M.

Meyyappan
NASA Ames Research Center
Moffett Field, CA 94035

email: mmeyyappan@mail.arc.nasa.gov
web: http://www.ipt.arc.nasa.gov
Nanometer
One billionth (10
-9
) of a meter
Hydrogen atom 0.04 nm
Proteins ~ 1-20 nm
Feature size of computer chips 90 nm
(in 2005)
Diameter of human hair ~ 10 m
Nanotechnology is the creation of USEFUL/FUNCTIONAL
materials, devices and systems (of any useful size) through
control/manipulation of matter on the nanometer length scale and
exploitation of novel phenomena and properties which arise because
of the nanometer length scale:
Physical
Chemical
Electrical
Mechanical
Optical
Magnetic


Research and technology development aimed
to understand and control matter at
dimensions of approximately 1 - 100
nanometer the nanoscale
Ability to understand, create, and use
structures, devices and systems that have
fundamentally new properties and functions
because of their nanoscale structure
Ability to image, measure, model, and
manipulate matter on the nanoscale to exploit
those properties and functions
Ability to integrate those properties and
functions into systems spanning from nano- to
macro-scopic scales
Corral of Fe Atoms D. Eigler
Nanoarea Electron Diffraction
of DW Carbon Nanotube
Zuo, et.al
What Is Nanotechnology?
Source: Clayton Teague, NNI
(Definition from the NNI)
Examples
- Carbon Nanotubes
- Proteins, DNA
- Single electron transistors

Not just size reduction but phenomena
intrinsic to nanoscale
- Size confinement
- Dominance of interfacial phenomena
- Quantum mechanics

New behavior at nanoscale is not
necessarily predictable from what we
know at macroscales.
AFM Image of DNA
Quantum size effects result in unique mechanical, electronic, photonic,
and magnetic properties of nanoscale materials
Chemical reactivity of nanoscale materials greatly different from more
macroscopic form, e.g., gold
Vastly increased surface area per unit mass, e.g., upwards of 1000 m
2

per gram
New chemical forms of common chemical elements, e.g., fullerenes,
nanotubes of carbon, titanium oxide, zinc oxide, other layered
compounds
Unique Properties of Nanoscale Materials
Source: Clayton Teague, NNI
Atoms and molecules are generally less than a nm and we study
them in chemistry. Condensed matter physics deals with solids
with infinite array of bound atoms. Nanoscience deals with the
in-between meso-world
Quantum chemistry does not apply (although fundamental laws
hold) and the systems are not large enough for classical laws of
physics
Size-dependent properties
Surface to volume ratio
- A 3 nm iron particle has 50% atoms on the surface
- A 10 nm particle 20% on the surface
- A 30 nm particle only 5% on the surface
MORE IN SECTION II
Many existing technologies already depend on nanoscale materials
and processes
- photography, catalysts are old examples
- developed empirically decades ago

In existing technologies using nanomaterials/processes, role of
nanoscale phenomena not understood until recently; serendipitous
discoveries
- with understanding comes opportunities for improvement

Ability to design more complex systems in the future is ahead
- designer material that is hard and strong but low weight
- self-healing materials
Recently, there has been an explosion of research
on the nanoscale behavior
- Nanostructures through sub-micron self
assembly creating entities from bottom-up
instead of top-down
- Characterization and applications
- Highly sophisticated computer simulations to
enhance understanding as well as create
designer materials
1959 Feynman Lecture There is Plenty of Room at the
Bottom provided the vision of exciting new discoveries if
one could fabricate materials/devices at the atomic/molecular
scale.

Emergence of instruments in the 1980s; STM, AFM
providing the eyes, fingers for nanoscale manipulation,
measurement
STM
Image of Highly Oriented
Pyrolitic Graphite
Cluster
- A collection of units (atoms or reactive molecules) of up to
about 50 units
Colloids
- A stable liquid phase containing particles in the 1-1000 nm
range. A colloid particle is one such 1-1000 nm particle.
Nanoparticle
- A solid particle in the 1-100 nm range that could be
noncrystalline, an aggregate of crystallites or a single
crystallite
Nanocrystal
- A solid particle that is a single crystal in the nanometer range
Source: Nanoscale Materials in Chemistry, Ed. K.J. Klabunde, Wiley, 2001
Spherical iron nanocrystals

J. Phys. Chem. 1996,
Vol. 100, p. 12142
For example, 5 cubic centimeters about 1.7 cm per side of
material divided 24 times will produce 1 nanometer cubes and
spread in a single layer could cover a football field
Repeat 24 times
Nanoscale = High Ratio of Surface Area to Vol.
Source: Clayton Teague, NNI
In materials where strong chemical bonding is present, delocalization of valence
electrons can be extensive. The extent of delocalization can vary with the size
of the system.

