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A/Prof Jeffrey Funk
Division of Engineering and
Technology Management
National University of Singapore
When Will NanoTechnology-Based
Products Become Economically
Feasible for Specific Applications?
For information on other technologies, see http://www.slideshare.net/Funk98/presen
Session Technology
1 Objectives and overview of course
2 Two types of improvements: 1) Creating materials that
better exploit physical phenomena; 2) Geometrical scaling
4 Semiconductors, ICs, electronic systems
5 MEMS and Bio-electronic ICs
6 Nanotechnology and DNA sequencing
7 Superconductivity and solar cells
8 Lighting and Displays
9 Human-computer interfaces (also roll-to roll printing)
10 Telecommunications and Internet
11 3D printing and energy storage
This is Part of the Sixth Session of MT5009
Objectives
 What are the important dimensions of
performance for nanotechnologies and their
higher level systems?
 What are the rates of improvement?
 What drives these rapid rates of improvement?
 Will these improvements continue?
 What kinds of new systems will likely emerge
from the improvements in nanotechnology?
 What does this tell us about the future?
As Noted in Previous Session, Two
main mechanisms for improvements
 Creating materials (and their associated processes)
that better exploit physical phenomenon
 Geometrical scaling
 Increases in scale
 Reductions in scale
 Some technologies directly experience
improvements while others indirectly experience
them through improvements in ―components‖
A summary of these ideas can be found in
1) What Drives Exponential Improvements? California Management Review, Spring 2013
2) Technology Change and the Rise of New Industries, Stanford University Press, 2013
3) Exponential Change: what drives it? What does it tell us about the future?
Both are Relevant to Nanotechnology
 Creating materials (and their associated processes)
that better exploit physical phenomenon
 Creating materials such as carbon nanotubes that better
exploit small dimensions
 Geometrical scaling
 Increases in scale: larger production equipment
 Reductions in scale: exploiting phenomena at small
dimensions; ability to create smaller dimensions enables
more phenomena to be exploited. Some people argue that
―thin film‖ is part of every important technology
 Some technologies directly experience
improvements while others indirectly experience
them through improvements in ―components‖
 Better nanotechnology-based products lead to better
electronic systems
Both Relevant to Nanotechnology
(cont)
 Rapid improvements in integrated circuits (ICs),
magnetic storage, other electronic technologies
over last 50 years
 Moore‘s Law
 Areal recording density of hard disk platters
 These improvements have enabled many new
forms of electronic products and improvements in
them
 Computers, Mobile Phones, Internet
 Is there a similar or greater potential for
nanotechnology?
 Are there indications of this potential in a
Outline
 What is nanotechnology?
 Fullerene, Graphene and Carbon
Nanotubes
 Quantum Dots
 Nanoparticles
 Nanofibers
 Common issues
What is NanoTechnology? (1)
 Things on the nano-meter (10-9) level: 1-100 nm
 ICs, MEMS, and bio-electronics can be considered
nano-technology
 But,
 nano-technology should take us to smaller
scale, molecular or even atomic level
 like ICs, these technologies should benefit from the
reductions in scale that these nano-dimensions
represent
 involve self-assembly (like with snowflakes and
biological reproduction) so that the costs of making
them are low
 Have progress that is measurable and identifiable
http://www.nanostart.de/index.php/en/nanotechnology/tiny-structures-with-a-
big-future
(Currently, mostly
semiconductors and
pharmaceuticals)
Too Much
Hype!!!!
http://www.nanowerk.
com/spotlight/spotid
=1792.php
What is NanoTechnology? (2)
 One-dimensional nanoproducts
 thin film devices, coatings (antireflection, corrosion),
graphene and quantum wells (stacked thin film layers)
 found in semiconductor, metallic, and dielectric films
 • Two-dimensional (2-D) nanoproducts
 single or multiwall nanotubes
 nanowires, nanorods
 Three-dimensional (3-D) nanoproducts
 fullerenes,
 dendrimers
 nanoparticles
 polymeric dispersions
Why do we care? From Large to Small
 A number of physical phenomena become
pronounced as the size of the system decreases
 increase in surface area to volume ratio altering
mechanical, thermal and catalytic properties
 statistical and quantum mechanical effects at less than
100 nanometers
 hydrogen bonding, molecular forces, van der waals
forces
 Different properties appear at the nano-scale,
enabling unique applications
 opaque substances become transparent (copper)
 stable materials turn combustible (aluminum)
 insoluble materials become soluble (gold)
 high thermal and electrical conductivities and strength
(carbon)
As the size of a
particle
becomes smaller,
van der walls (vdw)
forces (i.e., electro-
magnetic forces
between neutral
atoms) become
much more
important than
gravitational forces
(earth-particle and
particle-particle)
Source: Treavor A. Kendall,
Once we have Small Things, How
can we Make Big Things?
 Top-down approaches are too expensive
 Micro-machining
 Photolithography
 Electron-beam lithography
 Focused ion beams
 Bottom-up, or so-called self assembly is
needed
 Modern synthetic chemistry enables synthesis of
chemicals from molecules
 New methods are needed
Manufacturing Processes are Critical
 Processes determine costs and performance of nano-
products
 Needed characteristics of processes
 High purity: often need 99.9999999%
 High material yields: low yields are common in many
processes such as molecular beam epitaxy (3-10%) or
metal organic CVD (theoretical limit is 50%)
 Small number of process steps
 Low temperature and vacuum requirements as these
raise costs
 Benefits from increases in scale of equipment, such as
those that exist in chemical plants and production of liquid
Outline
 What is nanotechnology?
 Fullerene, Graphene and Carbon
Nanotubes
 Quantum Dots
 Nanoparticles
 Nanofibers
 Common issues
Fullerenes, Graphene, and Carbon
Nanotubes
Fullerenes
specific number of carbon
atoms
arranged as sphere
20 is the smallest, many
other
stable numbers
Graphene
flat sheet of carbon atoms
Carbon Nanotubes
flat sheet is rolled so that
sides
are connected, thus
Fullerenes
As size of fullerenes increases, energy gap between highest
and lowest orbital also decreases where this gap is
analogous to the band gap in semiconductors
One can also dope fullerenes by inserting atoms inside of
them
Thus, one can design fullerenes with specific electronic
properties as with semiconductors
Depending on purity, price of fullerenes is more than $100 per
gram
Graphene
 A single layer of carbon atoms
 Very low electrical resistance, high thermal conductivity
(4,000 W/m-K), and high mobility (about 200,000
cm2/Vs at room temperature, compared to 1,400 in
silicon and 77,000 in indium antimonide)
 One of strongest materials, but yet flexible
 Unusual optical behavior: equally transparent to
ultraviolet, visible and infrared light
 Two current markets (composites for strength and
electrodes for conductivity) but also displays, computer
chips, and solar cells
 http://www.youtube.com/watch?v=XDJRlBSXsow
Source: Segal, Michael (2009). "Selling graphene by the ton". Nature Nanotechnology 4 (10): 612–4
Nature 483, S29 (15 March 2012). Also http://www.azom.com/news.aspx?newsID=11679
One Measure of Improvement
 Diameter of the sheets that can be fabricated
 According to Prof..Tomas Palacios of MIT, the
size of graphene sheets has been increased from
a few microns to about 30 inches in the last few
years. Further increases will open up new
applications as will cost reductions.
 http://edition.cnn.com/2013/04/29/tech/graphene-
miracle-material/index.html?hpt=hp_c3
300 square
centimeter
graphene film from
Graphene
frontiers
Graphene Frontiers claims
it will
have a roll-to-roll machine
prototype ready within a
few years. The three big
applications will be
desalinization and filtration,
biosensing and electronics.
http://www.azonano.com/article.aspx?ArticleID=3185
But lots of controversy!!!!
Many argue these large sheets do not have consisten
performance (including flatness) across the sheets
Another Measure of Improvement is Price
(Euros/cm2)
http://www.graphenea.com/pages/graphene-
price#.Ut8YMRAZ6Uk
What About Graphene Composites?
 Alternate layers of graphene with other materials
 grow single layer of graphene on a metallic deposited
substrate using chemical vapor deposition, then add
another metal layer
 repeat the steps, resulting in multilayer metal-graphene
composite of 0.00004% in weight of graphene
 The graphene makes copper 500 times and
nickel 180 times stronger
 Big application for aircraft?
