A Brief Introduction to Nanotechnology

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 Nanotechnology Defined
“The development and use of devices that have a size of only a few
nanometres.” physics.about.com
“Research and technology development at the atomic, molecular or
macromolecular level in the length scale of approximately 1 - 100 nm range,
to provide a fundamental understanding of phenomena and materials at the
nanoscale and to create and use structures, devices and systems that have
novel properties and functions because of their small and/or intermediate
size.” www.nano.gov
“Branch of engineering that deals with things smaller than 100 nm
(especially with the manipulation of individual molecules).”
www.hyperdictionary.com
“Nanotechnology, or, as it is sometimes called, molecular manufacturing, is
a branch of engineering that deals with the design and manufacture of
extremely small electronic circuits and mechanical devices built at the
molecular level of matter.” www.whatis.com
“The art of manipulating materials on an atomic or molecular scale
especially to build microscopic devices.” Miriam Webster Dictionary
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 Perspective of Length Scale
1 km
Top Down Aircraft Carrier
Boeing 747
Car
1m Humans
Laptop
Butterfly
Size of a Microprocessor
1 mm Gnat
Resolving power of the eye ~ 0.2 mm
Micromachines

Biological cell
1 m Nucleus of a cell
Wavelength of Visible Light
Smallest feature in microelectronic chips
Nanostructures & Quantum Devices
Proteins http://www.dod.gov/news/
Width of DNA
electron

Bottom Up 1 nm Dec1997/
neutron

n12301997_9712302.html
proton

Not for distribution Size of an atom

 Perspective of Size

Water molecules – 3 atoms

Protein molecules – thousands of atoms
DNA molecules – millions of atoms water molecule

Nanowires, carbon nanotubes – millions of atoms

Carbon
nanotube
Molecule of DNA
Protein molecule
www.iacr.bbsrc.ac.uk/notebook/ courses/guide/dnast.htm
www.phys.psu.edu/~crespi/research/_carbon.1d/public
student.biology.arizona.edu/.../ group2/crystallography.htm
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 How Small is a nm?

1 µm = one millionth of a meter

1 nm = one billionth of a meter
≈ 1/50,000 thickness of a hair!
≈ a string of 3 atoms

If we shrunk all distances by 110,000,000,000 X Human hair

The sun and earth would be separated by 1 m thickness ~ 50 µm

A football field would be 1 nm 110 m

110,000,000 km

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 Surface vs. Volume
a
Si has a diamond structure with a = 5.43 Å
A Si nanocube 10 nm on a side is composed of:
~6250 unit cells
~50,000 atoms
Each nanocube face is composed of: Diamond unit cell
~340 unit cells per face
~680 surface atoms per face
Si nanocube
Total surface area is:
~4080 atoms (~10% surface atoms)
A bulk Si film 1 µm thick on a 10 cm square:
~6.3 X 1019 unit cells
~5 X 1020 atoms Bulk Si film
~1.4 X 1017 surface atoms (~0.03% surface atoms)
In a nanoscale material, the surface/boundary/interface plays an important role!
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 More than just size…
Interesting phenomena:
Chemical – take advantage of large
surface to volume ratio, interfacial
and surface chemistry important,
systems too small for statistical analysis

Electronic – quantum confinement,

bandgap engineering, change in STM of dangling bonds on a
density of states, electron tunneling Si:H surface

b
Magnetic – giant magnetoresistance
by nanoscale multilayers, change in
magnetic susceptibility

http://pubweb.acns.nwu.edu/~mhe663/ Electron tunneling

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 More than just size …
Interesting phenomena:
Mechanical – improved strength
hardness in light-weight nanocomposites
and nanomaterials, altered bending,
compression properties, nanomechanics
of molecular structures
Fluorescence of quantum dots
Optical – absorption and fluorescence of of various sizes
nanocrystals, single photon phenomena,
photonic bandgap engineering
Fluidic – enhanced flow properties with
nanoparticles, nanoscale adsorbed films
important
Thermal – increased thermoelectric
performance of nanoscale materials,
interfacial thermal resistance important.
Phonon tunneling

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 Development of Nanotechnology

Fundamental
Understanding

Characterization
Modeling and
and
Simulation
Experimentation
Synthesis and
Integration
Nano to Macro
Inorganic and Organic
Optical with Mechanical
with Electrical with
Magnetic with …