Structure also changes with size.

The above two changes can lead to different physical and chemical
properties, depending on size
- Optical properties
- Bandgap
- Melting point
- Specific heat
- Surface reactivity
-
-
Even when such nanoparticles are consolidated into macroscale solids, new
properties of bulk materials are possible.
- Example: enhanced plasticity
For semiconductors such as ZnO, CdS, and Si, the bandgap
changes with size
- Bandgap is the energy needed to promote an electron
from the valence band to the conduction band
- When the bandgaps lie in the visible spectrum, a change
in bandgap with size means a change in color

For magnetic materials such as Fe, Co, Ni, Fe
3
O
4
, etc., magnetic
properties are size dependent
- The coercive force (or magnetic memory) needed to
reverse an internal magnetic field within the particle is
size dependent
- The strength of a particles internal magnetic field can be
size dependent
In a classical sense, color is caused by the partial absorption of
light by electrons in matter, resulting in the visibility of the
complementary part of the light

On most smooth metal surfaces, light is totally reflected by the
high density of electrons no color, just a mirror-like
appearance.

Small particles absorb, leading to some color. This is a size
dependent property.
Example: Gold, which readily forms nanoparticles but not easily
oxidized, exhibits different colors depending on particle size.
- Gold colloids have been used to color glasses since early
days of glass making. Ruby-glass contains finely dispersed
gold-colloids.
- Silver and copper also give attractive colors
C = Q/mT; the amount of heat Q required to raise the
temperature by T of a sample of mass m
J/kg K or cal/g K; 1 calorie is the heat needed to raise the temp. of
1 g of water by 1 degree.
Specific heat of polycrystalline materials given by Dulong-Petit law
- C of solids at room temp. (in J/kg k) differ widely from one to
another; but the molar values (in J/moles k) are nearly the
same, approaching 26 J/mol K; C
v
= 3 Rg/M
where M is molecular weight
C
v
of nanocrystalline materials are higher than their bulk
counterparts. Example:
- Pd: 48% | from 25 to 37 J/mol.K at 250 K for 6 nm crystalline
- Cu: 8.3% | from 24 to 26 J/mol.K at 250 K for 8 nm
- Ru: 22% | from 23 to 28 J/mol.K at 250 K for 6 nm
The melting point of gold particles decreases dramatically as
the particle size gets below 5 nm
Source: Nanoscale Materials in Chemistry, Wiley, 2001
Start from an energy balance; assume the change in internal energy
(U) and change in entropy per unit mass during melting are
independent of temperature

Au =2T
o
o/Lr
u = Deviation of melting point from the bulk value
T
o
= Bulk melting point
o = Surface tension coefficient for a liquid-solid interface
= Particle density
r = Particle radius
L = Latent heat of fusion
Lowering of the melting point is proportional to 1/r

Au can be as large as couple of hundred degrees when the
particle size gets below 10 nm!

Most of the time, o the surface tension coefficient is unknown;
by measuring the melting point as a function of radius, o can be
estimated.

Note: For nanoparticles embedded in a matrix, melting point may
be lower or higher, depending on the strength of the interaction
between the particle and matrix.
For metals, conductivity is based on their band structure. If the
conduction band is only partially occupied by electrons, they can
move in all directions without resistance (provided there is a perfect
metallic crystal lattice). They are not scattered by the regular
building blocks, due to the wave character of the electrons.

