M.

Meyyappan
Center for Nanotechnology
NASA Ames Research Center
Moffett Field, CA 94035

email: mmeyyappan@mail.arc.nasa.gov
Nanotechnology is the creation of USEFUL/FUNCTIONAL
materials, devices and systems (of any 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 Me
ltin
• Mechanical gp
oin
t - 10
64
• Optical C

• Magnetic
•
• Source: K.J. Klabunde, 2001
 Unique Properties of Nanoscale Materials

• 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 m2 per gram

• New chemical forms of common chemical elements, e.g.,

fullerenes, nanotubes of carbon, titanium oxide, zinc
oxide, other layered compounds
Source: Clayton Teague, NNI
 NNI Program Component Areas (PCAs)

• Fundamental Nanoscale Phenomena and

Processes
• Nanomaterials
• Nanoscale Devices and Systems
• Instrumentation Research, Metrology, and
Standards for Nanotechnology
• Nanomanufacturing
• Major Research Facilities and
Instrumentation Acquisition
• Societal Dimensions
Source: Clayton Teague, NNI
 Sensors,
Organic Inorganic Nanoelectronics
and Related NEMS

Structural
Bio Applications

Nanomaterials Applications
• Nanocrystalline materials • Molecular electronics
• Nanoparticles • Quantum dots
• Nanocapsules • NEMS, Nanofluidics
• Nanoporous materials • Nanophotonics, Nano-optics
• Nanofibers • Nanomagnetics
• Nanowires • Nanofabrication
• Fullerenes • Nanolithography
• Nanotubes • Nanomanufacturing
• Nanosprings • Nanomedicine
• Nanobelts • Nano-bio
• Dendrimers •
• •
 • Information Technology
- Computing, Memory and Data Storage
- Communication
• Materials and Manufacturing
• Health and Medicine
• Energy
• Environment
• Transportation
• National Security
Nanotechnology is an • Space exploration
enabling technology •
•
• Ability to synthesize nanoscale building blocks with control on size,
composition etc. further assembling into larger structures with
designed properties will revolutionize materials manufacturing
- Manufacturing metals, ceramics, polymers, etc. at exact shapes without
machining
- Lighter, stronger and programmable materials
- Lower failure rates and reduced life-cycle costs
- Bio-inspired materials
- Multifunctional, adaptive materials
- Self-healing materials

• Challenges ahead
- Synthesis, large scale processing
- Making useful, viable composites
- Multiscale models with predictive capability
- Analytical instrumentation
• Carbon Nanotubes
• Nanostructured Polymers
• Optical fiber performs through sol-gel
processing of nanoparticles
• Nanoparticles in imaging systems
• Nanostructured coatings
• Ceramic Nanoparticles for netshapes

Source: IWGN Report

• Nanostructured metals, ceramics at exact shapes without machining
• Improved color printing through better inks and dyes with
nanoparticles
• Membranes and filters
• Coatings and paints (nanoparticles)
• Abrasives (using nanoparticles)
• Lubricants
• Composites (high strength, light weight)
• Catalysts
• Insulators
Past
Shared computing thousands of
people sharing a mainframe computer

Present
Personal computing

Future
Ubiquitous computing thousands of computers sharing each
and everyone of us; computers embedded in walls, chairs, clothing,
light switches, cars….; characterized by the connection of things in
the world with computation.
 “There is at least as far to go (on a logarithmic scale) from the present as
we have come from ENIAC. The end of CMOS scaling represents both
opportunity and danger.”
-Stan Williams, HP

• A few more CMOS generations left but cost of building fabs going up faster than
sales. Physics has room for 109x current technology based on 1 Watt
dissipation, 1018 ops/sec no clear ways to do it!
- Molecular nanoelectronics ?
- Quantum cellular automata ?
- Chemically synthesized circuits ?

• Self assembly to reduce manufacturing costs, defect tolerant architectures

may be critical to future nanoelectronics
• Quantum Computing
- Takes advantage of quantum mechanics
instead of being limited by it
- Digital bit stores info. in the form of ‘0’ and
‘1’; qubit may be in a superposition state of
‘0’ and ‘1’ representing both values
simultaneously until a measurement is made
- A sequence of N digital bits can represent
one number between 0 and 2N-1; N qubits
can represent all 2N numbers simultaneously
• Carbon nanotube transistors by several groups
• Molecular electronics: Fabrication of logic gates
from molecular switches using rotaxane
molecules
• Defect tolerant architecture, TERAMAC computer
by HP architectural solution to the
problem of defects in future molecular electronics

1938 1998

Technology engine: Technology engine:

Vacuum tube CMOS FET

Proposed improvement: Proposed improvement:

Solid state switch Quantum state switch

Fundamental research: Fundamental research:

