Think small !

Think small !
Think small !

R.P.H. Chang
Director
National Center for Learning and Teaching in
Nanoscale Science and Engineering
Northwestern University
with contributions from Professors Chen and
Hersam
 Five questions to ponder!!

• How small is small?

• What ways are there to measure the size
of objects? Characteristic length scales
• Can small objects be useful?
• How do we go about making small things
and measure them?
• Do small objects have the same physical
properties as the big ones?
 The Scale of Things -- Nanometers and More
Things Natural Things Manmade
10-2 m 1 cm
10 mm
Head of a pin
1-2 mm

1,000,000 nanometers = 21st Century

Ant
~ 5 mm
10-3 m 1 millimeter (mm) MicroElectroMechanical devices Challenge
10 -100 µm wide

Microwave
Dust mite
200 µm 0.1 mm
10-4 m
100 µm

Fly ash

Microworld
Human hair ~ 10-20 µm
~ 10-50 µm wide
The 0.01 mm
10-5 m
10 µm P
O
O O

Infrared
Red blood cells
O O O O

Red blood cells

Pollen grain
O O O O O O O O

with white cell O O O O O O O O

~ 2-5 µm 1,000 nanometers = S S S S S S S S

10-6 m 1 micrometer (µm) Zone plate x-ray “lens”

Outermost ring spacing
Visible

~35 nm

10-7 m 0.1 µm
Combine nanoscale building
100 nm blocks to make novel
Ultraviolet

functional devices, e.g., a

The Nanoworld

photosynthetic reaction
center with integral
semiconductor storage
10-8 m 0.01 µm
~10 nm diameter 10 nm Nanotube electrode Nanotube transistor

ATP synthase

10-9 m 1 nanometer (nm)

Soft x-ray

DNA Carbon nanotube

~2-1/2 nm diameter 10-10 m 0.1 nm Quantum corral of 48 iron atoms on copper surface ~2 nm diameter
Atoms of silicon positioned one at a time with an STM tip Office of Basic Energy Sciences
spacing ~tenths of nm Corral diameter 14 nm Office of Science, U.S. DOE
Version 03-05-02
 Ways to measure objects

• Use a ruler? What scale?

• Big objects vs tiny objects; objects at
distance
• What happens if you are stranded on an
island without a ruler?
• Characteristic lengths and scales
What’s the Difference?
 Different Length Scales,
Different Measurement Techniques

atoms molecules depth of cell thickness Width of

pit on CD of paper notebook paper

10-10 m 10-9 m 10-8 m 10-7 m 10-6 m 10-5 m 10-4 m 10-3 m 10-2 m 10-1 m 1m
Transmission Scanning Magnifying
Light Microscope naked eye
Electron Microscope Electron Microscope Glass
Scanning Probe
Microscope
 Optical Microscopy

Typical Length Scales: 1 micron larger, depending on chosen magnification.

Resolution is limited by diffraction to 200 nm and larger.

For more information:

http://en.wikipedia.org/wiki/Optical_microscope
 Scanning Electron Microscope

Typical Length Scales: 100 nm and larger, depending on chosen magnification.

Resolution depends on the instrument the condenser lenses. Typically 1- 20 nm.

For more information:

http://en.wikipedia.org/wiki/Scanning_electron_microscope
 Scanning Probe Microscope

Typical Length Scales: atomic length scales and larger, depending on

chosen magnification.

Resolution depends on the instrument, particularly the tip size, but can
be atomic (10-11 m)

http://en.wikipedia.org/wiki/Scanning_probe_microscopy
 Can small objects be useful?

• Insert examples several slides here

• Connection to the macro world is

important!!
 Size Scale & Material Properties
Water at macro scale— Water at nano-micro
a lubricant scale—an adhesive

Concept: The size and dimension of objects/materials affect material

properties and how we can use them.

Standards: NSES/5-8/B/1/a, Properties and changes of properties in matter;

NSES/5-8/B/3/a, Transfer of energy; 2061/6-8/4D/1, The structure of matter;
2061/6-8/4E/4, Energy transformation; 2061/6-8/11D/1, Scale; 2061/6-8/12B/9,
Computation and estimation
 Surface Smoothness & Friction

Close-up view of friction

between surfces:

bottom of an object
Nanolubricants

floor
Nanosphere Nanotube

Concept: Surface smoothness reduces friction.

Standards: NSES/5-8/B/2/c, Motions and forces; 2061/6-8/4F/3, Motion ;

2061/6-8/11D/1, Scale; 2061/6-8/12B/9, Computation and estimation
 Size Scale & Dominant Force
What happens when we drop…?