 Another material, a nanocoating, reduced fuel
consumption by 2 percent and enabled one airline to
save $22 million per year
http://spectrum.ieee.org/nanoclast/semiconductors/nanotechnology/for-first-time-graphene-and-metal-
make-strong-composite
Not Just Graphene, i.e., Carbon
 As of April 2013, >10 materials found that are one or a
few atoms thick
 Transition metal dichalcogenides for solar cells
http://gizmodo.com/super-thin-graphene-solar-panels-could-pave-the-way-for-489111383
 Boron nitride (insulator) has been fabricated in one-
atom sheet as has Molybdenum Sulfide
 Molybdenum Sulfide is semiconductor, Boron Nitride is
insulator, Graphene is for interconnect
 Together one atom thick flash memory devices have been
constructed (http://www.thessdreview.com/daily-news/latest-buzz/flash-memory-to-be-based-
on-2d-materials-a-single-atom-thick/)
 More complex devices can be constructed by doping one of the
layers
http://thessdreview.com/daily-news/latest-buzz/flash-memory-to-be-based-on-2d-materials-a-single-atom-
thick/
April 29, 2013. http://edition.cnn.com/2013/04/29/tech/graphene-miracle-material/index.html?hpt=hp_c3
Other Materials have Similar Hexagonal Lattice
Structures to Graphene
Source: Nature, Vol 497, 23 May 2013
Returning to Graphene, Why Might it Get
Dramatically Cheaper?
Material costs are obviously low…………
How much Cheaper will Graphene or
other Ultra-thin materials become?
 Will new processes be found?
 Will increases in scale help?
 The large number of possible processes and
composites makes people optimistic
 What applications will become possible as
the cost of graphene falls?
Source: http://www.multibriefs.com/briefs/spe/Graphene-based%20nanocomposites.pdf
http://iopscience.iop.org/1402-4896/2012/T146/014024/article
Methods of Making Graphene Film
http://iopscience.iop.org/1402-4896/2012/T146/014024/article
CVD-Based Graphene Growth on Ni, Cu,
Growing Graphene on Cu Films
http://iopscience.iop.org/1402-4896/2012/T146/014024/article
Different Methods of Synthesis, Different Application
What about applications?
And Market Growth?
A likely early application: Flexible
Transparent Electrodes
 Replace indium tin oxide in solar cells, light-
emitting diodes (LEDs), organic light-emitting
diodes (OLEDs), touch screens, smart windows
LCD displays
 Different levels of sheet resistance are
needed for each
 Composites have highest levels of conductance
and transmittance (FeCl3-FLG [few layer
graphene])
 Problems with indium tin oxide
 High deposition temperature, brittle and fragile
http://iopscience.iop.org/1402-4896/2012/T146/014024/article
http://onlinelibrary.wiley.com/doi/10.1002/adma.201200489/abstract;jsessionid=2450
8C91658C71CB5F94C7AED94D5BC8.d03t01
http://iopscience.iop.org/1402-4896/2012/T146/014024/article
Transparent
Electrodes,
continued
Looking Further to the Future:
Graphene Aircraft?
 What about making aircraft from
grapheme?
 Why would we want to do this?
 How might we estimate the cost of making
aircraft from grapheme?
Looking Further to the Future:
Graphene Aircraft?
 If graphene is 0.1 Euro/cm2(Graphena‘s estimate for
2020) would Airbus or Boeing use graphene as the
material for fuselage or wings?
 How would you do a rough calculation?
 Roughly speaking, since a Boeing 777‘s fuselage
and wings have a surface area of about 3000 square
meters, it would cost about 3 million Euros for a
single layer of Graphene to be used on their
fuselage and wings or about 1/100 the current price
of a Boeing 777. The fuselage of Boeing 777 has a
length of about 80 meters and a diameter of about 6
meters
One Possible Future
 All structures and products are made from single atom
thick materials
 Would lead to much lower material usage
 And thus less energy needed to make materials?
 Steel and other materials require lots of energy
 Lower energy usage by transportation equipment
 Lighter equipment leads to lower energy usage
 More interesting structures
 Taller structures
 More interesting shapes that are not constrained by
weight
 Carbon fiber has been moving us in these directions
for many years, but single atom thick materials can
Will Graphene Make these Highways Economically
http://nextgenlog.blogspot.sg/2012/07/materials-graphene-rising-to-1-
billion.html
Back to Reality, the market is still small….How fast
will it grow?
Replacement of existing component in an existing
product. Replace:
carbon black, carbon fibre, graphite, carbon
nanotubes, silver
nanowires, Indium Tin Oxide, silver flakes, copper
nanoparticles,
aluminium, silicon, GaAs, ZnO, etc.
The strength of graphene's value proposition is
different for each target market.
http://www.printedelectronicsworld.com/articles/idtechex-forecasts-a-100-million-graphene-market-in-
2018-00004721.asp?sessionid=1
IDTechEx forecasts $100 million Graphene
market in 2018
(on 12 September 2012)
Outline
 What is nanotechnology?
 Fullerene, Graphene and Carbon
Nanotubes
 Quantum Dots
 Nanoparticles
 Nanofibers
 Common issues
Single (SWNT) and Multi-Walled Nano Tube
(MWTB)
Carbon nanotubes can be made with single or multiple walls, in
different diameters, and with different axes
Like fullerenes, only certain diameters exist and each design
has different
properties
Carbon Nanotubes (1)
 Diameters and axes impact on
 levels of conduction and thus
 whether the carbon nanotube is a conductor,
semiconductor, or an insulator
 Conducting nanotubes
 1000 times higher conductivities than copper
 100 times higher current densities than
superconductors
 but only if there is one continuous piece of nanotube
(which is quite difficult)
 Easier to make long superconductors (but
even this is difficult) than long nanotubes
 Thus, carbon nanotubes will probably be used
for short distances, for example for IC or board
level interconnect
Carbon Nanotubes (2)
 Carbon nanotubes are the strongest materials known
in terms of tension
 However, lack of consistency means that these
strengths may not be maintained at the macroscopic
level with many nanotubes
 One application is cutting thin slices of biologic material
(<100 nm)
 Very high levels of thermal conductivity: 5000 W/m-K
 Because its characteristics (e.g., conduction,
strength) vary by design (e.g., diameter) and process,
much research is still trying to understand the
relationship between design, process, and
characteristics
Price is critical: Price per gram of Single
Walled Carbon Nanotubes has steadily
fallen
(Aluminum is $2.50 per kg or 1/400,
Gold is 60$/gram or about 2/3)
From Nanotechnology by Ben Rogers, Sumita Pennathur, Jesse Adams, CRC Press, 2011
Another Source of Price Data (Multi-ton
orders)Price(USD/gram)
0.000
0.001
0.010
0.100
1.000
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015
2016
SWNT (90wt%) Indium
Silicon MWNT
Carbon Fibre Steel
Year
Source: MT5009 fall semester 2013, group project
Environmental Assessment of Single-Walled Carbon Nanotube Processes, Journal of Industrial Ecology, Vol
12, No. 3
Meagan L. Healy, Lindsay J. Dahlben, and Jacqueline A. Isaacs
Electrical Energy Requirements are One Reason for
High Prices
Source: Minimum Exergy Requirements for the Manufacturing of Carbon Nanotubes, Timothy G.
Gutowski, John Y. H. Liow, Dusan P. Sekulic, IEEE, International Symposium on Sustainable Systems
and Technologies, Washington D.C., May 16-19, 2010
for Carbon Nanotubes
But the Energy Requirements are Falling
Will Costs Fall?
 Like Graphene, Carbon NanoTubes have low
material costs
 But how much will the processing costs fall?
Large Variety of Processes Makes Many
Optimistic about Carbon Nanotubes
 Carbon nanotubes are made by several methods
 Chemical Vapor Deposition (CVD)
 arc discharge
 laser ablation
 HIPCO®: Hi-pressure carbon monoxide
 surface mediated growth of vertically-aligned tubes by
Plasma Enhanced Chemical Vapor Deposition
(PECVD)
 Understanding their growth in these processes is
critical to making them cheaper
 Costs will probably fall as scale increases of HIPCO
process (see later slide on nano-fibers made from
carbon nanotubes)
Researchers at USC have solved a long-standing challenge with carbon
nanotubes: how to actually build them with specific, predictable atomic
structures.―We are now working on scale up the process,‖ Zhou said.