=
e
4tc
o
m
e
v
v = electron speed
c
o
= dielectric constant in vacuum
t, mean time between collisions, is /v

For Cu, v = 1.6 x 10
6
m/s at room temp.; = 43 nm, t = 2.7 x 10
-14
s

Scattering mechanisms
(1) By lattice defects (foreign atoms, vacancies, interstitial
positions, grain boundaries, dislocations, stacking disorders)
(2) Scattering at thermal vibration of the lattice (phonons)

Item (1) is more or less independent of temperature while item #2
is independent of lattice defects, but dependent on temperature.

Electric current collective motion of electrons; in a bulk metal,
Ohms law: V = RI

Band structure begins to change when metal particles become
small. Discrete energy levels begin to dominate, and Ohms law is
no longer valid.
If a bulk metal is made thinner and thinner, until the electrons can
move only in two dimensions (instead of 3), then it is 2D quantum
confinement.
Next level is quantum wire
Ultimately quantum dot
Source: Nanoscale Materials in Chemistry, Wiley, 2001
Adsorption is like absorption except the adsorbed material is held near the surface
rather than inside

In bulk solids, all molecules are surrounded by and bound to neighboring atoms
and the forces are in balance. Surface atoms are bound only on one side, leaving
unbalanced atomic and molecular forces on the surface. These forces attract gases
and molecules Van der Waals force, physical adsorption or physisorption

At high temperatures, unbalanced surface forces may be satisfied by electron
sharing or valence bonding with gas atoms chemical adsorption or
chemisorption
- Basis for heterogeneous catalysis (key to production of fertilizers,
pharmaceuticals, synthetic fibers, solvents, surfactants, gasoline, other
fuels, automobile catalytic converters)
- High specific surface area (area per unit mass)
Frequently encountered powders:
- Cement, fertilizer, face powder, table salt, sugar, detergents, coffee
creamer, baking soda

Some products in which powder incorporation is not obvious
- Paint, tooth paste, lipstick, mascara, chewing gum, magnetic recording
media, slick magazine covers, floor coverings, automobile tires

For most applications, there is an optimum particle size
- Taste of peanut butter is affected by particle size
- Extremely fine amorphous silica is added to control the ketchup flow
- Medical tablets dissolve in our system at a rate controlled by particle size
- Pigment size controls the saturation and brilliance of paints
- Effectiveness of odor removers is controlled by the surface area of
adsorbents.
From: Analytical methods in Fine Particle Technology, Webb and Orr
Adding certain inorganic clays to rubber dramatically improves
the lifetime and wear-characteristics of tires.

Why ?

The nanoscale clay particles bind to the ends of the polymer
molecules - which you can think of as molecular strings - and
prevent them from unraveling.
CNT is a tubular form of carbon with diameter as small as 1 nm.
Length: few nm to microns.

CNT is configurationally equivalent to a single or mutliple two
dimensional graphene sheet(s) rolled into a tube (single wall vs.
multiwalled).
CNT exhibits extraordinary mechanical
properties: Youngs modulus over
1 Tera Pascal, as stiff as diamond, and tensile
strength ~ 200 GPa.

CNT can be metallic or semiconducting,
depending on (m-n)/3 is an integer (metallic)
or not (semiconductor).
See textbook on
Carbon Nanotubes:
Science and
Applications,
M. Meyyappan,
CRC Press, 2004.
The strongest and most flexible molecular
material because of C-C covalent bonding
and seamless hexagonal network architecture

Youngs modulus of over 1 TPa vs 70 GPa for
Aluminum, 700 GPa for C-fiber
- strength to weight ratio 500 time > for Al;
similar improvements over steel and
titanium; one order of magnitude
improvement over graphite/epoxy

Maximum strain 10%; much higher than any
material

Thermal conductivity ~ 3000 W/mK in the axial
direction with small values in the radial direction
See http://www.ipt.arc.nasa.gov/gallery.html for videos of bending, compression, etc., of CNTs
Electrical conductivity higher than copper

Can be metallic or semiconducting depending on chirality
- tunable bandgap
- electronic properties can be tailored through application of external
magnetic field, application of mechanical deformation

Very high current carrying capacity
(10
7
- 10
9
A/cm
2
)

Excellent field emitter; high aspect ratio
and small tip radius of curvature are
ideal for field emission

Other chemical groups can be attached
to the tip or sidewall (called functionalization)
Sensors, Bio, NEMS