Materials purity Materials size/shape

- Stan Williams, HP
• Processors with declining energy use and cost per gate, thus
increasing efficiency of computer by 106
• Higher transmission frequencies and more efficient utilization of
optical spectrum to provide at least 10 times the bandwidth now
• Small mass storage devices: multi-tera bit levels
• Integrated nanosensors: collecting, processing and
communicating massive amounts of data with minimal size,
weight, and power consumption
• Quantum computing
• Display technologies
 • Expanding ability to characterize genetic makeup will
revolutionize the specificity of diagnostics and
therapeutics
- Nanodevices can make gene sequencing more
efficient

• Effective and less expensive health care using remote

and in-vivo devices

• New formulations and routes for drug

delivery, optimal drug usage

• More durable, rejection-resistant artificial

tissues and organs
Nanotube-based
biosensor for
cancer diagnostics • Sensors for early detection and prevention
• DNA microchip arrays using advances for IC industry

• ‘Gene gun’ that uses nanoparticles

to deliver genetic material to
target cells

• Semiconductor nanocrystals
as fluorescent biological labels

Source: IWGN Report

• Energy Production
- Clean, less expensive sources enabled by novel nanomaterials
and processes
- Improved solar cells
• Energy Utilization
- High efficiency and durable home and
industrial lighting
- Solid state lighting can reduce total
electricity consumption by
10% and cut carbon emission
by the equivalent of 28 million tons/year
(Source: Al Romig, Sandia Lab)
• Materials of construction sensing changing conditions and in
response, altering their inner structure
• Nanomaterials have a large surface area. For example, single-walled
carbon nanotubes show ~ 1600 m2/g. This is equivalent to the size of a
football field for only 4 gms of nanotubes. The large surface area enables:
- Large adsorption rates of various gases/vapors
- Separation of pollutants
- Catalyst support for conversion
reactions
- Waste remediation
• Filters and Membranes
- Removal of contaminants
from water
- Desalination
• Reducing auto emissions, NOx conversion
- Rational design of catalysts
• More efficient catalytic converters
• Thermal barrier and wear resistant coatings

• Battery, fuel cell technology

• Improved displays

• Wear-resistant tires
• High temperature sensors for ‘under the hood’; novel
sensors for “all-electric” vehicles

• High strength, light weight composites for increasing fuel

efficiency
• Improved collection, transmission, protection of information

• Very high sensitivity, low power sensors for detecting

chem/bio/nuclear threats

• Light weight military platforms, without sacrificing

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

• Reduce carry-on weight of

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

• Revolutions in electronics and computing will allow reconfigurable,

autonomous, “thinking” spacecraft Europa Submarine

• Nanotechnology presents a whole new

spectrum of opportunities to build
device components and systems for
entirely new space architectures
- Networks of ultrasmall
probes on planetary surfaces
- Micro-rovers that drive,
hop, fly, and burrow
- Collection of microspacecraft
making a variety of measurements
CNT is a tubular form of carbon with diameter as small as 1 nm. See textbook on
Length: few nm to microns.
Carbon Nanotubes:
CNT is configurationally equivalent to a two dimensional graphene
Science and
sheet rolled into a tube (single wall vs. multiwalled). Applications,
M. Meyyappan,
CRC Press, 2004.

CNT exhibits extraordinary mechanical

properties: Young’s 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 (semicon).
• The strongest and most flexible molecular material because of C-C
covalent bonding and seamless hexagonal network architecture

• Strength to weight ratio ~500 times greater than Al, steel,

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

• Very high current carrying capacity

• 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’)
 Electronics Sensors, Bio, NEMS

• CNT quantum wire interconnects • CNT based microscopy: AFM, STM…

• Diodes and transistors for • Nanotube sensors: bio, chemical…

computing • Molecular gears, motors, actuators
• Data Storage • Batteries (Li storage), Fuel Cells, H 2 storage
• Capacitors • Nanoscale reactors, ion channels
• Field emitters for instrumentation • Biomedical
- Nanoelectrodes for implantation
• Flat panel displays - Lab on a chip
- DNA sequencing through AFM imaging
- Artificial muscles
- Vision chip for macular degeneration,
retinal cell transplantation
Challenges Challenges
• Control of diameter, chirality • Controlled growth
• Doping, contacts • Functionalization with
• Novel architectures (not CMOS based!) probe molecules, robustness
• Development of inexpensive manufacturing • Integration, signal processing
processes • Fabrication techniques
• CNT has been grown by laser ablation (pioneered at Rice
University) and carbon arc process
(NEC, Japan) - early 90s.
- SWNT, high purity, purification methods
• CVD is ideal for patterned growth (electronics, sensor
applications)
- Well known technique from microelectronics
- Hydrocarbon feedstock
- Growth needs catalyst
(transition metal)
- Numerous parameters
influence CNT growth
(temperature, choice of
feedstock, H2 and other
diluents, choice of catalyst
and preparation)
• SWNTs: Methane, 900° C, 10 nm Al/1.0 nm Fe

