ. of Tokyo --- production technology
to get ultra fine accuracy and precision – 1nm

• 1981 IBM invented STM scanning tunneling
microscope which can move single atoms around

• 1985 new form of carbon discovered --- C60
buckminister fullerene 60 carbon atoms arranged in
a sphere made of 12 pentagons and 20 hexagons


Lycurgus chalice 4th Century A.D.
Appears green in reflected light and red if light is directed
through it (70 nm particles of silver and gold in the glass)

Lycrugus
Lycrugus cup with
cup with
focused light
diffused
light


• 1991 carbon nanotubes discovered “graphitic
carbon needles ranging from 4 nm – 30 nm and up to
1 micron in length”
( Sumino Iijima)

• 1993 First high quality quantum dots prepared ---
very small particles with controlled diameters of CdS,
CdSe, CdTe


• 2000 First DNA motor made similar to
motorized tweezers may make computers
1000 more powerful.

DNA motors can be attached to
electrically conducting
molecules – act as basic
switches

Nature 406 (6796) 2000, 605-608.


• 2001 prototype fuel cell made with nanotubes

• 2002 Nanomaterials make stain repellant
trousers Nano-care khakis have nanowhiskers
(10-100 nm in length)

Lesson from Nature

• Nano airborne particles (100 -1000 nm) cause
water to condense and form raindrops or
snowflakes
• Plankton – varies in sizes from (1- 100 nm)
Marine bacteria and viruses

Glucose and Glucose oxidase

All cells require glucose (0.6 nm)
as a fuel for metabolism.

Energy is released from glucose
when it is precisely positioned
relative to the glucose oxidase
enzyme
( 5 nm)

Lock and key mechanism
common in biology

Actin and Myosin

Actin and myosin
molecules form the system
responsible for muscle
contraction.
The system operates by a
series of steps where the
head of myosin molecule
pulls the actin past itself by
10–28 nm each step.

NATURE - Gecko Power

Gecko foot hairs typically have diameters
of 200 – 500 nm. Weak chemical interaction
between each hair and surface (each foot has
over 1 million of these hairs) provides a force
of10 N/cm2.
This allows Gecko’s to walk upside down across
glass ceilings.

Nanoparticles in Smoke from Fires

Bucky Balls (C60) were discovered in soot!

Ferrofluids
Coated Iron oxide nanoparticles

(wikipedia)

•Great demo
•Buy ferrofluid, use
•Synthesize ferrofluid

Nanoscience Is Everywhere
in Nature

• Living cells have been using their own nanoscale
devices to create structures one atom or
molecule at a time for millions of years.
• To be specific, DNA is copied, proteins are
formed, and complex hormones are
manufactured by cellular devices far more
complex than the most advanced manufacturing
processes we have today.

http://dallas.bizjournals.com/dallas/stories/2001/09/10/focus2.html?page=3

So How Did We Get Here?

New Tools!
As tools change, what we can see
and do changes

Using Light to See

• The naked eye can see to about 20 microns
• A human hair is about 50-100 microns thick
• Light microscopes let us see to about 1 micron
• Bounce light off of surfaces to create images

to see red blood cells
Light microscope (400x)
(magnification up to 1000x)

Sources: http://www.cambridge.edu.au/education/PracticeITBook2/Microscope.jpg
http://news.bbc.co.uk/olmedia/760000/images/_764022_red_blood_cells300.jpg

Using Electrons to See
• Scanning electron microscopes (SEMs),
invented in the 1930s, let us see objects as
small as 10 nanometers
– Bounce electrons off of surfaces to create images
– Higher resolution due to small size of electrons

(4000x)

Greater resolution to see things like blood cells in greater detail
Sources: http://www.biotech.iastate.edu/facilities/BMF/images/SEMFaye1.jpg
http://cgee.hamline.edu/see/questions/dp_cycles/cycles_bloodcells_bw.jpg

Touching the Surface

• Scanning probe
microscopes,
developed in the
1980s, give us a
new way to “see”
at the nanoscale
• We can now see
really small About 25 nanometers

things, like atoms,
and move them
too! This is about how big atoms are
compared with the tip of the
microscope
Source: Scientific American, Sept. 2001

Scanning Probe Microscopes

• Atomic Force Microscope (AFM)
– A tiny tip moves up and down in response to the
electromagnetic forces between the atoms of the
surface and the tip
– The motion is recorded and used to create an image
of the atomic surface
• Scanning Tunneling Microscope (STM)
– A flow of electrical current occurs between the tip
and the surface
– The strength of this current is used to create an image
of the atomic surface

Is Gold Always “Gold”?