CNT based microscopy: AFM, STM

Nanotube sensors: bio, chemical

Molecular gears, motors, actuators

Batteries (Li storage), Fuel Cells, H
2
storage

Nanoscale reactors, ion channels

Biomedical
- Nanoelectrodes for implantation
- Lab on a chip
- DNA sequencing through AFM imaging
- Artificial muscles
- Vision chip for macular degeneration,
retinal cell transplantation
Electronics

CNT quantum wire interconnects

Diodes and transistors for
computing

Data Storage

Capacitors

Field emitters for instrumentation

Flat panel displays
Challenges
Challenges
Control of diameter, chirality
Doping, contacts
Novel architectures (not CMOS based!)
Development of inexpensive manufacturing
processes
Controlled growth
Functionalization with
probe molecules, robustness
Integration, signal processing
Fabrication techniques
SWNT
MWNT
Tower
Close view of MWNT Tower
MWNT Structures
Courtesy: Alan Cassell
Certain applications such as nanoelectrodes, biosensors would
ideally require individual, freestanding, vertical (as opposed to
towers or spaghetti-like) nanostructures

The high electric field within the sheath near the substrate in a plasma
reactor helps to grow such vertical
structures

dc, rf, microwave, inductive
plasmas (with a biased substrate)
have been used in PECVD of
such nanostructures
Cassell et al., Nanotechnology, 15 (1), 2004
Biosensor
High specificity
Direct, fast
response
High sensitivity
Single molecule
and cell signal
capture and
detection
3+
2+
e
3+
2+

Ru bPy ( )
3
2 +
| |
Probe molecules for a given target can be attached to
CNT tips for biosensor development

Electrochemical approach: requires nanoelectrode
development using PECVD grown vertical nanotubes

The signal can be amplified with metal ion mediator
oxidation catalyzed by Guanine.
Courtesy: Jun Li

CNT tips are at the scale close
to molecules

Dramatically reduced
background noise
Traditional Macro- or
Micro- Electrode
Nanoelectrode
Array
Nanoscale electrodes create a dramatic improvement in signal
detection over traditional electrodes
Electrode
Scale difference between macro-
/micro- electrodes and molecules is
tremendous
Background noise on electrode
surface is therefore significant
Significant amount of target
molecules required
Multiple electrodes results in
magnified signal and desired
redundance for statistical reliability.
Can be combined with other
electrocatalytic mechanism for
magnified signals.
Nano-
Electrode
Insulator

Source: Jun Li
Functionalization of DNA
CO
2
H
N
C
N
CH
3
N
CH
3
H
Cl
-
O
CH
3
H
N
H
2
N ATGCCTTCCy
3
ATGCCTTCCy
3
CH
3
H
Cl
-
TACGGAAGGGGGGGGGGCy
5
N
O
O
HO
SO
3
Na
CH
3
C
O
NH
C
N
CH
3
N
O
O
O N
O
O
SO
3
Na
O
H
N ATGCC TTCCy3
TACGGAAGGGGGGGGGGCy
5
+
EDC
+
Sulfo-NHS
DNA probe
Target DNA
Cy3 image
Cy5 image
C. Nguyen et al, NanoLett., 2002, Vol. 2, p. 1079.
Electrochemical Detection
of DNA Hybridization
- by AC Voltammetry
1
st
, 2
nd
, and 3
rd
scan in AC voltammetry
1
st
2
nd
scan: mainly DNA signal
2
nd
3
rd
scan: Background
1st
2
nd
and 3rd
#1-#2
#2-#3
Lower CNT Density Lower Detection Limit
J. Li, H.T. Ng, A. Cassell, W. Fan, H. Chen,
J. Koehne, J. Han, M. Meyyappan,
NanoLetters, 2003, Vol. 3, p. 597.
30 dies on a 4 Si wafer
200 m
300 m
Potential applications:
(1) Lab-on-a-chip applications
(2) Early cancer detection
(3) Infectious disease detection
(4) Environmental monitoring
(5) Pathogen detection
Target
Molecule
1. Chen, G.Y., Thundat, T. Wachter, E. A., Warmack, R. A., Adsorption-induced surface stress and its
effects on resonance frequency of microcantilevers, J. Appl. Phys 77, pp. 3618-3622 (1995).
2. Ratierri, R. et al., Sensing of biological substances based on the bending of microfabricated
cantilevers, Sensors and Actuators B 61, 213-217 (1999).
3. Fritz, J. et al. Translating Biomolecular Recognition into Nanomechanics, Science 288, 316-318 (2000).
4. Wu, G. et al. Origin of nanomechanical cantilever motion generated from biomolecular interactions,
PNAS 98(4), 1560-1564 (2001).