―Our method can revolutionize the field and significantly push forward
the real applications of nanotube in many fields.‖
Until now, scientists were unable to ―grow‖ carbon nanotubes with
specific attributes — say metallic rather than semiconducting — instead
getting mixed, random batches and then sorting them. The sorting
process also shortened the nanotubes significantly, making the material
less practical for many applications.
Chirality-Dependent Vapor-Phase Epitaxial Growth and Termination of Single-Wall Carbon Nanotubes,
Bilu Liu †, Jia Liu †, Xiaomin Tu ‡, Jialu Zhang †,Ming Zheng *‡, and Chongwu Zhou *, nanoletters, Augu
Improved Control over Production of CNTs
Electrical/Electronic Applications
 Transparent Electrodes for
displays, batteries and solar cells
 Transistors and Interconnect for integrated
circuits
 Cables and Wires
 Ultra-capacitors for energy storage
 Sensors
 Medical – vibrations of nanotubes from
radio waves (pass through tissue) or their
emission of light can kill cancer cells
For Transparent and Conductive Sheets on
Electronic Paper
(Trying to find lower resistance and higher transmittance)
http://www.osa-direct.com/osad-news/654.html
Another Application Might be
Flywheels
 May be a large market for carbon nanotubes and/or
grapheme
 Energy density of flywheels is a function of strength-
to weight ratio
 E/m = K (sigma/rho)
 E= kinetic energy of rotor; M = mass
 K = rotor‘s geometric shape factor
 Sigma = tensile strength of material
 Rho = material‘s density
 Flywheels have about same energy density as Li-ion
batteries but much faster rate of improvement
 Carbon fibers are now being used in formula 1 cars
 But CNTs have 10 times higher strength to weight
ratios than do carbon fiber. Thus 10 times higher
energy densities are possible
Source: Presentation by MT5009 students on April 11, 2013. Slides can be found on http://www.slideshare.net/Fun
For Transistors and Integrated
Circuits
 I.B.M. scientists were able to pattern an array of
carbon nanotubes on the surface of a silicon
wafer and use them to build hybrid chips with
more than 10,000 working transistors
 They did this by using a process they described
as ―chemical self-assembly‖ to create patterned
arrays in which nanotubes stick in some areas of
the surface while leaving other areas untouched
 Perfecting the process will require a more highly
purified form of the carbon nanotube material
http://bits.blogs.nytimes.com/2012/10/28/i-b-m-reports-nanotube-chip-breakthrough/
Improvements in Purity of CNTs (and Increases in
Source: Electronics: The road to carbon nanotube transistors, Aaron D. Franklin
Nature 498, 443–444 (27 June 2013)
For Transistors and Integrated
Circuits (2)
 In the short term, high purity CNTs will probably
be used to achieve higher conductivity channel
length and perhaps interconnect
 Mentioned in previous session
 In the long run, different types of CNTs may be
used for the conducting, insulating, and
semiconducting regions
 Thus creating a new form of integrated circuit
http://bits.blogs.nytimes.com/2012/10/28/i-b-m-reports-nanotube-chip-breakthrough/
Market Size for Carbon Nanotubes
Production
Capacity, Producers, and
Applications for Carbon
NanoTubes
http://www.nanowerk.com/spotlight/spotid=23118.ph
p
Outline
 What is nanotechnology?
 Fullerene, Graphene and Carbon
Nanotubes
 Quantum Dots
 Nanoparticles
 Nanofibers
 Common issues
Quantum Dots
 Semiconductors also exhibit interesting behavior as
sizes reach the nano-scale, single nanometer levels
 Quantum dot is semiconductor whose electronic
characteristics are closely related to size and shape
of individual crystal
 Generally, the smaller the size of crystal, the larger
the band gap and thus
 the greater the difference in energy between the
highest and 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
Quantum Dots (2)
 For example, some can emit light like a laser
 Size of the dot determines the wavelength, i.e., color of
the light, that is emitted
 Power consumption is very low
 Efficiency and switching speeds can be very high
 While others can absorb light
 Size of the dot determines the wavelength, i.e., color of
the light, that is absorbed (i.e., solar cells)
 One problem is that they are very expensive
(thousands of dollars per gram)
Source: Semiconductor II-VI Quantum Dots with Interface States and Their Biomedical Applications
By Tetyana Torchynska and Yuri Vorobiev
Different Size Dots Emit Different Wavelengths of Light
Applications of Quantum Dots
 Lasers and Displays
 Different size dots on a single substrate each emitting
different wavelengths with lower power consumption
 Lasers can be smaller, faster, and consume less power than
current ones for telecommunication and computing
applications
 Solar cells/Photosensors
 different size quantum dots absorb different wavelengths of
light
 Thus a single substrate can absorb different wavelengths of
light and thus have much higher efficiencies than current
solar cells
 Higher sensitivities for photosensors
 Medical applications
 Different dots are coated with different layers, which enable
different dots to bond with different targets
http://www.photonics.com/Article.aspx?AID=14668
Quantum Well and Dot-Based Lasers
Materials Today 14(9) September 2011, Pages 388–397
Reductions in Threshold Current, i.e., Minimum Current
Needed for Lasing to Occur (by reducing sizes of devices)
Source: Changhee Lee, Seoul National University
http://www.andrew.cmu.edu/org/nanotechnology-forum/Forum_7/Presentation/CH_Lee.pdf
JH Kwak PhD Thesis (2010)
Improvements in Efficiency of Quantum Dots for Dis
Manufacturing is One Challenge
 These dots can be manufactured by depositing a
vapor of the relevant compound, e.g., molecular
beam epitaxy
 For example, the atomic lattice mismatch between
InAs and GaAs causes the deposition of InAs onto
GaAs where the InAs self-assembles into nanoscale
islands that show quantum dot behavior
 Quantum dots are much more expensive than
quantum wells
 Can costs be reduced? By how much?
 As the costs/prices are reduced, what kinds of
applications become economically feasible?http://www.photonics.com/Article.aspx?AID=14668
Is the Market for Quantum Dots
Growing
A key barrier is
price: quantum dots
can cost anywhere
from US$3,000 to
$10,000 per
gram, restricting
their use to highly
specialized
applicationsSource:
http://www.nature.com/news/
2009/090610/full/459760a.ht
ml (2009)
Source: http://bccresearch.blogspot.sg/2012/09/global-market-for-quantum-dots-to-grow
Market for Quantum Dots, Forecasted in Septemb
Outline
 What is nanotechnology?
 Fullerene, Graphene and Carbon
Nanotubes
 Quantum Dots
 Nanoparticles
 Nanofibers
 Common issues
Characteristics of NanoParticles
 Greater percentage of atoms at
surface, which leads to unique properties
 Changes in wavelengths absorbed and
emitted
 Higher reactance
 Higher magnetic moment
 Higher strength
 Ability to enter living organisms
 But finding the appropriate material and
matching it to the application is a major
challenge
Source: Binns, C. 2010. Introduction to Nanoscience and Nanotechnology
Absorption Varies by Size of
Nanoparticle
 Like quantum dots, absorbed
wavelengths vary by size
 For example, small particles of zinc oxide
and titanium dioxide absorb ultraviolet but
not visible light
 Thus, the sunscreen is invisible to visible
light
Reactanc
e
increases
as Size
decrease
s;
How
much
more can
be
achieved
?
High Reactivity is Useful for some
Applications
 Can be used for stain resistant pants
 Small particles react with stains to eliminate
them
 How about other applications?
 Can other materials be found whose
reactance varies by size?
 Will these new materials lead to applications
other than stain resistant pants?
 Or maybe just help in existing applications.
For example, high reactance can lead to
Source: Binns, C. 2010. Introduction to Nanoscience and Nanotechnology
Magnetic moments increase as
particle size decreases; how much
more can be achieved?