… Nano-
particles
Spores Flour

Van der Waals Forces

Submicron-sized
flour sticks to the
sides of the
measuring cup
Concept: Electrostatic forces dominate in the nanoworld.

Standards: NSES/5-8/B/2/c, Motions and Forces; 2061/6-8/4E/4, Energy

transformation; 2061/6-8/4G/1, Forces of Nature; 2061/6-8/11D/1, Scale;
2061/6-8/12B/9, Computation and estimation
 Structure & Light Property

Concept: Material structure determines the absorption, transmission, and

reflection of light.

Standards: NSES/5-8/B/3/a, Transfer of energy; 2061/6-8/4D/1, The structure

of matter; 2061/6-8/4F/1-4, Motion; 2061/6-8/11D/1, Scale; 2061/6-8/12B/9,
Computation and estimation
 Surface Area & Chemical Reaction
Surface area increases while total
volume remains constant

Honeycomb

Concept: Surface area affects

the rate of chemical reaction.

Standards: NSES/5-8/B/1/a, Properties and changes of properties in matter;

NSES/5-8/B/3/e, Transfer of energy; 2061/6-8/4D/1, The structure of matter;
2061/6-8/4E/4, Energy transformation; 2061/6-8/11D/1, Scale; 2061/6-8/12B/9,
Computation and estimation
Nanoparticles in Colloids & Suspensions
Mayonnaise/Whole Milk Gelatin/Jelly/Jam Mist & Aerosols
Nanosized liquid Nanosized Nanosized liquid
droplets in liquid clusters droplets suspended
another liquid in a solid in a gas

Smoke
Marshmallows/Whipped Cream Stained Glass Nanosized
solid
Nanosized
particles
gas bubbles
suspended
in a solid Nanosized solid
in a gas
particles in a solid
Solutions 1 nm Colloids 100 nm Suspensions

Concept: Molecular clusters create unique properties.

Standards: NSES/5-8/B/1/a, Properties and changes of properties in matter;
NSES/5-8/B/3/a, Transfer of energy; 2061/6-8/4D/1, The structure of matter;
2061/6-8/4E/4, Energy transformation; 2061/6-8/11D/1, Scale; 2061/6-8/12B/9,
Computation and estimation
 Ways of making small things?

• Insert examples from Prof. Hersam

 Nanofabrication
Top-down: Chisel away material to make nanoscale
objects

Bottom-up: Assemble nanoscale objects out of even

smaller units (e.g., atoms and molecules)

Ultimate Goal: Dial in the properties that you want by

designing and building at the scale of nature (i.e., the
nanoscale)
 Top-Down: Photolithography
PREPARED
1 PHOTORESIST
Si WAFER
PROJECTED
LIGHT
SiO2 LAYER

Si3N4 LAYER

Si SUBSTRATE

RETICLE
(OR MASK)

SIMILAR CYCLE IS REPEATED
TO LAY DOWN METAL LINKS
6 BETWEEN TRANSISTORS
NEW PHOTORESIST IS SPUN
METAL ON WAFER AND STEPS 2 TO 4
CONNECTOR ARE REPEATED
1 µm
2 LENS
Ferromagnetic/superconducting
PATTERNS ARE PROJECTED
devices (e-beam lithography)
REPEATEDLY ONTO WAFER

IONS SHOWER THE ETCHED

5 AREAS, DOPING THEM
3

4 EXPOSED
DOPED PHOTORESIST
REGION IS REMOVED

AREAS UNPROTECTED
BY PHOTORESIST ARE Molecular electronics
ETCHED BY GASES
(e-beam lithography)
Top-Down: Nanoimprint Lithography
Mold
1. Imprint
• Press Mold Resist
Substrate

• Remove Mold

2. Pattern Transfer
• RIE
Top-Down: Nanosphere Lithography
Bottom-Up: Carbon Nanotube Synthesis

100 nm
 Bottom-Up: Molecular Self-Assembly
• Spontaneous organization of molecules into stable, structurally
well-defined aggregates (nanometer length scale).
• Molecules can be transported to surfaces through liquids to
form self-assembled monolayers (SAMs).