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 Nanotech – The next new thing?
Old Nanotechnology New Nanotechnology
Vastly improved catalysts enhance
surface area to volume ratios

Stained-glass windows – Designer drugs

Silver-Halide Photography Cheap, sensitive medical

diagnostics
AR-coated lenses
Transparent Sunblock
Viruses are nanomachines
Nanotube-strengthened cables
The difference between
old and new nano:

Now, we are designing and manipulating at the molecular level whereas

before it was either evolution that did it for us or results happened which
we never really understood and so couldn’t optimize.
Not for distribution nanopedia.cwru.edu
 Ohio’s Position in Nanotechnology

Not for distribution James Murday, Naval Research Laboratory

 Nanofabrication

Nanofabrication can generally be divided into

two categories based on the approach:
“Top-Down”: Fabrication of device
structures via monolithic
processing on the nanoscale.
“Bottom-Up”: Fabrication of device structures
via systematic assembly of
atoms, molecules or other
basic units of matter.

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 Integrated Circuits and Nanotech

The IC industry is
approaching a period
where nanotech
approaches will be
required to sustain
technology growth

J.D. Plummer, M.D. Deal, and P.B. Griffin, “Silicon VLSI Technology – Fundamentals, Practice and Modeling” Prentice Hall, NJ
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 Nanotech and Microfabrication
• Microfabrication is a top-down technique
utilizing the following processes in
sequential fashion:
– Film Deposition
• CVD, PVD
– Photolithography
• Optical exposure, PR
– Etching
• Aqueous, plasma

Many of these techniques are useful, directly or indirectly in

nanofabrication
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 Top - Down Nanofabrication

at input of Cryoamp (nV)

15
8T

Signal Amplitude
10 7T
6T
5T
5 4T
3T

-5

-10

Length: 1.1 m 1.00 1.01 1.02 1.03 1.04

Frequency (GHz)
Width: 120 nm
Thickness: 75 nm

SEM showing one of the two doubly-clamped 3C-SiC beams in a

device structure. The device was fabricated using top-down techniques.
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 What are Nanostructures?
At least one dimension is between 1 - 100 nm
2-D structures (1-D confinement):
• Thin films
• Planar quantum wells
• Superlattices
1-D structures (2-D confinement):
• Nanowires 2 m
• Quantum wires
• Nanorods Si Nanowire Array
• Nanotubes
0-D structures (3-D confinement): Multi-wall carbon
• Nanoparticles nanotube
• Quantum dots
Dimensionality, confinement depends on
structure:
• Bulk nanocrystalline films
• Nanocomposites
http://www.aip.org/mgr/png/2003/186.htm
Si0.76Ge0.24 / Si0.84Ge0.16 superlattice
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 Thin Films
Nanoscale Thin Film
• Single “two dimensional” film, thickness < ~100 nm
• Electrons can be confined in one dimension;
affects wavefunction, density of states
• Phonons can confined in one dimension; affects thermal
transport
• Boundaries, interfaces affect transport
a
Thin film
Bulk
crystal

Substrate

Free
standing d
thin film http://scsx01.sc.ehu.es/waporcoj/
charlas/cursodoctorado/12
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 Thin Film Applications

Solid Fuel Cells: (nanostructured) thin

film solid electrolytes and electrodes
with high conductance
Thin Film Transistors for liquid crystal
displays: requires high mobility and
flexible substrates
100 nm sputtered YSZ
Gas sensing applications film for solid oxide fuel
cells
Thin layers in electronic devices

Wagner et al, Thin Solid Films, Vol.

490, pp. 12 – 19 (2003).
http://www.bu.edu/mfg/pdf/Tuller.pdf Amorphous Si TFT on a SiNx
Not for distribution passivated polyimide foil
 Nanowires
• Solid, “one dimensional”
• Can be conducting, semiconducting, insulating
• Can be crystalline, low defects
• Can exhibit quantum confinement effects
(electron, phonon)
• Narrowing wire diameter results in increase in 2 m
band gap Si Nanowire Array
• Narrowing wire diameter can result in
decrease in thermal conductivity
• New forms include core-shell and
superlattice nanowires