Rh
Magnetic Nanoparticles
 Can make single particle magnetic storage
possible
 Increases limit of platters to 100 Tb/in2, or 1000 times
more than existing densities
 But medical applications may be bigger
 Aids in detection by improving contrast of MRI via higher
magnetic moments; improvements are possible
 Can be steered to cancer cells with external magnetic
field
 Can destroy cells by oscillating magnetic field that
creates heat
 Trials on humans have started
Improved Relaxivity (better detection) with Higher Magnet
Moments (Dotted line shows expected improvements
Source: Binns, C. 2010. Introduction to Nanoscience and Nanotechnology
Source: Binns, C. 2010. Introduction to Nanoscience and Nanotechnology
Cancer cells can be killed by
Hyperthemia
Hyperthemia
 Power of about 0.1 W/cm3 is needed to kill
cancer cells
 Effectiveness of nanoparticles at heating can
be measured by specific absorption rate
(SAR)
 Typical rate for magnetic nanoparticles is 10
W/g
 Thus
 0.01 g of nanoparticle is required to achieve 0.1 W and
 Thus hundreds of thousands of nanoparticles are
needed for cancer cells, which is probably far more
than is possible for many receptors
Are These Values for SAR Sufficient?
Other Treatments for Killing Cancer
Cells
 Current treatments (e.g., chemotherapy) kill patients
 Nanoparticles can be ―programmed/designed‖ to find
and kill specific cancer cells
 Several thousand have been reported in literature
 Lipsomes, protocells release drugs on contact with cancer
cells
 Dendrimers are tree-like polymers with many active sites
for bonding external agents – each targeting cancer cells
 Reflectivity of light from gold and silver particles depends
on their binding to cancer cells and some of them can be
made to vibrate and kill cancer cells via absorption of
infrared light
 Vibrations of nanotubes from radio waves (pass through
tissue) or their emission of light can kill cancer cells
Part of Finding Cancer Cells Involves
Biological Targeting
 Selective binding to cancer cells enhances
treatment
 Antibodies are the oldest and most studied
 but too large (can‘t enter cells) and expensive
 Nanobodies contain fragments of antibodies
 Aptamers
 artificially short section of DNA
 much cheaper than antibodies
 Peptides are even smaller
 Composed of 20 amino acid building blocks
 Smallest method of targeting is folates/folic acid: only 51
atoms
 Finding the appropriate biological material and
Big Challenge is Price
 Nanoparticles are made by condensation of a
supersaturated vapor into particles particularly
with a vacuum source
 But since the cost of a vacuum is high, many
search for a cheaper process such as one using
high voltage sparks
 Since magnetic nanoparticles are often used for
living organisms and are produced by some
bacteria, some use bacteria to synthesize them.
 On the other hand, only a small number of
particles may be needed for each patient…
Outline
 What is nanotechnology?
 Fullerene, Graphene and Carbon
Nanotubes
 Quantum Dots
 Nanoparticles
 Nanofibers
 Common issues
Examples
 Cargo nets
 Ultra-high-molecular-weight polyethylene
 15 times stronger on a weight basis than steel, but 4
times more expensive than typical polyester net
 Robotic cables
 Vectran
 Fire resistant textiles
 Textiles that
 absorb body odor
 block radiation
Smaller Diameters Lead to Higher
Strength
 This is true for many materials such as
electrospun Polyamide 6.6 fibers
 The increased strength of fine diameter fibers
(<500 nm) is attributed to the oriented fragments
of amorphous chains
 The fibers display remarkably improved properties
when the size of this oriented amorphous part is
comparable to overall fiber diameter
 But finding the appropriate materials and
applications for them is a challenge
Decreasing the size of
the fiber leads to higher
tensile strength
(breaking point) and
tensile modulus
(tension)
(Hi-Tensile Steel is
1860 and 200)
Source:
Effect of fiber diameter on the
deformation behavior of self-
assembled carbon nanotube
reinforced electrospun Polyamide
6,6 fibers Avinash Baji, Yiu-Wing
Maia, Shing-Chung Wong.
Materials Science and Engineering
A 528 (2011) 6565– 6572
Big Challenge is Manufacturing/Process
 Electrospinning is the main manufacturing
technique, but still quite expensive
 Improvements over the last ten years in
productivity of single nozzle setup from 0.5
grams per hour to 6.5 kilograms per hour
(Source: Chem. Soc. Rev., 2012, 41, 4708–
4735)
 To what extent can further improvements be
made?
 What applications will be made possible through
these reductions in cost/price?
What About Using Carbon NanoTubes to
Make these Fibers?
 Since they have nano-level dimensions, we would
expect the fibers made from them to have high
strength
 Manufacturing techniques:
 spinning from a lyotropic liquid crystalline suspension
of nanotubes, in a wet-spinning process similar to that
used for polymeric fibers such as aramids
 spinning directly from an aerogel of single walled
carbon nanotube (SWCNTs) and multi-walled CNTs
(MWCNTs) as they are formed in a chemical vapor
deposition reactor
 spinning from MWCNTs previously grown on a
substrate as ‗‗semialigned‖
Carbon
NanoTube
(CNT)-based
fibers
can have Higher
strengths than
do
other High-
performance
fibers
Source:
An assessment of the science and
technology of carbon nanotube-
based fibers and composites,
Tsu-Wei Chou b,*, Limin Gao
a, Erik T. Thostenson b, Zuoguang
The Main Challenge is
Process/Manufacturing
 Strength, other performance dimensions and
cost depends on process so need improvements
in process
 Cost data could not be found but…
 Energy requirements are still high
 Four orders of magnitude less than that of carbon
nanotubes
 Similar energy per kg as Aluminum
 But carbon nanotubes must be made before the fiber
can be made…….
Source: Minimum Exergy Requirements for the Manufacturing of Carbon Nanotubes, Timothy G. Gutowski, John Y. H.
Liow, Dusan P. Sekulic, IEEE, International Symposium on Sustainable Systems and Technologies, Washington D.C., May
16-19, 2010
Energy Intensity vs. Process Rate for Production of Carbon
Nano-fibers
to put these
process rates in
perspective,
ethylene is
made
in factories one
million times
larger than this
Market forecasted to grow from US$ 140M
in 2010 to US$ 4B by 2020
http://www.adsaleata.com/Publicity/MarketNews/lang-
eng/article-112763/Article.aspx
Outline
 What is nanotechnology?
 Fullerene, Graphene and Carbon Nanotubes
 Quantum Dots
 Nanoparticles
 Nanofibers
 Common issues
Common Issues (1)
 Need to find materials that better exploit small
dimensions and that are appropriate for specific
application
 Nanoparticles that selectively bind to cancer cells and
kill them
 Materials for quantum dots and nanofibers
 Need to find new processes that produce more
appropriate and better nano-materials
 But at what rate and for what applications are we
finding these new materials?
 And what does this tell us about when new
applications become economically feasible?
Common Issues (2)
 Costs are too high
 Nanoparticles, Quantum Dots, Nanofibers
 Fullerene, Graphene and Carbon Nanotubes
 How fast will costs fall?
 They will probably fall at slower rate than what has been
seen with ICs (i.e., Moore‘s Law)
 No discernible benefit from reductions in scale
 Costs may fall as scale of production is increased or as new
processing methods are found
 See Sessions 2 and session on roll-to roll printing for more
details on impact of increases in scale of production
equipment on manufacturing costs
 Which applications will become economically feasible as
the production costs for nanotechnology fall?
 Appendix
Price of carbon fiber
http://www.zoltek.com/carbonfiber/the-history-of-carbon-fiber/
Carbon fiber in vehicles
http://auto.howstuffworks.com/fuel-efficiency/fuel-economy/carbon-fiber-oil-crisis2.htm
Roadmap for graphene
http://www.nature.com/nature/journal/v490/n7419/full/nature11458.html?WT.ec_id=NATURE-
20121011
http://www.graphenea.com/pages/graphene-price#.UonUjnASbTp Euros per square
Graphene transistors
http://phys.org/news/2012-07-graphene-transistor.html
Improve strength of material by combining it with graphene in sandwich composite
http://spectrum.ieee.org/nanoclast/semiconductors/nanotechnology/for-first-time-
graphene-and-metal-make-strong-composite
Graphene applications
http://www.graphenea.com/pages/graphene-uses-applications#.UonTB3ASbTr
http://www.ft.com/cms/s/0/6f4717b6-66f9-11e2-a83f-
00144feab49a.html#axzz2ktOs2EWw
Transparent conductors
http://onlinelibrary.wiley.com/doi/10.1002/adma.201200489/abstract;jsessionid=245
08C91658C71CB5F94C7AED94D5BC8.d03t01
http://www.luxresearchinc.com/blog/coveragearea/advanced-materials/

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Nanotechnology and its Economic Feasibility

  • 1. A/Prof Jeffrey Funk Division of Engineering and Technology Management National University of Singapore When Will NanoTechnology-Based Products Become Economically Feasible for Specific Applications? For information on other technologies, see http://www.slideshare.net/Funk98/presen
  • 2. Session Technology 1 Objectives and overview of course 2 Two types of improvements: 1) Creating materials that better exploit physical phenomena; 2) Geometrical scaling 4 Semiconductors, ICs, electronic systems 5 MEMS and Bio-electronic ICs 6 Nanotechnology and DNA sequencing 7 Superconductivity and solar cells 8 Lighting and Displays 9 Human-computer interfaces (also roll-to roll printing) 10 Telecommunications and Internet 11 3D printing and energy storage This is Part of the Sixth Session of MT5009
  • 3. Objectives  What are the important dimensions of performance for nanotechnologies and their higher level systems?  What are the rates of improvement?  What drives these rapid rates of improvement?  Will these improvements continue?  What kinds of new systems will likely emerge from the improvements in nanotechnology?  What does this tell us about the future?