Supramolecular rodcoil Polythiophene wires Supramolecular rodcoil

“mushrooms” nanoribbons
Dip Pen Nanolithography
 Unique properties of small objects

• Give examples here

 Size-Dependent Properties
At the nanometer scale, properties become size-dependent.
For example,
(1) Chemical properties – reactivity, catalysis
(2) Thermal properties – melting temperature
(3) Mechanical properties – adhesion, capillary forces
(4) Optical properties – absorption and scattering of light
(5) Electrical properties – tunneling current
(6) Magnetic properties – superparamagnetic effect
Æ New properties enable new applications
 Macroscale Surface Area to Volume Ratio
A typical material possesses:
~1023 atoms/cm3 (volume density)
~1015 atoms/cm2 (surface density)

Assume that we have a cube with side of length = 1 cm.

Total number of atoms ~ 1023 atoms/cm3 × (1 cm)3 ~ 1023

Total number of surface atoms ~ 1015 atoms/cm2 × 6 × (1 cm)2 ~ 6×1015

Ratio of surface to total atoms ~ 6×1015/1023 ~ 6×10-8

 Nanoscale Surface Area to Volume Ratio
A typical material possesses:
~1023 atoms/cm3 (volume density)
~1015 atoms/cm2 (surface density)

Assume that we have a cube with side of length = 1 nm = 10-7 cm.

Total number of atoms ~ 1023 atoms/cm3 × (10-7 cm)3 ~ 100

Total number of surface atoms ~ 1015 atoms/cm2 × 6 × (10-7 cm)2 ~ 60

Ratio of surface to total atoms ~ 60/100 ~ 0.6

 Surface Energy
Surface atoms possess more energy than bulk atoms.

Consequently, surface atoms are more chemically reactive.

Nanoparticles possess enhanced chemical reactivity.

Example: NASA is exploring aluminum nanoparticles

for rocket propulsion due to their explosiveness
 Nanoparticle Catalysts

Macroscopic gold is chemically inert.

Gold nanoparticles are used to catalyze

chemical reactions.

Example: Reduced pollution in oxidation

reactions (i.e., environmentally friendly)

Nanoparticle Catalysis Resarch Group, Tsukuba, Japan

http://unit.aist.go.jp/isc/english_ver/each_groups_e/nano-cat_e/nano-cat_e.htm
 Macroscale Melting Temperature
At macroscopic length scales, the melting temperature of materials
is size-independent.

For example, an ice cube and a glacier both melt at the same
temperature (32ºF).
 Nanoscale Melting Temperature
Nanocrystal size decreases

surface energy increases

melting point decreases

e.g., 3 nm CdSe nanocrystal melts at 700 K compared to

bulk CdSe at 1678 K
 Mechanical Properties
• At the nanoscale, surface and interface forces become dominant.

For example,

(1) Adhesion forces

(2) Capillary forces
(3) Strain forces } These forces can exceed forces that
are normally dominant at macroscopic
length scales (e.g., gravity)

• Surface coatings are extremely important to prevent sticking in

nanoscale electro-mechanical systems (NEMS)
 Carbon Nanotube Tweezers

P. Kim and C. M. Lieber, Science, 286, 2148 (1999).

 Mechanical Motion: Small = Fast

• With decreasing size, mechanical motion can occur more quickly.

• For example, for a mass on a spring, the resonant frequency is

inversely proportional to the square root of the mass.

• Similar relationships can be determined for rotational motion.

• Consequently, molecular rotors are expected to have exceptionally

high rotational frequencies (as high as 100 – 1000 GHz).
Examples of nanotechnology products
 Car Wax
Microemulsion of tiny particles of Carnauba wax
and proprietary polishing nanoparticles

Eagle One
Nanowax

• smoother coating minimizes smearing, allows light

to reflect more evenly to give deep, glossy shine
• easy to remove, no white residue
• nanoparticles fill fine scratches and conceal swirl
marks to create a more even surface
 Ski Polymer (“Nanowax”)

Self-assembling fluoride (CF3) polymers and

multifunctiontal nanoparticles create lamellar
(thin layer) structure on skis and snowboards
• superior adhesive behaviour more resistant to aggressive
types of snow and minimally responsive to temperature
• hard, highly fluorinated surface gives excellent gliding ability

CERAX Racing Polymer

Nanogate Coating Sytems GmbH
Optical Properties of Nanoparticles
particles on the nanoscale are too small to scatter
visible light and appear transparent to the naked eye
 Sunscreen
Nano-dispersed zinc oxide (30 nm)
provides protection against UVA and UVB
rays and is transparent

• cosmetic clarity (no pasty white look)

• higher SPF ratings
• nongreasy, easy application
Grandel PR Vitamin Keys Solar Rx
Nano-Depot Day Nano-Zincoxide