Nanotube defined – a long cylinder with

inner and outer nm-sized diameters
Nanowire defined – a long, solid wire
with nm diameter
Abramson et al, JMEMS (2003) Si/SiGe Nanowires
Not for distribution Wu et al, Nanoletters, Vol. 2, 83 – 86 (2002)
 Nanowires Applications
Field effect transistors
Thermoelectric materials
Light emitting diodes
Detectors
Sensors
Nanolasers
Superlattice nanowires
in applications requiring
superlattices
Nanolaser from 100 nm
CdSe nanowire

http://www.photonics.com/spectra/tech/
XQ/ASP/techid.1525/QX/read.htm 5 nm Si nanowire FET
Cui et al, Nanoletters, Vol. 3, 149 – 152 (2003).

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 Carbon Nanotubes
Carbon nanotube properties:
• One dimensional sheets of hexagonal
network of carbon rolled to form tubes
• Approximately 1 nm in diameter
• Can be microns long
• Essentially free of defects
• Ends can be “capped” with half a buckyball
• Varieties include single-wall and multi- wall Multi-wall carbon
nanotubes,ropes, bundles, arrays nanotube
• Structure (chirality, diameter)
influences properties: Armchair
– Semiconducting vs. metallic
– Thermal, electrical conductance
Zigzag
– Mechanical strength, elasticity
http://physicsweb.org/article/world/11/1/9/1
http://www.aip.org/mgr/png/2003/186.htm Chiral
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 Other Nanotubes…
Boron nitride nanotubes Boron nitride
• Resistance to oxidation, nanotubes
suited for high temperatures adopt various
shapes
• Young’s modulus of 1.22 TPa (red=boron,
• Semiconducting blue=nitrogen):

• Predictable electronic
properties independent of
diameter and # of layers
SiC nanotubes:
• Resistance to oxidation SiC nanotubes
• Suitable for harsh grown at NASA
environments Glenn:

• Can functionalize surface Si

atoms
http://www.grc.nasa.gov/WWW/RT2002/5000/5510lienhard.html
http://pubs.acs.org/cen/topstory/7912/7912notw1.html
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 Nanoparticles/Quantum Dots
• “Zero-dimensional” particle Radius of particle or cluster
• Surface effects/chemistry important 105 nm
• Radius < 100 nm
• < 10 atoms per nanoparticle
6 104
nm bulk
• Size smaller than critical length scales 103 nm
(e.g. mean free path, wavelength)
• Nano/quantum physical phenomena 102 nm
present
• “Large” nanoparticles have same structure 10 nm nanoparticles
as bulk; “small” may be different
• Synthesis: RF plasma, chemical, 1 nm quantum dots
thermolysis, pulsed laser molecules
• “Old” examples 1A
– Stained glass – small metal oxide clusters
comparable in size to the wavelength of light
– Photography – small colloidal silver particles
for image formation
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 Nanoparticles/Quantum Dots

Metalic nanoparticles Gradient of gold nanoparticles

on a silica surface

http://www.bnl.gov/bnlweb/pubaf/
pr/2002/bnlpr071802.htm
Bapat et al, J Appl Phys, Vol. 94,
1969 – 1974 (2003) Si nanoparticle; single-
www.aveka.com crystal; hexagonal shape
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 Semiconductor Nanoparticles
• Nanoparticles comprised of “bulk semiconductor” elements
exhibit unique optical properties
• Shift in optical absorption particle toward shorter
wavelengths with reduced size
• For particle radius > exciton radius
photon induced transitions in exciton energy levels
produce series of discrete optical absorption levels
• For particle radius < exciton radius
no exciton and individual electron and hole transitions
of discrete optical absorption levels observed

Fluorescence at different
wavelengths from a single
UV light due to quantum
confinement in
semiconductor quantum
www.nanosysinc.com
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dots
 Nanoparticle Probes
• Objective: To detect and “kill” individual cancer cells before
they manifest as tumors using functionalized nanoparticles
– 5 to 10 nm particles (small enough to interact with intracellular
markers)
– nanoparticles are coated and functionalized with antibodies,
oligonucleotides, peptide ligands and drugs
– Introduced to body via bloodstream
– “Look” for markers inside cell by MRI or deliver agent or irradiate