  • 4. As Noted in Previous Session, Two main mechanisms for improvements  Creating materials (and their associated processes) that better exploit physical phenomenon  Geometrical scaling  Increases in scale  Reductions in scale  Some technologies directly experience improvements while others indirectly experience them through improvements in ―components‖ A summary of these ideas can be found in 1) What Drives Exponential Improvements? California Management Review, Spring 2013 2) Technology Change and the Rise of New Industries, Stanford University Press, 2013 3) Exponential Change: what drives it? What does it tell us about the future?
  • 5. Both are Relevant to Nanotechnology  Creating materials (and their associated processes) that better exploit physical phenomenon  Creating materials such as carbon nanotubes that better exploit small dimensions  Geometrical scaling  Increases in scale: larger production equipment  Reductions in scale: exploiting phenomena at small dimensions; ability to create smaller dimensions enables more phenomena to be exploited. Some people argue that ―thin film‖ is part of every important technology  Some technologies directly experience improvements while others indirectly experience them through improvements in ―components‖  Better nanotechnology-based products lead to better electronic systems
  • 6. Both Relevant to Nanotechnology (cont)  Rapid improvements in integrated circuits (ICs), magnetic storage, other electronic technologies over last 50 years  Moore‘s Law  Areal recording density of hard disk platters  These improvements have enabled many new forms of electronic products and improvements in them  Computers, Mobile Phones, Internet  Is there a similar or greater potential for nanotechnology?  Are there indications of this potential in a
  • 7. Outline  What is nanotechnology?  Fullerene, Graphene and Carbon Nanotubes  Quantum Dots  Nanoparticles  Nanofibers  Common issues
  • 8. What is NanoTechnology? (1)  Things on the nano-meter (10-9) level: 1-100 nm  ICs, MEMS, and bio-electronics can be considered nano-technology  But,  nano-technology should take us to smaller scale, molecular or even atomic level  like ICs, these technologies should benefit from the reductions in scale that these nano-dimensions represent  involve self-assembly (like with snowflakes and biological reproduction) so that the costs of making them are low  Have progress that is measurable and identifiable
  • 10. What is NanoTechnology? (2)  One-dimensional nanoproducts  thin film devices, coatings (antireflection, corrosion), graphene and quantum wells (stacked thin film layers)  found in semiconductor, metallic, and dielectric films  • Two-dimensional (2-D) nanoproducts  single or multiwall nanotubes  nanowires, nanorods  Three-dimensional (3-D) nanoproducts  fullerenes,  dendrimers  nanoparticles  polymeric dispersions
  • 11. Why do we care? From Large to Small  A number of physical phenomena become pronounced as the size of the system decreases  increase in surface area to volume ratio altering mechanical, thermal and catalytic properties  statistical and quantum mechanical effects at less than 100 nanometers  hydrogen bonding, molecular forces, van der waals forces  Different properties appear at the nano-scale, enabling unique applications  opaque substances become transparent (copper)  stable materials turn combustible (aluminum)  insoluble materials become soluble (gold)  high thermal and electrical conductivities and strength (carbon)
  • 12. As the size of a particle becomes smaller, van der walls (vdw) forces (i.e., electro- magnetic forces between neutral atoms) become much more important than gravitational forces (earth-particle and particle-particle) Source: Treavor A. Kendall,
  • 13. Once we have Small Things, How can we Make Big Things?  Top-down approaches are too expensive  Micro-machining  Photolithography  Electron-beam lithography  Focused ion beams  Bottom-up, or so-called self assembly is needed  Modern synthetic chemistry enables synthesis of chemicals from molecules  New methods are needed
  • 14. Manufacturing Processes are Critical  Processes determine costs and performance of nano- products  Needed characteristics of processes  High purity: often need 99.9999999%  High material yields: low yields are common in many processes such as molecular beam epitaxy (3-10%) or metal organic CVD (theoretical limit is 50%)  Small number of process steps  Low temperature and vacuum requirements as these raise costs  Benefits from increases in scale of equipment, such as those that exist in chemical plants and production of liquid
  • 15. Outline  What is nanotechnology?  Fullerene, Graphene and Carbon Nanotubes  Quantum Dots  Nanoparticles  Nanofibers  Common issues
  • 16. Fullerenes, Graphene, and Carbon Nanotubes Fullerenes specific number of carbon atoms arranged as sphere 20 is the smallest, many other stable numbers Graphene flat sheet of carbon atoms Carbon Nanotubes flat sheet is rolled so that sides are connected, thus
  • 17. Fullerenes As size of fullerenes increases, energy gap between highest and lowest orbital also decreases where this gap is analogous to the band gap in semiconductors One can also dope fullerenes by inserting atoms inside of them Thus, one can design fullerenes with specific electronic properties as with semiconductors Depending on purity, price of fullerenes is more than $100 per gram
  • 18. Graphene  A single layer of carbon atoms  Very low electrical resistance, high thermal conductivity (4,000 W/m-K), and high mobility (about 200,000 cm2/Vs at room temperature, compared to 1,400 in silicon and 77,000 in indium antimonide)  One of strongest materials, but yet flexible  Unusual optical behavior: equally transparent to ultraviolet, visible and infrared light  Two current markets (composites for strength and electrodes for conductivity) but also displays, computer chips, and solar cells  http://www.youtube.com/watch?v=XDJRlBSXsow Source: Segal, Michael (2009). "Selling graphene by the ton". Nature Nanotechnology 4 (10): 612–4 Nature 483, S29 (15 March 2012). Also http://www.azom.com/news.aspx?newsID=11679
  • 19. One Measure of Improvement  Diameter of the sheets that can be fabricated  According to Prof..Tomas Palacios of MIT, the size of graphene sheets has been increased from a few microns to about 30 inches in the last few years. Further increases will open up new applications as will cost reductions.  http://edition.cnn.com/2013/04/29/tech/graphene- miracle-material/index.html?hpt=hp_c3
  • 20. 300 square centimeter graphene film from Graphene frontiers Graphene Frontiers claims it will have a roll-to-roll machine prototype ready within a few years. The three big applications will be desalinization and filtration, biosensing and electronics.