Wet Dreams sunscreen

with ZinClear ZnO
 Cosmetics
Nano-capsules (200 nm) contain active
ingredients and can easily penetrate skin

• delivers Vitamins A, C, & E, or pro-retinol A

• more effective means of delivery than emulsions
• goes on light and sheer; no residue
• affects skin at the “molecular level”

zinc oxide nanoparticles

for UV protection in nanosomes (small liposomes)
Olay Complete in L'Oréal Revitalift
Water repellent surfaces in Nature
many small tubes or whiskers
water
droplet keep water and solid at minimal
contact for superhydrophobia
(extreme water repellency)

peach fuzz and the lotus leaf as inspiration

 Fabrics
• spill proof
• stain resistant
• wrinkle free

Billions of nanowhiskers (10 nm long)

create a thin cushion of air above the cotton
fabric, smoothing out wrinkles and allowing
liquids to bead up and roll off without a trace.

Levi’s Dockers Go Khaki with Stain Defender

Eddie Bauer’s Nano-Care chinos
 Surface Coatings
Nanoparticulate coatings make surfaces
superhydrophobic (extremely water-repellent)
and self-cleaning

• reduces contact area between water

and surface to a minimum
• decreases the forces of adhesion;
water droplets assume globular form
• dirt particles rinsed away
• surfaces stay clean for a long time
BASF MincorTM
superhydrophic coating
Self-cleaning Surfaces
• water droplets form spherical globules
• rough nanoscale surface picks up dirt
• water and dirt roll off
• biomimicry

self-cleaning window
 Sunglasses
Nanocoating on eyeglass lenses:
antireflective polymer coating
(3-10 nm) self assembles

Hard and strong coating:

• excellent scratch, chip resistance
• resistant to dirt and moisture
• anti-reflective

Native Eyewear Nano Sunglasses

With Nanofilm coating
 NANOCOMPOSITE MORPHOLOGIES

Spherical Particle Disc-Shaped Particle Rod-Shaped Particle

Fiber Intergranular Film Layered

Critical Dimensions:
Particle Diameter, Separation Distance, Aspect Ratio,
Fiber Diameter, Layer Thickness, Grain Diameter, …
 Golf Club Shafts
Nanoparticles within fiber reinforced composites
AccuFLEX shafts: “longer, straighter, more consistent”
nanoparticles

fibers
 Golf Club Shafts and Heads
Nanoparticles reinforces carbon
(graphite) composite material

Wilson Nano-Technology Crown:

• high strength and low density
• improved torsion stability (longer, straighter shots)

Carbon nanotubes in club heads

Wilson Clubs Dd5 Pd5 FwC:
• reduced weight (thus faster club head speed)
 Baseball Bats
Carbon nanotubes within
carbon fiber composites

Easton Stealth CNT bats

• improved strength in resin

area with Zyvex nanotubes
• greater strength/density
 Tennis Racquets
Nanosized SiO2 within voids of carbon fibers
Wilson nSix-One Tour racquet:
• greater strength, stability, power
Roger Federer 2004 Wimbledon

Carbon nanotubes around racquet head

Babolat’s VS NCT (Nano Carbon Technology):
• greater stiffness, flex resistance, rigidity
• lightweight, responsive
• larger sweet spot
 Tennis Balls
Nano-clay platelets (1 nm thick)
within rubber polymer matrix

Wilson Double Core tennis balls with InMat Air D-Fense:

• better air retention (tortuous path for air to escape)
• more consistent bounce
• longer life
 Plastic Bottles Gas Barrier
Nanoclay composites
in multi-layer PET bottles

less CO2 escape and less O2 absorption:

• increases shelf life, efficiently preserves flavor
• greater light and fire resistance
• stronger mechanical and thermal performance

Honeywell’s optically clear if individual clay

Aegis nylon 6 thickness < λ of visible light
nanocomposites
 Portable Water Filtration System

Porous plastic bag coated with

nanoclays to filter water

contaminated water goes in, but only

pure water seeps through self-hydrating
membrane pouch by osmotic pressure

Hydration Technologies X-Pack

• filters at 50 nm level (virus, bacteria, parasites)

• light weight
• military and recreational applications

Hydration Technologies’ Life-Sustaining Water Filtration

Bags Deployed To Hurricane Katrina Victims
 Nano-clay Composites
Clay platelets
10 Angstroms thick, but
over 200 times that in width
Intercalated Material