Courtesy: Prof. A. Majumdar, U.C. Berkeley
Thiolated ssDNA
5-HS
ATCCGCATTACGTCAATC
TAGGCGTAATGCAGTTAG-5
(Complementary Strand)
Au
Self-Assembly of ssDNA
PB = Sodium Phosphate Buffer Solution
-
-
-
-
-
-
-
-
+
+
+
+
+
+
+
Wu, G. et al. Origin of nanomechanical cantilever motion generated from biomolecular interactions,
PNAS 98(4), 1560-1564 (2001).
Courtesy: Prof. A. Majumdar, U.C. Berkeley
Probe
ssDNA Target ssDNA
Wu, G. et al. Origin of nanomechanical cantilever motion generated from biomolecular interactions,
PNAS 98(4), 1560-1564 (2001).
Courtesy: Prof. A. Majumdar, U.C. Berkeley
Time [min]
0 60 120 180 240
D
e
f
l
e
c
t
i
o
n
,

h

[
n
m
]
-40
-20
0
20
40
60
80
Injections
[HSA] = 1 mg/ml
[fPSA]
6 ng/ml
60 ng/ml
No PSA Ab
([fPSA] = 60 g/ml)
HP only
([HP] = 1 mg/ml)
No PSA

Time [min]
0 60 120 180 240 300
D
e
f
l
e
c
t
i
o
n
,

h

[
n
m
]
-50
0
50
100
150
200
[BSA] = 1 mg/ml
Injections
60 g/ml
6 g/ml
60 ng/ml
6 ng/ml
No fPSA
No PSA Ab
([fPSA] = 60 g/ml)
[fPSA]
SiN
x
Au
DTSSP
Rabbit Anti-
Human PSA
Glass
Analyte
SiN
x
Au
DTSSP
Rabbit Anti-
Human PSA
Glass
Analyte
PSA
Wu, G. et al., Bioassay of Prostate Specific
Antigen (PSA) Using Microcantilevers,
Nature Biotechnology (Sept., 2001)
HSA: Human Serum Albumin
HP: Human Plasminogen
fPSA: free PSA
cPSA: complex PSA
Courtesy: Prof. A. Majumdar, U.C. Berkeley
DNA Sequencing
Using Nanopores
Goal: Very rapid gene sequencing
(~2nm diameter)
- Nanopore in membrane
- DNA in buffer
- Voltage clamp
- Measure current
G. Church, D. Branton , J. Golovchenko , Harvard
D. Deamer , UC Santa Cruz
o-hemolysin pore
Axial View
Side View
(very first, natural
pore)
Open nanopore
DNA translocation event
When there is no DNA translocation, there is a
background ionic current

When DNA goes through the pore, there is a drop in
the background signal

The goal is to correlate the extent and duration of the
drop in the signal to the individual nucleotides
Source: Viktor Stolc
After a decade of using protein pores, efforts are
underway in many groups to develop synthetic pores
(such as in Si
3
N
4
)
Interaction with single nuclotides
- ~20 nucleotides in oHL simultaneously
Slower translocation
- 1-5 s /nucleotide in oHL
Resistance to extreme conditions
- Temperature
- pH
- Voltage
o - hemolysin is toxic and hard to work with
Source: Viktor Stolc
Voltage-clamp amplifier designed to measure pA
level currents
Fast (up to 1GHz) data acquisition
Software for automatic blocking event detection
and recording
A
g
C
l

A
g
C
l

Voltage Clamp
Amplifier
nanopore
chip
KCl KCl
Data Acquisition
G G
A A A A
G
C C
T T
Present Future
A A
G G G G
C C
Tree-like polymers, branching out from a central
core and subdividing into hierarchical branching
units
- Not more that 15 nm in size, Mol. Wt very high
- Very dense surface surrounding a relatively
hollow core (vs. the linear structure in traditional
polymers)