• Cutting down a cube of gold
– If you have a cube of pure
gold and cut it, what color
would the pieces be?
– Now you cut those pieces.
What color will each of the
pieces be?
– If you keep doing this - cutting
each block in half - will the
pieces of gold always look
“gold”?

Source: http://www.uwgb.edu/dutchs/GRAPHIC0/GEOMORPH/SurfaceVol0.gif

Nanogold

• Well… strange things happen at
the small scale
– If you keep cutting until the
gold pieces are in the nanoscale
range, they don’t look gold
anymore… They look RED!
– In fact, depending on size, they 12 nm gold particles look red
can turn red, blue, yellow, and
other colors Other sizes are other colors

• Why?
– Different thicknesses of materials
reflect and absorb light differently

Source: http://www.nano.uts.edu.au/pics/au_atoms.jpg

Nanostructures

What kind of nanostructures can we
make?

What kind of nanostructures exist in
nature?

Carbon Nanotubes

• Using new techniques,
we’ve created amazing
structures like carbon
nanotubes
• 100 time stronger than
steel and very flexible
• If added to materials
like car bumpers,
increases strength and
flexibility
Model of a carbon nanotube

Source: http://www.library.utoronto.ca/engineering-computer-science/news_bulletin/images/nanotube.jpeg

Carbon Buckyballs (C60)

• Incredible strength due
to their bond structure
and “soccer ball”
shape
• Could be useful
“shells” for drug
delivery
• Can penetrate cell walls
• Are nonreactive (move
safely through blood
stream)
Model of Buckminsterfullerene

Source: http://digilander.libero.it/geodesic/buckyball-2Layer1.jpg

Biological Nanomachines in Nature

• Life begins at the
nanoscale
– Ion pumps move
potassium ions into and
sodium ions out of a cell
– Ribosomes translate RNA
sequences into proteins
– Viruses infect cells in
biological organisms and
reproduce in the host cell

Source: http://faculty.abe.ufl.edu/~chyn/age2062/lect/lect_06/lect_06.htm
Influenza virus
http://www.zephyr.dti.ne.jp/~john8tam/main/Library/influenza_site/influenza_virus.jpg

Building Nanostructures

How do you build things that are so
small?

Fabrication Methods

• Atom-by-atom assembly
– Like bricklaying, move atoms into
place one at a time using tools like the
AFM and STM IBM logo assembled
• Chisel away atoms from individual xenon
atoms
– Like a sculptor, chisel out material
from a surface until the desired
structure emerges
• Self assembly
– Set up an environment so atoms
assemble automatically. Nature uses
self assembly (e.g., cell membranes) Polystyrene
spheres self-
assembling
Source: http://www.phys.uri.edu/~sps/STM/stm10.jpg; http://www.nanoptek.com/digitalptm.html

Example: Self Assembly By Crystal Growth

• Grow nanotubes like trees
– Put iron nanopowder crystals
on a silicon surface
– Put in a chamber
– Add natural gas with carbon
(vapor deposition)
– Carbon reacts with iron and
Growing a forest of nanotubes!
forms a precipitate of carbon
that grows up and out
• Because of the large number of structures you can create
quickly, self-assembly is the most important fabrication
technique
Source: http://www.chemistry.nmsu.edu/~etrnsfer/nanowires/

Arrested Precipitation: General Approach

• Aqueous reduction of metal salts (Ag, Au) in the presence of
• citrate ions
• – Chemisorption of organic ligands for handling
• – Distribution varies > 10%
II-VI ME nanocrystals (NCs) (M =
Zn, Cd, Hg; X = S, Se, Te)
• – Metal alkyls + organophosphine
chalcogenides
• – Phosphine binding to M
controlled by temperature
• – Ostwald ripening allows for size-
selective aliquots; growth time for
1-2 nm NCs in minutes

Synthesis of Nanomaterials

• CdSe nanocrystals

• CdO + oleic acid + octadecene
• Heat to 250° C to dissolve the CdO

• Selenium + octadecene + tributylphosphine
• Heat to 150° C to dissolve the selenium

• Transfer Se solution to the Cd solution
• Take aliquots

Potential Impacts of Nanotechnology

• Materials • Technology
– Stain-resistant clothes – Better data storage
• Health Care and computation
– Chemical and biological • Environment
sensors, drugs and – Clean energy, clean air
delivery devices