Polymer
molecular chains bind
clay platelets together
Exfoliated Material

very large surface areas of contact between dispersed

nano-platelets (1 nm thick) & polymer matrix result in:

• tortuous path for gases to travel through → barrier

• high strength, good toughness, low density → composites
 Step Assists & Car Parts
Nanocomposites of clay platelets
in polymer matrix
Chevrolet Impala body side molding, 2004
Hummer H2 SUT cargo bed, 2005

very low loadings of filler (< 5 wt%) needed:

• high strength and stiffness
• less brittle in cold
• low weight
• more recyclable
• wider processing window

Chevrolet Astro & GMC Safari

vans step assists, 2002
 Advances in nanotechnology development

• Insert cnt FED, photonic crystal laser

• Nano-wire transistor, sensor
 Properties

• Carbon nanotubes (CNTs) have been of

interest due to remarkable properties
– Electrical
• Resistivity - 10-4 Ω-cm (Copper ~ 10-6 Ω-cm)
• Maximum current density - 1013 A/m2
– Mechanical
• Young’s modulus ~ 1 TPa (5x higher than
steel)
• Maximum tensile strength ~ 30 GPa
 Applications

• Composite Materials
– 1% of MWNTs increased the modulus of
polystyrene by 42%.1
• Nanoscale Electronic Devices
– NTs can act as nanoscale wires for
devices, such as field effect transistors.2

1. Quan, D., et al., Appl. Phys. Lett., 2000, 76, 2868. 2. Collins, P.G., et al., Science, 2001, 292, 706.
 Applications

• Field Emission
Devices
– Sharp tip of NTs
produces high field
emission.
– Flat panel displays
have been created
using NTs as the
field emitter.1

1. Wang, Q., et al., Appl. Phys. Lett., 1998, 72, 2912. Choi, W.B., et. al., Appl. Phys. Lett. 75 20 (1999) p. 3129.
 Applications

• Nanoscale Probes:
– The mechanical robustness and high
aspect ratio allow NTs to be used as high
resolution tips for atomic probe
microscopes.1 Carbon nanotube

1. Hafner,
Hafner, J.H., et al., Nature, 1999,
1999, 398, 761.
 Field Emission

• Theory vacuum level

When high electric

field is applied to a metal
or semiconductor
surface, the surface
potential is deformed so
that electrons can tunnel
and emit into the vacuum

φ = work function
 Field Emission
• Emitter design
Fowler-Nordheim equation
– To maximize current
density (j) ⎛ Eloc ⎞
2 ⎡ − BΦ 2 ⎤
3

• Create a emitter with a j = A⎜⎜ ⎟ exp ⎢

⎟ ⎥
sharp tip (β∝1/r) ⎝ Φ ⎠ ⎢⎣ Eloc ( β ) ⎥⎦
• Use a material with a where Eloc = β ⋅ E 0
low work function (Φ)
β = field amplification factor
 Field Emission Displays

• Traditional displays use cathode ray tubes (CRT)

• Field emission displays replace the electron gun
with field emitters allowing the display to be thin,
flat, and light-weight
 Chang’s group diode design
• Pixels formed at
intersection of cathode
and anode stripes
• Cathode processing
– Etched micro channels in glass
substrate
– Filled with nanotube-epoxy paste
– Polished to expose nanotubes
• Anode processing
– Patterned ITO by lithography
– Coated patterned ITO with
phosphor
Wang, Q.H., et. al., Appl. Phys. Lett. 72 22 (1998) p. 2912. Anode Cathode
 Chang’s group diode design
• I-V curves consistent
across device
• No degradation and little
current fluctuation (8%) in
12 hour run

Operating parameters
Emission current
76 µA/mm2
density
Applied voltage 300 V

Pixel definition 200x200 µm2

Wang, Q.H., et. al., Appl. Phys. Lett. 72 22 (1998) p. 2912.

 Chang’s group triode design

Glass

ZnO
V anode phosphor
Glass spacer
0.2 mm Mo gate
Nanotube emitter
V gate FOTURAN
substrate

Spin-on glass
Back contact to emitters

Wang, Q.H., et. al., Appl. Phys. Lett. 78 9 (2001) p. 1294.

 Recent Developments
• Solid-state method for high-crystallinity
CNTs
– Able to produce high quality CNTs using
high-temperature oven with solid precursor
Carbon Nanotube Field Emission Display
 Summary

• How does nano link to macro

phenomena?
• What is the impact of nano technology in
the future?
• Will there be job opportunities in nano?
• Why study nanoscale science?