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 Nanostructured Bulk Materials
Includes:
• Amorphous/glassy materials (atomic scale ordering)
• Any material with nanostructured grain sizes (nm ordering)
• Nanoporous materials (nm ordering)
• Multilayer nanoscale thin films (nm ordering – SL period)
Solid formations crystalline, amorphous, polycrystalline

Polycrystalline
materials can be
nanostructured if
grain sizes < 100 nm

Characteristics (Å to nano to micro) affect chemical, physical,

mechanical properties, which are usually enhanced
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 Nanostructured Bulk Materials
Applications
Manufacturing – thermal barrier coatings
ceramic films
problem: require lower thermal
conductivity/high strength
solution: nanostructured films?
Other applications:
Catalysts Nanocrystalline thermal
Solar cells barrier coating of YSZ
Stronger, long lasting materials applications
Electronics
Batteries
Sensors http://
www.msd.anl.gov/
Flat panel displays groups/im/highlights/
thermal/
thermalconductivity.ht Nanocrystalline diamond
http://www.msd.anl.gov/groups/im/highlights/
ml coatings for field emission tips
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diamondemission/emission.html
 Nanocomposites
• Nanocomposite – consists of two or more synthesized
materials of which at least one has nanoscale dimensions
• Can exhibit enhanced chemical, optical, physical,
mechanical properties as compared with constituent bulk
• Multiple material possibilities
– Organic + organic
– Organic + inorganic
– Inorganic + inorganic
Nanoparticle or nanowire or nanotube + matrix material

Why nano and not micro?

Micro also gives increase elastic modulus, but microparticles
act as stress concentrators, decrease in strain to failure,
decrease in strength and toughness
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 Nanocomposite Applications
Luminescent nanocomposites for
opto-electronics
Electronics (e.g. dielectric layers)
Intracellular manipulation
Thermoelectric materials
High-strength, toughness structural
materials
Electrolytes in batteries
Insulation
Coatings
Gas separation
Fire barriers TiO2-oligonucleotide
nanocomposites hybridized with
Merkel et al, Science, DNA for cellular manipulation
Vol. 296, 519 – 522 Polymer containing 40 wt%
(2002) silica particles for use as a gas
Not for distribution separation membrane
 What can we measure?
strain
defects
atomic species crystallinity
surface roughness
concentration
diffusion composition structure
segregation

properties

electrical/optical mechanical
magnetic Seebeck
coefficient band yield failure
carrier density gap
tensile stiffness
susceptibility electron dielectric strength
constant
magneto- states hardness modulus of
resistance conductivity elasticity
thermal
conductivity specific heat
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 Atomic Force Microscopy
The optical microscope – cannot
see features smaller than ~half
the wavelength of light
Can we use something other
than light and lenses?
AFM basic components:
• Tip (<~10 nm diameter) on a
cantilever
• Detector (generally position)
• Raster-scan (to drag tip)
• Force/height control
• Image processing software
Lateral resolution 0.1 nm
Vertical resolution 0.02 nm Image of graphite
using an AFM
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 AFM modes
contact mode non-contact mode

Tip angstroms from surface Tip hundreds of angstroms from

(repelled) surface (attracted)
Constant force Variable force measured
Highest resolution Lowest resolution
May damage surface Non-destructive
tapping mode Intermittent tip contact
Variable force measured
Improved resolution
Non-destructive
Courtesy
Courtesy of
of F.
F. Ernst
Ernst
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 AFM images

Cu Nanowires

Ge islands on Si

K.
K. Brunner
Brunner et
et al.
al.
R.
R. Adelung
Adelung et
et al.
al. Courtesy
Courtesy of
of F.
F. Ernst
Ernst
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 Scanning Electron Microscopy
Instead of light, the SEM uses
electrons to see 3-D images
SEM operation:
• Air pumped out (vacuum)
• e- gun emits beam of high
energy electrons
• e- beam focused via lenses
• Scanning coils move beam
across sample
• Secondary electrons are
“knocked off” surface
• Detector counts electrons
• Image given by # e-
Resolution ~5 nm Courtesy
Courtesy of
of F.
F. Ernst
Ernst
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 SEM and AFM images