• MWNTs: Ethylene, 750º C, 20 nm

Al/10 nm Fe
L. Delzeit et al., Chem. Phys. Lett., Vol. 365, p. 368 (2001);
J. Phys. Chem. B, Vol. 106, p. 5629 (2002).
• 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 Cassell et al., Nanotechnology, 15 (1), 2004
structures

• dc, rf, microwave, inductive

plasmas (with a biased substrate)
have been used in PECVD of
such nanostructures
Atomic Force Microscopy is a powerful technique for imaging; also CD metrology,
nanomanipulation, as platform for sensor work, nanolithography...
Conventional silicon and other tips wear out quickly. 2 nm thick Au on Mica imaged with SWNT
CNT tip is robust, offers amazing resolution.

Simulated Mars dust

Written using multiwall tube

Nguyen et al., Nanotechnology, 12, 363 (2001)
Profilometry in Semiconductor Manufacturing

193 nm IBM Version 2 Resist

DUV Photoresist Patterns Generated by

Interferometric Lithography

Nguyen et al.,
App. Phys. Lett.,
81 (5), 901 (2002).
• 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
2+
[Ru (bPy)3 ]
oxidation catalyzed by Guanine.

2+
2+ • High specificity
• Direct, fast
3+ response
• High sensitivity
• Single molecule
and cell signal
3+
capture and
e
detection
 300 m
200 m

30 dies on a 4” Si wafer
Potential applications:
(1) Lab-on-a-chip applications
(2) Early cancer detection
(3) Infectious disease detection
(4) Environmental monitoring
(5) Pathogen detection
 Applications
•Industrial Toxic
Chemicals, Safety
•Explosive Detection
Single Wall Carbon Nanotube •Earth Observation
•Leak Detection
•Every atom in a single-walled nanotube is on
the surface and exposed to environment
Charge transfer or small changes in the charge-
environment of a nanotube can cause drastic
changes to its electrical properties
Monitoring the change in conductivity forms
the basis for sensing
32-channel sensor chip
 (INWs)
• All these have been grown as 2-d
thin films in the last three decades
• Current focus is to grow 1-d
nanowires

Motivation

• One-dimensional quantum
confinement
• Bandgap varies with wire diameter
• Single crystal with well-defined
surface structural properties
• Tunable electronic properties
by doping
• Truly bottom-up integration
possible

V.S. Vavilov (1994)

Down to 0.4 eV
 ZnO Nanowires Germanium Nanowires

H.T. Ng et al., Science, Vol. 300, p. 2149 (2003). P. Nguyen et al., Advanced Materials, Vol. 17, p. 549 (2005).
• Low Thermal Energy for Programming
– Reduced melting point at 1-D
– Reduced programmable element volume
– Reduced activation energy at 1-D

• Device Scalability
– Ultra-low current / voltage / power operation
– Reduced thermal interference between neighboring memory cells

Top electrode
PCM layer PCM nanowire

Bottom electrode

2-D Thin film PRAM 1-D Nanowire PRAM

 Liquid GeTe

In-situ Tm measurement of GeTe nanowire under TEM image monitoring (a)

The GeTe nanowire is under room temperature. (b) The GeTe nanowire is
heated up to 400C when the nanowire is molten and its mass is gradually lost
through evaporation. The remaining oxide shell can be seen from the image.
 Tm of bulk GeTe: 725oC

46% reduction!

Tm of GeTe nanowires: ~390oC

The melting temperature of the nanowire is identified as the point at which the
electron diffraction pattern disappears and the nanowire starts to be evaporated.

Lower Tm is translated into potentially much reduced thermal programming

energy of data storage device.
 Future Outlook for Inorganic Nanowires

Nanowire-based
Ultra-high Density
Nanowire-based
Data Storage
Detector Sensory
Systems

Nanowire-based
Hybrid Energy
Nanowire-based
Conversion/Storage
Peripheral Optical
Unit
Interconnect/
Transmitter
Nanowire-based
Radiation-harden
Central Processing Unit
• Nanotechnology is an enabling technology that will impact electronics,
computing, data storage, communications, materials and manufacturing,
health and medicine, energy, transportation, environment, national security…

• Though commercial applications have started to emerge, it is still early and long
way to go before realizing true potential. Lot more work needed on:
- Novel synthesis techniques
- Characterization and understanding of nanoscale properties
- Large scale production of materials
- Application and product development

• Opportunities and rewards are great and hence, tremendous worldwide interest

• Integration of this emerging field into engineering and science curriculum is

important to prepare the future generation of scientists and engineers