  • 22. But lots of controversy!!!! Many argue these large sheets do not have consisten performance (including flatness) across the sheets
  • 23. Another Measure of Improvement is Price (Euros/cm2) http://www.graphenea.com/pages/graphene- price#.Ut8YMRAZ6Uk
  • 24. What About Graphene Composites?  Alternate layers of graphene with other materials  grow single layer of graphene on a metallic deposited substrate using chemical vapor deposition, then add another metal layer  repeat the steps, resulting in multilayer metal-graphene composite of 0.00004% in weight of graphene  The graphene makes copper 500 times and nickel 180 times stronger  Big application for aircraft?  Another material, a nanocoating, reduced fuel consumption by 2 percent and enabled one airline to save $22 million per year http://spectrum.ieee.org/nanoclast/semiconductors/nanotechnology/for-first-time-graphene-and-metal- make-strong-composite
  • 25. Not Just Graphene, i.e., Carbon  As of April 2013, >10 materials found that are one or a few atoms thick  Transition metal dichalcogenides for solar cells http://gizmodo.com/super-thin-graphene-solar-panels-could-pave-the-way-for-489111383  Boron nitride (insulator) has been fabricated in one- atom sheet as has Molybdenum Sulfide  Molybdenum Sulfide is semiconductor, Boron Nitride is insulator, Graphene is for interconnect  Together one atom thick flash memory devices have been constructed (http://www.thessdreview.com/daily-news/latest-buzz/flash-memory-to-be-based- on-2d-materials-a-single-atom-thick/)  More complex devices can be constructed by doping one of the layers http://thessdreview.com/daily-news/latest-buzz/flash-memory-to-be-based-on-2d-materials-a-single-atom- thick/ April 29, 2013. http://edition.cnn.com/2013/04/29/tech/graphene-miracle-material/index.html?hpt=hp_c3
  • 26. Other Materials have Similar Hexagonal Lattice Structures to Graphene Source: Nature, Vol 497, 23 May 2013
  • 27. Returning to Graphene, Why Might it Get Dramatically Cheaper? Material costs are obviously low…………
  • 28. How much Cheaper will Graphene or other Ultra-thin materials become?  Will new processes be found?  Will increases in scale help?  The large number of possible processes and composites makes people optimistic  What applications will become possible as the cost of graphene falls? Source: http://www.multibriefs.com/briefs/spe/Graphene-based%20nanocomposites.pdf
  • 31. Growing Graphene on Cu Films http://iopscience.iop.org/1402-4896/2012/T146/014024/article
  • 32. Different Methods of Synthesis, Different Application
  • 34. A likely early application: Flexible Transparent Electrodes  Replace indium tin oxide in solar cells, light- emitting diodes (LEDs), organic light-emitting diodes (OLEDs), touch screens, smart windows LCD displays  Different levels of sheet resistance are needed for each  Composites have highest levels of conductance and transmittance (FeCl3-FLG [few layer graphene])  Problems with indium tin oxide  High deposition temperature, brittle and fragile http://iopscience.iop.org/1402-4896/2012/T146/014024/article
  • 37. Looking Further to the Future: Graphene Aircraft?  What about making aircraft from grapheme?  Why would we want to do this?  How might we estimate the cost of making aircraft from grapheme?
  • 38. Looking Further to the Future: Graphene Aircraft?  If graphene is 0.1 Euro/cm2(Graphena‘s estimate for 2020) would Airbus or Boeing use graphene as the material for fuselage or wings?  How would you do a rough calculation?  Roughly speaking, since a Boeing 777‘s fuselage and wings have a surface area of about 3000 square meters, it would cost about 3 million Euros for a single layer of Graphene to be used on their fuselage and wings or about 1/100 the current price of a Boeing 777. The fuselage of Boeing 777 has a length of about 80 meters and a diameter of about 6 meters
  • 39. One Possible Future  All structures and products are made from single atom thick materials  Would lead to much lower material usage  And thus less energy needed to make materials?  Steel and other materials require lots of energy  Lower energy usage by transportation equipment  Lighter equipment leads to lower energy usage  More interesting structures  Taller structures  More interesting shapes that are not constrained by weight  Carbon fiber has been moving us in these directions for many years, but single atom thick materials can
  • 40. Will Graphene Make these Highways Economically
  • 42. Replacement of existing component in an existing product. Replace: carbon black, carbon fibre, graphite, carbon nanotubes, silver nanowires, Indium Tin Oxide, silver flakes, copper nanoparticles, aluminium, silicon, GaAs, ZnO, etc. The strength of graphene's value proposition is different for each target market. http://www.printedelectronicsworld.com/articles/idtechex-forecasts-a-100-million-graphene-market-in- 2018-00004721.asp?sessionid=1 IDTechEx forecasts $100 million Graphene market in 2018 (on 12 September 2012)
  • 43. Outline  What is nanotechnology?  Fullerene, Graphene and Carbon Nanotubes  Quantum Dots  Nanoparticles  Nanofibers  Common issues
  • 44. Single (SWNT) and Multi-Walled Nano Tube (MWTB) Carbon nanotubes can be made with single or multiple walls, in different diameters, and with different axes Like fullerenes, only certain diameters exist and each design has different properties
  • 45. Carbon Nanotubes (1)  Diameters and axes impact on  levels of conduction and thus  whether the carbon nanotube is a conductor, semiconductor, or an insulator  Conducting nanotubes  1000 times higher conductivities than copper  100 times higher current densities than superconductors  but only if there is one continuous piece of nanotube (which is quite difficult)  Easier to make long superconductors (but even this is difficult) than long nanotubes  Thus, carbon nanotubes will probably be used for short distances, for example for IC or board level interconnect
  • 46. Carbon Nanotubes (2)  Carbon nanotubes are the strongest materials known in terms of tension  However, lack of consistency means that these strengths may not be maintained at the macroscopic level with many nanotubes  One application is cutting thin slices of biologic material (<100 nm)  Very high levels of thermal conductivity: 5000 W/m-K  Because its characteristics (e.g., conduction, strength) vary by design (e.g., diameter) and process, much research is still trying to understand the relationship between design, process, and characteristics
  • 47. Price is critical: Price per gram of Single Walled Carbon Nanotubes has steadily fallen (Aluminum is $2.50 per kg or 1/400, Gold is 60$/gram or about 2/3) From Nanotechnology by Ben Rogers, Sumita Pennathur, Jesse Adams, CRC Press, 2011
  • 48. Another Source of Price Data (Multi-ton orders)Price(USD/gram) 0.000 0.001 0.010 0.100 1.000 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 SWNT (90wt%) Indium Silicon MWNT Carbon Fibre Steel Year Source: MT5009 fall semester 2013, group project
  • 49. Environmental Assessment of Single-Walled Carbon Nanotube Processes, Journal of Industrial Ecology, Vol 12, No. 3 Meagan L. Healy, Lindsay J. Dahlben, and Jacqueline A. Isaacs Electrical Energy Requirements are One Reason for High Prices
  • 50. Source: Minimum Exergy Requirements for the Manufacturing of Carbon Nanotubes, Timothy G. Gutowski, John Y. H. Liow, Dusan P. Sekulic, IEEE, International Symposium on Sustainable Systems and Technologies, Washington D.C., May 16-19, 2010 for Carbon Nanotubes But the Energy Requirements are Falling
  • 51. Will Costs Fall?  Like Graphene, Carbon NanoTubes have low material costs  But how much will the processing costs fall?