SEM: Cu Nanowires

AFM: Cu Nanowires

R.
R. Adelung
Adelung et
et al.
al. Courtesy
Courtesy of
of F.
F. Ernst
Ernst
Not for distribution
 Transmission Electron Microscopy
A TEM works like a slide projector but
with e- instead of light
TEM operation:
• Air pumped out (vacuum) sample
• e- gun emits beam of high energy e-
• e- beam focused via lenses lens
• Beam strikes sample and some e-
are transmitted
• Transmitted e- are focused, amplified
• Image contrast enhanced by
blocking out high-angle diffracted e-
• Image passed through lenses and
enlarged
• When image hits phosphor screen,
light is generated
Resolution ~<1 nm Courtesy
Courtesy of
of F.
F. Ernst
Ernst
Not for distribution
 TEM of Ge on Si
HRTEM Cross-Sectional View

Courtesy
Courtesy of
of F.
F. Ernst
Ernst
Not for distribution
 TEM comparison

Standard TEM High resolution TEM

Courtesy
Courtesy of
of F.
F. Ernst
Ernst
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 Carbon Nanotube Applications

Not for distribution G. Dusburg, Infineon Technologies, Munchen Germany

 Carbon Nanotube Applications

Not for distribution G. Dusburg, Infineon Technologies, Munchen Germany

 Carbon Nanotube Applications

Not for distribution G. Dusburg, Infineon Technologies, Munchen Germany

 Carbon Nanotube Applications

Not for distribution G. Dusburg, Infineon Technologies, Munchen Germany

 Materials for Interconnects
Carbon
Aluminum Copper Nanotubes

1999 When?

Resistivity of Al Resistivity of Cu Very low electrical

= 2.6 μΩ-cm = 1.7 μΩ-cm resistivity of CNTs

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 Fabrication of CNT interconnects

Via etch Sputter deposit Lift-off MWNT growth by

Fe catalyst CVD using
H2,C2H2 at 700 oC

F. Kreupl et al.,
Microelectronic Engg.,
64, 399 (2002).

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 Energy Applications: Conversion,
Generation and Storage
Cold
Metal organic
framework for
hydrogen storage

Hot
2 m
I
Dresselhaus group, MIT
Replace conventional
material with nanocomposite
to enhance performance

Abramson et al, JMEMS, in review.

Rosi et al, Science, Vol. 300, pp. 1127
-1129 (2003).

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 Energy Applications: Catalysis
Oil refinement: zeolites are
nanoporous (pores 3 – 10 Å)
crystalline solids with well-defined
structures (“molecular sieves”) used
in oil refinement – increases
gasoline yield from each barrel of
crude oil by 50% Porous zeolite structure

http://www.iaee.org/
documents/p03eagan.pdf

http://www.bza.org/
zeolites.html 2 atomic layer thick Au
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nanoclusters on TiO2
 Energy Applications: LEDs
Change the nanostructure
of Si (a very cheap
material) to become
nanoporous and visible
light is emitted!
Use quantum dots
(quantum confinement) for
light emission
Cross-hairs of p-type and
n-type nanowires (to get a
p-n junction)
Network of nanowires

http://www.trnmag.com/Stories/011701/
Crossed_nanowires_make_Lilliputian_LEDs_011701.
html
Quantum dot layers

http://www.trnmag.com/Stories/2002/103002/Nanoscale_LED_debuts_103002.html
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 Energy Applications: LEDs
Quantum dots/
nanocrystals are smaller
than the wavelength of
light, so they do not
scatter light; scattering
can reduce optical
efficiency by up to 50%!

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 Energy Applications: Batteries
Change electrode materials by nanostructuring (texturing) to
improved electrical performance; nanoscale particles boost
energy storage and power delivery by reducing the distance
Li ions travel during diffusion
Nanobattery: Fill a nanoscale membrane with an electrolyte,
cap with electrodes; contact with a probe tip

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 Energy Applications: Solar
Solar cells integrated into roof
shingles
Nanoscale crystals of semiconductor
coated with light-absorbing dye emit
electrons
Nanostructured diamond
Nanostructured diamond solar thermal solar thermal cells
cells capture light, which heats the
lattice, which emits electrons; small tip
gives high energy electrons
Tetrapods (the light absorbing
materials) double the efficiency of
plastic solar cells because they always
point in the right direction Branched tetrapod
http://www.spacer.com/news/solarcell-01b.html
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 Web-based Resources

nanopedia.cwru.edu
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