Thin layers of gold are used in Carbon nanotubes can be used Possible entry point for
tiny medical devices
47 for H fuel storage nanomedical device

Materials: Stain Resistant Clothes

• Nanofibers create cushion of air around fabric
– 10 nm carbon whiskers bond with cotton
– Acts like peach fuzz; many liquids roll off

Nano pants that refuse to stain; Nano-Care fabrics with water, cranberry juice,
Liquids bead up and roll off vegetable oil, and mustard after 30 minutes (left)
and wiped off with wet paper towel (right)

48
Sources: http://www.sciencentral.com/articles/view.php3?article_id=218391840&cat=3_5
http://mrsec.wisc.edu/Edetc/IPSE/educators/activities/nanoTex.html

Materials: Paint That Doesn’t Chip

• Protective nanopaint
for cars
– Water and dirt
repellent
– Resistant to chipping
and scratches Mercedes covered with tougher, shinier
– Brighter colors, nanopaint

enhanced gloss
– In the future, could
change color and self-
repair?

49
Sources: http://www.supanet.com/motoring/testdrives/news/40923/

Environment: Paint That Cleans Air

• Nanopaint on buildings
could reduce pollution
– When exposed to
ultraviolet light, titanium
dioxide (TiO2)
nanoparticles in paint
break down organic and
inorganic pollutants that Buildings as air purifiers?
wash off in the rain
– Decompose air pollution
particles like formaldehyde

50
Sources: http://english.eastday.com/eastday/englishedition/metro/userobject1ai710823.html

Environment: Nano Solar Cells

• Nano solar cells mixed in plastic could be
painted on buses, roofs, clothing
– Solar becomes a cheap energy alternative!

] 200 nm

Nano solar cell: Inorganic nanorods embedded in semiconducting
polymer, sandwiched between two electrodes

51
Source: http://www.berkeley.edu/news/media/releases/2002/03/28_solar.html

Technology: A DVD That Could Hold a Million Movies

• Current CD and DVD media have
storage scale in micrometers
• New nanomedia (made when gold
self-assembles into strips on
silicon) has a storage scale in
nanometers
…or 1,000,000
– That is 1,000 times more storage
along each dimensiontimes greater
(length,
storage density
width)… in total!
52
Source: Images adapted from http://uw.physics.wisc.edu/~himpsel/nano.html

Technology: Building Smaller Devices and Chips

• Nanolithography to create tiny patterns
– Lay down “ink” atom by atom

Transporting molecules to a surface by
Mona Lisa, 8 microns tall, created by
dip-pen nanolithography
AFM nanolithography

53
Sources: http://www.ntmdt.ru/SPM-Techniques/Principles/Lithographies/AFM_Oxidation_Lithography_mode37.html
http://www.chem.northwestern.edu/~mkngrp/dpn.htm

Health Care: Nerve Tissue Talking to Computers

• Neuro-electronic networks interface nerve
cells with semiconductors
– Possible applications in brain research,
neurocomputation, prosthetics, biosensors

Snail neuron grown on a chip that records the neuron’s activity

54
Source: http://www.biochem.mpg.de/mnphys/publications/05voefro/abstract.html

Health Care: Detecting Diseases Earlier

• Quantum dots glow in UV light
– Injected in mice, collect in tumors
– Could locate as few as 10 to 100 cancer cells

Quantum Dots: Nanometer-sized crystals that
contain free electrons and emit photons when
submitted to UV light

Early tumor detection,
55
Sources: http://vortex.tn.tudelft.nl/grkouwen/qdotsite.html
studied in mice
http://www.whitaker.org/news/nie2.html

Health Care: Growing Tissue to Repair Hearts

• Nanofibers help heart muscle grow in the lab
– Filaments ‘instruct’ muscle to grow in orderly way
– Before that, fibers grew in random directions

Cardiac tissue grown with the help of nanofiber filaments

56
Source: http://www.washington.edu/admin/finmgmt/annrpt/mcdevitt.htm

Health Care: Preventing Viruses from Infecting Us

• Nanocoatings over proteins on viruses
– Could stop viruses from binding to cells
– Never get another cold or flu?