  • 52. Large Variety of Processes Makes Many Optimistic about Carbon Nanotubes  Carbon nanotubes are made by several methods  Chemical Vapor Deposition (CVD)  arc discharge  laser ablation  HIPCO®: Hi-pressure carbon monoxide  surface mediated growth of vertically-aligned tubes by Plasma Enhanced Chemical Vapor Deposition (PECVD)  Understanding their growth in these processes is critical to making them cheaper  Costs will probably fall as scale increases of HIPCO process (see later slide on nano-fibers made from carbon nanotubes)
  • 53. Researchers at USC have solved a long-standing challenge with carbon nanotubes: how to actually build them with specific, predictable atomic structures.―We are now working on scale up the process,‖ Zhou said. ―Our method can revolutionize the field and significantly push forward the real applications of nanotube in many fields.‖ Until now, scientists were unable to ―grow‖ carbon nanotubes with specific attributes — say metallic rather than semiconducting — instead getting mixed, random batches and then sorting them. The sorting process also shortened the nanotubes significantly, making the material less practical for many applications. Chirality-Dependent Vapor-Phase Epitaxial Growth and Termination of Single-Wall Carbon Nanotubes, Bilu Liu †, Jia Liu †, Xiaomin Tu ‡, Jialu Zhang †,Ming Zheng *‡, and Chongwu Zhou *, nanoletters, Augu Improved Control over Production of CNTs
  • 54. Electrical/Electronic Applications  Transparent Electrodes for displays, batteries and solar cells  Transistors and Interconnect for integrated circuits  Cables and Wires  Ultra-capacitors for energy storage  Sensors  Medical – vibrations of nanotubes from radio waves (pass through tissue) or their emission of light can kill cancer cells
  • 55. For Transparent and Conductive Sheets on Electronic Paper (Trying to find lower resistance and higher transmittance) http://www.osa-direct.com/osad-news/654.html
  • 56. Another Application Might be Flywheels  May be a large market for carbon nanotubes and/or grapheme  Energy density of flywheels is a function of strength- to weight ratio  E/m = K (sigma/rho)  E= kinetic energy of rotor; M = mass  K = rotor‘s geometric shape factor  Sigma = tensile strength of material  Rho = material‘s density  Flywheels have about same energy density as Li-ion batteries but much faster rate of improvement  Carbon fibers are now being used in formula 1 cars  But CNTs have 10 times higher strength to weight ratios than do carbon fiber. Thus 10 times higher energy densities are possible Source: Presentation by MT5009 students on April 11, 2013. Slides can be found on http://www.slideshare.net/Fun
  • 57. For Transistors and Integrated Circuits  I.B.M. scientists were able to pattern an array of carbon nanotubes on the surface of a silicon wafer and use them to build hybrid chips with more than 10,000 working transistors  They did this by using a process they described as ―chemical self-assembly‖ to create patterned arrays in which nanotubes stick in some areas of the surface while leaving other areas untouched  Perfecting the process will require a more highly purified form of the carbon nanotube material http://bits.blogs.nytimes.com/2012/10/28/i-b-m-reports-nanotube-chip-breakthrough/
  • 58. Improvements in Purity of CNTs (and Increases in Source: Electronics: The road to carbon nanotube transistors, Aaron D. Franklin Nature 498, 443–444 (27 June 2013)
  • 59. For Transistors and Integrated Circuits (2)  In the short term, high purity CNTs will probably be used to achieve higher conductivity channel length and perhaps interconnect  Mentioned in previous session  In the long run, different types of CNTs may be used for the conducting, insulating, and semiconducting regions  Thus creating a new form of integrated circuit http://bits.blogs.nytimes.com/2012/10/28/i-b-m-reports-nanotube-chip-breakthrough/
  • 60. Market Size for Carbon Nanotubes
  • 61. Production Capacity, Producers, and Applications for Carbon NanoTubes http://www.nanowerk.com/spotlight/spotid=23118.ph p
  • 62. Outline  What is nanotechnology?  Fullerene, Graphene and Carbon Nanotubes  Quantum Dots  Nanoparticles  Nanofibers  Common issues
  • 63. Quantum Dots  Semiconductors also exhibit interesting behavior as sizes reach the nano-scale, single nanometer levels  Quantum dot is semiconductor whose electronic characteristics are closely related to size and shape of individual crystal  Generally, the smaller the size of crystal, the larger the band gap and thus  the greater the difference in energy between the highest and 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
  • 64. Quantum Dots (2)  For example, some can emit light like a laser  Size of the dot determines the wavelength, i.e., color of the light, that is emitted  Power consumption is very low  Efficiency and switching speeds can be very high  While others can absorb light  Size of the dot determines the wavelength, i.e., color of the light, that is absorbed (i.e., solar cells)  One problem is that they are very expensive (thousands of dollars per gram)
  • 65. Source: Semiconductor II-VI Quantum Dots with Interface States and Their Biomedical Applications By Tetyana Torchynska and Yuri Vorobiev Different Size Dots Emit Different Wavelengths of Light
  • 66. Applications of Quantum Dots  Lasers and Displays  Different size dots on a single substrate each emitting different wavelengths with lower power consumption  Lasers can be smaller, faster, and consume less power than current ones for telecommunication and computing applications  Solar cells/Photosensors  different size quantum dots absorb different wavelengths of light  Thus a single substrate can absorb different wavelengths of light and thus have much higher efficiencies than current solar cells  Higher sensitivities for photosensors  Medical applications  Different dots are coated with different layers, which enable different dots to bond with different targets
  • 68. Materials Today 14(9) September 2011, Pages 388–397 Reductions in Threshold Current, i.e., Minimum Current Needed for Lasing to Occur (by reducing sizes of devices)
  • 69. Source: Changhee Lee, Seoul National University http://www.andrew.cmu.edu/org/nanotechnology-forum/Forum_7/Presentation/CH_Lee.pdf JH Kwak PhD Thesis (2010) Improvements in Efficiency of Quantum Dots for Dis
  • 70. Manufacturing is One Challenge  These dots can be manufactured by depositing a vapor of the relevant compound, e.g., molecular beam epitaxy  For example, the atomic lattice mismatch between InAs and GaAs causes the deposition of InAs onto GaAs where the InAs self-assembles into nanoscale islands that show quantum dot behavior  Quantum dots are much more expensive than quantum wells  Can costs be reduced? By how much?  As the costs/prices are reduced, what kinds of applications become economically feasible?http://www.photonics.com/Article.aspx?AID=14668
  • 71. Is the Market for Quantum Dots Growing A key barrier is price: quantum dots can cost anywhere from US$3,000 to $10,000 per gram, restricting their use to highly specialized applicationsSource: http://www.nature.com/news/ 2009/090610/full/459760a.ht ml (2009)
  • 73. Outline  What is nanotechnology?  Fullerene, Graphene and Carbon Nanotubes  Quantum Dots  Nanoparticles  Nanofibers  Common issues
  • 74. Characteristics of NanoParticles  Greater percentage of atoms at surface, which leads to unique properties  Changes in wavelengths absorbed and emitted  Higher reactance  Higher magnetic moment  Higher strength  Ability to enter living organisms  But finding the appropriate material and matching it to the application is a major challenge
  • 75. Source: Binns, C. 2010. Introduction to Nanoscience and Nanotechnology
  • 76. Absorption Varies by Size of Nanoparticle  Like quantum dots, absorbed wavelengths vary by size  For example, small particles of zinc oxide and titanium dioxide absorb ultraviolet but not visible light  Thus, the sunscreen is invisible to visible light
  • 78. High Reactivity is Useful for some Applications  Can be used for stain resistant pants  Small particles react with stains to eliminate them  How about other applications?  Can other materials be found whose reactance varies by size?  Will these new materials lead to applications other than stain resistant pants?  Or maybe just help in existing applications. For example, high reactance can lead to
  • 79. Source: Binns, C. 2010. Introduction to Nanoscience and Nanotechnology Magnetic moments increase as particle size decreases; how much more can be achieved? Rh
  • 80. Magnetic Nanoparticles  Can make single particle magnetic storage possible  Increases limit of platters to 100 Tb/in2, or 1000 times more than existing densities  But medical applications may be bigger  Aids in detection by improving contrast of MRI via higher magnetic moments; improvements are possible  Can be steered to cancer cells with external magnetic field  Can destroy cells by oscillating magnetic field that creates heat  Trials on humans have started
  • 81. Improved Relaxivity (better detection) with Higher Magnet Moments (Dotted line shows expected improvements Source: Binns, C. 2010. Introduction to Nanoscience and Nanotechnology
  • 82. Source: Binns, C. 2010. Introduction to Nanoscience and Nanotechnology Cancer cells can be killed by Hyperthemia
  • 83. Hyperthemia  Power of about 0.1 W/cm3 is needed to kill cancer cells  Effectiveness of nanoparticles at heating can be measured by specific absorption rate (SAR)  Typical rate for magnetic nanoparticles is 10 W/g  Thus  0.01 g of nanoparticle is required to achieve 0.1 W and  Thus hundreds of thousands of nanoparticles are needed for cancer cells, which is probably far more than is possible for many receptors
  • 84. Are These Values for SAR Sufficient?