Dendrimers consist of series of chemical shells built on a
small core molecule
- Surface may consist of acids or amines means to attach functional groups
control/modify properties
- Each shell is called a generation (G0, G1, G2.)
- Branch density increases with each generation
- Contains cavities and channels can be used to trap guest molecules for
various applications.
Courtesy of: http://www.uea.ac.uk/cap/wmcc/anc.htm
Desired features of effective drug delivery
- Targeted delivery, controlled release (either timed or in response to an external
signal)

Desirable characteristics of dendrimers
- Uniform size - Water Solubility
- Modifiable surface functionality - Availability of internal cavity
- Control of molecular weight - Control of the surface and internal structure

Number of different drugs can be encapsulated in dendrimers and injected into the body
for delivery
- Incorporating sensors would allow release of drugs where needed

Gene Therapy
- Current problem is getting enough genes into enough cells to make a difference.
Using viruses for this triggers immune reactions. Dendrimers provide an
alternative without triggering immune response

Cancer Therapy

Antimicrobial and Antiviral Agents
Dissolution kinetics may be the rate limiting step in the absorption process
for many drugs
- Decreasing the particle size increases surface area and the dissolution
kinetics.

Liposomes are normally used as carrier for hydrophilic drugs. Typical
difficulties: physical instability, low activity, drug leakage
- Alternative: water-soluble polymer based nanoparticles. These are
more site-specific and exhibit better controlled-release characteristics.
- To overcome toxicity issues, solid lipid nanospheres as carrier systems
have been reported
*
. This is a lipid that is solidified and stabilized by
a surfactant.

Advantages: physical stability
Disadvantage: low drug loading (25%)
* S.A. Wissing et al., Adv. Drug. Del. Rev. 56, p. 1257 (2004).
Synthetic droplets containing anything from a single electron to
thousands of atoms but behave like a single huge atom.

Size: nanometers to microns

These are nanocrystals with extraordinary optical properties
- The light emitted can be tuned to desired wavelength by
altering the particle size
- QDs absorb light and quickly re-emit but in a different color
- Colors from blue to IR

Common QDs: CdS, CdSe, PbS, PbSe, PbTd, CuCl

Manufacturing
- Wet chemistry
- Template synthesis (zeolites, alumina template)

E
n
e
r
g
y

l
e
v
e
l
s

Absorption
Radiationless
decay
Fluorescence
V
a
l
e
n
c
e


B
a
n
d

Band gap
Small
Molecules
Qdots Semiconductors
C
o
n
d
u
c
t
i
o
n

B
a
n
d

Source: Bala Manian, Quantum Dot Corp.

Size Dependent Absorbance
and Emission
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
350 450 550 650
Wavelength (nm)

(
A
U
)
2.2 nm
CdSe
5.0 nm
CdSe
E
g
~ 1/L
2

L L
Source: Bala Manian, Quantum Dot Corp.


Quantum dots change color with size because additional
energy is required to confine the semiconductor
excitation to a smaller volume.

Ordinary light excites all color quantum dots.
(Any light source bluer than the dot of interest works.)
Source: Bala Manian, Quantum Dot Corp.
Material band-gap determines the emission range;
particle size tunes the emission within the range
Nanocrystal quantum yields are as high as 80%
Narrow, symmetric emission spectra minimize
overlap of adjacent colors
350 400 450 500 550 600 650 700 750
Emission Wavelength (nm)
Excitation: ZnSe @ 290 nm, others 365 nm
N
o
r
m
a
l
i
z
e
d

I
n
t
e
n
s
i
t
y
ZnSe CdSe
CdTe
Source: Bala Manian, Quantum Dot Corp.
LEDs, solar cells, solid state lighting

Biomedical
- Bioindicators
- Lateral flow assays
- DNA/gene identification, gene chips
- Cancer diagnostics

Biological Labeling Agent
Broad output spectrum Sharper spectrum
Fades quickly ~ 100 ps 5-40 ns
Unstable Stable output over time
One dye excited at a time Multicolor imaging, multiple
dyes excited simultaneously