Gold tethered to the
Influenza virus: Note proteins on
protein shell of a virus
outside that bind to cells

57
Sources: http://www.zephyr.dti.ne.jp/~john8tam/main/Library/influenza_site/influenza_virus.jpg
http://pubs.acs.org/cen/topstory/8005/8005notw2.html

Health Care: Making Repairs to the Body

• Nanorobots are imaginary, but nanosized
delivery systems could…
– Break apart kidney stones, clear plaque from
blood vessels, ferry drugs to tumor cells

58
Source: http://www.genomenewsnetwork.org/articles/2004/08/19/nanorobots.php

The Nano Industry
• Biotechnology
– Platypus
• Equipment suppliers – Bioforce Nanoscience
– Imago Instruments – Atom probe – Ace Ethanol
microscope
– Hysitron Inc • Healthcare
– Thermo electron – Medtronic
– Boston Scientific
• Advanced materials
– 3M
– Cima Nanotech • Energy
– Nanodynamics – Fuel cells
• Electronics – A natural – Konarka – Flexible solar panels
progression – Cymbet
– Intel
– HP • Defense and security
– Motorola
– Detecting explosives and bio
– IBM agents
– MIT Institute of Soldier
Nanotechnologies

FNI 1A 59

The Nano Industry

• NNI http://www.nano.gov/
• NNIN http://www.nnin.org/
• MRSEC http://www.mrsec.wisc.edu/Edetc/
• NanoHUB http://www.nanohub.org/
• Conferences: NSTI, UMN,
– http://www.nsti.org/
– http://www.nano.umn.edu/conference2008/
• Nanorite Center http://www.nanorite.org/
• Nano in the News

FNI 1A 60

Future of Nanotechnology
“Nanotechnology products worldwide will be $2.6 Trillion or
15% of global manufacturing output.” Investing in
Nanotechnology -- Jack Uldrich

Enablers and tools: Hysitron, Imago

Nanomaterials: Carbon Nanotechnologies, Aspen Aerogels

Fortune 500 Companies: 3M, Affymetrix, Cabot, Dow, Dupont,
Kodak, Texaco, AMD, GE, HP, IBM, Intel, Motorola, NEC

Disrupters: Bioforce Nanoscience, Nanosolar

FNI 1A 61

Potential Risks of Nanotechnology
• Health issues
– Nanoparticles could be inhaled, swallowed,
absorbed through skin, or deliberately injected
– Could they trigger inflammation and weaken the
immune system? Could they interfere with
regulatory mechanisms of enzymes and proteins?
• Environmental issues
– Nanoparticles could accumulate in soil, water,
plants; traditional filters are too big to catch them
• New risk assessment methods are needed
– National and international agencies are beginning
to study the risk; results will lead to new
regulations
62

Summary: Science at the Nanoscale

• An emerging, interdisciplinary science
– Integrates chemistry, physics, biology, materials
engineering, earth science, and computer science
• The power to collect data and manipulate particles at
such a tiny scale will lead to
– New areas of research and technology design
– Better understanding of matter and interactions
– New ways to tackle important problems in
healthcare, energy, the environment, and
technology
– A few practical applications now, but most are
years or decades away

63

Mother Nature

Mankind has always found inspiration in
Mother Nature. Today developing
technologies allow us to probe and better understand the
nanoscience of Mother Nature.

Introduction to Nanoscience
1. Intro to Nano 2. The Nano Debate 3. History of Nano 4. Scale of Things
Nano Industry Ch 1, Smalley vs Drexler Future of Nano Ch 15 Nano Ch 1
2,16 Ch 15
5. Nanochemistry 6. The Atom Game 7. Quantum 8. Waves – Slinkys,
Ch 3 Ch 3 mechanics (Ch 6) Light and Orbitals Ch
Unit 1Test 3
9. Tools of Nano Ch 3 10. Microscopy 1 11. Electron 12. Microscopy 2
Optical and Electron microscopy Ch 3 Electron beam
Ch 3 specimen interactions
13. Scanning probe 14. Microscopy 3 15. Other Tools Ch 3 16. UWEC Field Trip
microscopy Ch 3 Scanning Probe Ch 3 Test 2
17. X-Ray Analysis 18. X-Ray Diffraction 19. Carbon 22. Carbon
Ch 3 Nanotubes Ch 4 Nanotubes

21. Nanomaterials Ch 20. Gold 23. Synthesis/self 24. Magnetic
5, 12 Nanoparticles assembly/Test 3 Nanoparticles

25. Special Topics 26. Alternative energy 27. Special Topics 28. Lab on a Chip
Energy Ch 9 applications of Nano Biomedical Ch 10-11
29. Student 30. Student 31. Final Exam 32. Last Day
Presentations
FNI 1A Presentations 65

Introduction to nanoscience and nanotechnology

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