  • 85. Other Treatments for Killing Cancer Cells  Current treatments (e.g., chemotherapy) kill patients  Nanoparticles can be ―programmed/designed‖ to find and kill specific cancer cells  Several thousand have been reported in literature  Lipsomes, protocells release drugs on contact with cancer cells  Dendrimers are tree-like polymers with many active sites for bonding external agents – each targeting cancer cells  Reflectivity of light from gold and silver particles depends on their binding to cancer cells and some of them can be made to vibrate and kill cancer cells via absorption of infrared light  Vibrations of nanotubes from radio waves (pass through tissue) or their emission of light can kill cancer cells
  • 86. Part of Finding Cancer Cells Involves Biological Targeting  Selective binding to cancer cells enhances treatment  Antibodies are the oldest and most studied  but too large (can‘t enter cells) and expensive  Nanobodies contain fragments of antibodies  Aptamers  artificially short section of DNA  much cheaper than antibodies  Peptides are even smaller  Composed of 20 amino acid building blocks  Smallest method of targeting is folates/folic acid: only 51 atoms  Finding the appropriate biological material and
  • 87. Big Challenge is Price  Nanoparticles are made by condensation of a supersaturated vapor into particles particularly with a vacuum source  But since the cost of a vacuum is high, many search for a cheaper process such as one using high voltage sparks  Since magnetic nanoparticles are often used for living organisms and are produced by some bacteria, some use bacteria to synthesize them.  On the other hand, only a small number of particles may be needed for each patient…
  • 88. Outline  What is nanotechnology?  Fullerene, Graphene and Carbon Nanotubes  Quantum Dots  Nanoparticles  Nanofibers  Common issues
  • 89. Examples  Cargo nets  Ultra-high-molecular-weight polyethylene  15 times stronger on a weight basis than steel, but 4 times more expensive than typical polyester net  Robotic cables  Vectran  Fire resistant textiles  Textiles that  absorb body odor  block radiation
  • 90. Smaller Diameters Lead to Higher Strength  This is true for many materials such as electrospun Polyamide 6.6 fibers  The increased strength of fine diameter fibers (<500 nm) is attributed to the oriented fragments of amorphous chains  The fibers display remarkably improved properties when the size of this oriented amorphous part is comparable to overall fiber diameter  But finding the appropriate materials and applications for them is a challenge
  • 91. Decreasing the size of the fiber leads to higher tensile strength (breaking point) and tensile modulus (tension) (Hi-Tensile Steel is 1860 and 200) Source: Effect of fiber diameter on the deformation behavior of self- assembled carbon nanotube reinforced electrospun Polyamide 6,6 fibers Avinash Baji, Yiu-Wing Maia, Shing-Chung Wong. Materials Science and Engineering A 528 (2011) 6565– 6572
  • 92. Big Challenge is Manufacturing/Process  Electrospinning is the main manufacturing technique, but still quite expensive  Improvements over the last ten years in productivity of single nozzle setup from 0.5 grams per hour to 6.5 kilograms per hour (Source: Chem. Soc. Rev., 2012, 41, 4708– 4735)  To what extent can further improvements be made?  What applications will be made possible through these reductions in cost/price?
  • 93. What About Using Carbon NanoTubes to Make these Fibers?  Since they have nano-level dimensions, we would expect the fibers made from them to have high strength  Manufacturing techniques:  spinning from a lyotropic liquid crystalline suspension of nanotubes, in a wet-spinning process similar to that used for polymeric fibers such as aramids  spinning directly from an aerogel of single walled carbon nanotube (SWCNTs) and multi-walled CNTs (MWCNTs) as they are formed in a chemical vapor deposition reactor  spinning from MWCNTs previously grown on a substrate as ‗‗semialigned‖
  • 94. Carbon NanoTube (CNT)-based fibers can have Higher strengths than do other High- performance fibers Source: An assessment of the science and technology of carbon nanotube- based fibers and composites, Tsu-Wei Chou b,*, Limin Gao a, Erik T. Thostenson b, Zuoguang
  • 95. The Main Challenge is Process/Manufacturing  Strength, other performance dimensions and cost depends on process so need improvements in process  Cost data could not be found but…  Energy requirements are still high  Four orders of magnitude less than that of carbon nanotubes  Similar energy per kg as Aluminum  But carbon nanotubes must be made before the fiber can be made…….
  • 96. Source: Minimum Exergy Requirements for the Manufacturing of Carbon Nanotubes, Timothy G. Gutowski, John Y. H. Liow, Dusan P. Sekulic, IEEE, International Symposium on Sustainable Systems and Technologies, Washington D.C., May 16-19, 2010 Energy Intensity vs. Process Rate for Production of Carbon Nano-fibers to put these process rates in perspective, ethylene is made in factories one million times larger than this
  • 97. Market forecasted to grow from US$ 140M in 2010 to US$ 4B by 2020 http://www.adsaleata.com/Publicity/MarketNews/lang- eng/article-112763/Article.aspx
  • 98. Outline  What is nanotechnology?  Fullerene, Graphene and Carbon Nanotubes  Quantum Dots  Nanoparticles  Nanofibers  Common issues
  • 99. Common Issues (1)  Need to find materials that better exploit small dimensions and that are appropriate for specific application  Nanoparticles that selectively bind to cancer cells and kill them  Materials for quantum dots and nanofibers  Need to find new processes that produce more appropriate and better nano-materials  But at what rate and for what applications are we finding these new materials?  And what does this tell us about when new applications become economically feasible?
  • 100. Common Issues (2)  Costs are too high  Nanoparticles, Quantum Dots, Nanofibers  Fullerene, Graphene and Carbon Nanotubes  How fast will costs fall?  They will probably fall at slower rate than what has been seen with ICs (i.e., Moore‘s Law)  No discernible benefit from reductions in scale  Costs may fall as scale of production is increased or as new processing methods are found  See Sessions 2 and session on roll-to roll printing for more details on impact of increases in scale of production equipment on manufacturing costs  Which applications will become economically feasible as the production costs for nanotechnology fall?
  • 102. Price of carbon fiber http://www.zoltek.com/carbonfiber/the-history-of-carbon-fiber/ Carbon fiber in vehicles http://auto.howstuffworks.com/fuel-efficiency/fuel-economy/carbon-fiber-oil-crisis2.htm Roadmap for graphene http://www.nature.com/nature/journal/v490/n7419/full/nature11458.html?WT.ec_id=NATURE- 20121011 http://www.graphenea.com/pages/graphene-price#.UonUjnASbTp Euros per square
  • 103. Graphene transistors http://phys.org/news/2012-07-graphene-transistor.html Improve strength of material by combining it with graphene in sandwich composite http://spectrum.ieee.org/nanoclast/semiconductors/nanotechnology/for-first-time- graphene-and-metal-make-strong-composite Graphene applications http://www.graphenea.com/pages/graphene-uses-applications#.UonTB3ASbTr http://www.ft.com/cms/s/0/6f4717b6-66f9-11e2-a83f- 00144feab49a.html#axzz2ktOs2EWw Transparent conductors http://onlinelibrary.wiley.com/doi/10.1002/adma.201200489/abstract;jsessionid=245 08C91658C71CB5F94C7AED94D5BC8.d03t01 http://www.luxresearchinc.com/blog/coveragearea/advanced-materials/

Editor's Notes

  1. After looking at the market demand of CNT, we’d want to know how much does CNT cost if we were to use it as raw material,Our team has been searching hi and low for the pricing trend of CNT but found out that most of the source are charging at least a few hundred dollars for it.Hence, based on various reports and all the possible information which we could get hold of, we plotted them into the nice looking graph with colourful data points.This graph shows the price trends of various materials such as CNTs (SWCNT, MWCNT), Indium, carbon fibre and steel when they are in mass production in terms of multi tonnes.First, we see that CNTs are becoming cheaper over the years and are currently in 2013, already cheaper than Indium, a material that’s used to produce TE by almost 8times.Secondly, though they are now still much more expensive than Carbon fibre (approximately 8 times), however, with its decreasing trend, we are confident that CNTs will be able to catch up with the price of carbon fibre in the near future.Then at the bottom of the graph, you can see that steel is hovering less than 1/thousandth of a dollar per gram which is relatively stable nowadays.It is at this price that we’d say, a very ambitious target that we foresee CNT would arrive at in the long term, not sure how long it’ll take, BUT there’re possibilities (these, I will show you in a short while)www.cheaptubesinc.com/carbon-nanotubes-prices.htmwww.helixmaterial.comNanotechnology by Ben Rogers, Sumita Pennathur, Jesse Adams, CRC Pres,s 2011New Methods for Continuous Production of Carbon Nanotubes, Science Daily, Apr. 10, 2012www.minerals.usgs.govhttp://www.ptonline.com/articles/carbon-nanotubes-lots-of-potentialif-the-price-is-righthttp://www.prnewswire.com/news-releases/production-and-application-of-carbon-nanotubes-carbon-nanofibers-fullerenes-graphene-and-nanodiamonds-a-global-technology-survey-and-market-analysis-131970098.html12% from 2012 to 2016Carbon fibre on 25 Sep 2013 -http://www.mypurchasingcenter.com/commodities/commodities-articles/carbon-fiber-prices-more-competitive/Carbon fibre 2011 - http://www.rmi.org/RFGraph-carbonfiber_vs_steel_manufacturinghttp://gizmodo.com/5843276/why-is-carbon-fiber-so-expensiveSteel - http://www.mypurchasingcenter.com/commodities/commodities-articles/steel-price-forecast-2014/Steel - http://www.meps.co.uk/World%20Carbon%20Price.htm