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
Nanometer • Chemical
• One billionth (10-9 ) of a meter • Electrical
• Hydrogen atom 0.04 nm • Mechanical
• Proteins ~ 1-20 nm • Optical
• Feature size of computer chips 90 nm • Magnetic
(in 2005) •
• Diameter of human hair ~ 10 µm •
 What Is Nanotechnology?
(Definition from the NNI)
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 Nanoarea Electron
fundamentally new properties and functions Diffraction of DW Carbon
because of their nanoscale structure Nanotube – Zuo, et.al

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
• Examples AFM Image of DNA

- 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.
 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
• 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
• 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
 • 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…

• Recently, there has been an explosion of research

on the nanoscale behavior
- Nanostructures through sub-micron self
assembly creating entities from “bottom-up”
STM
instead of “top-down”
- Characterization and applications
- Highly sophisticated computer simulations to
enhance understanding as well as create
Image of Highly Oriented ‘designer materials’
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
• Spherical iron nanocrystals

• J. Phys. Chem. 1996,

Vol. 100, p. 12142
 Nanoscale = High Ratio of Surface Area to Vol.
Repeat 24 times

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
• 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, Fe3O4, 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 particle’s 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/m∆T; 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; Cv = 3 Rg/M
where M is molecular weight
• Cv 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
• 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

θ
∆=2
Tσ
o ρ
/ L
r
∆θ = Deviation of melting point from the bulk value
To = Bulk melting point
σ = Surface tension coefficient for a liquid-solid interface
ρ = Particle density
r = Particle radius
L = Latent heat of fusion
• Lowering of the melting point is proportional to 1/r

• ∆ θ can be as large as couple of hundred degrees when the

particle size gets below 10 nm!

• Most of the time, σ the surface tension coefficient is unknown;

by measuring the melting point as a function of radius, σ 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.
eλ v = electron speed
µ=
4πεom ev ε o = dielectric constant in vacuum

τ , mean time between collisions, is λ /v

• For Cu, v = 1.6 x 106 m/s at room temp.; λ = 43 nm, τ = 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,

Ohm’s law: V = RI

• Band structure begins to change when metal particles become

small. Discrete energy levels begin to dominate, and Ohm’s law is
no longer valid.
 Source: Nanoscale Materials in Chemistry, Wiley, 2001

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

• Young’s 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
• 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

(107 - 109 A/cm2)

• 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…

• Nanotube sensors: bio, chemical…
• Diodes and transistors for
computing • Molecular gears, motors, actuators
• Data Storage • Batteries (Li storage), Fuel Cells, H2 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
 SWNT

MWNT
Tower

Close view of MWNT Tower

MWNT Structures
• 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
Biosensor
• 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 [ y) ]
(P2+
R
ub 3

oxidation catalyzed by Guanine.

2+ • High specificity
2+
• Direct, fast
3+ response
• High sensitivity
• Single molecule
and cell signal
3+ capture and
e
detection
 Nanoscale electrodes create a dramatic improvement in signal
detection over traditional electrodes
Traditional Macro- or Nanoelectrode
Electrode Micro- Electrode Array

• Scale difference between
macro-/micro- electrodes and
molecules is tremendous
• Background noise on electrode
surface is therefore significant
• Significant amount of target
molecules required
Insulator
Nano-
• CNT tips are at the scale close Electrode
to molecules
• Dramatically reduced
background noise
• Multiple electrodes results in
magnified signal and desired
redundance for statistical reliability.
• Can be combined with other
electrocatalytic mechanism for
magnified signals.
 Functionalization of DNA

CH3 CH3 Cl-

Cl- H N+ CH3
N N+
C H CH3
CH3 N
EDC
O
CO2H C N
O C
NH
O SO3Na
HO N CH3

O
Sulfo-NHS
H2N ATGCCTTCCy3
O O O
DNA probe
Cy3 image SO3Na
O N
HN ATGCCTTCCy3
O

TACGGAAGGGGGGGGGGCy5
Target DNA

TACGGAAGGGGGGGGGGCy5
HN ATGCC TTCCy3

Cy5 image
 Electrochemical Detection
of DNA Hybridization
- by AC Voltammetry

1st #1-#2

2nd and 3rd

#2-#3

1st , 2nd , and 3rd scan in AC voltammetry 1st – 2nd scan: mainly DNA signal
2nd – 3rd scan: Background

Lower CNT Density ⇒ Lower Detection Limit

 300 µ m
200 µ 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
Target
Molecule
 Self-Assembly of ssDNA
Thiolated ssDNA Au -
-+
- +
5’-HS ATCCGCATTACGTCAATC + --+
TAGGCGTAATGCAGTTAG-5’
+ -- +
(Complementary Strand) -+
PB = Sodium Phosphate Buffer Solution
Probe
ssDNA Target ssDNA
 200
PSA [BSA] = 1 mg/ml [fPSA]
150 60 µg/ml
Analyte

Deflection, h [nm]
6 µg/ml
Rabbit Anti- 100 Injections
Human PSA
50 60 ng/ml
DTSSP
Au 6 ng/ml
0
SiNx No PSA Ab
No fPSA ([fPSA] = 60 µg/ml)
Glass -50
0 60 120 180 240 300
Time [min]

HSA: Human Serum Albumin 80

[fP
S A
]
[HSA]=1mg/ml

60

HP: Human Plasminogen

60ng/ml

Deflection, h [nm]
40

fPSA: free PSA In

jectio
n s 6ng/ml

20

cPSA: complex PSA 0

-20 NoPSAAb HPonly NoPSA

([fPSA]=60 µg/ml) ([HP]=1mg/ml)

-40

0 60 120 180 240

Time[min]
DNA Sequencing
Using Nanopores
 - Nanopore in membrane
- DNA in buffer
- Voltage clamp (~2nm diameter)
- Measure current

α -hemolysin pore (very first, natural

pore)

Axial View Side View

 • When there is no DNA translocation, there is a
Open nanopore 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
DNA translocation event
After a decade of using protein pores, efforts are
underway in many groups to develop synthetic pores
(such as in Si3N4)
• Interaction with single nuclotides
- ~20 nucleotides in α HL simultaneously
• Slower translocation
- 1-5 µ s /nucleotide in α HL
• Resistance to extreme conditions
- Temperature
- pH
- Voltage
• α - hemolysin is toxic and hard to work with
 nanopore
chip

Voltage Clamp
Amplifier
AgCl

AgCl
KCl KCl

Data Acquisition

• Voltage-clamp amplifier designed to measure pA

level currents
• Fast (up to 1GHz) data acquisition
• Software for automatic blocking event detection
and recording
Spontaneous Blocking Events with
Smaller NASA Pores
+200 mV

100 pA
0.5 s
 C
C C
C
TT
A
G GA A
G G
A
GG
A G
A

Present Future
• 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) Courtesy of: http://www.uea.ac.uk/cap/wmcc/anc.htm

• 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.
• 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%)
• 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)
Energy levels

Radiationless

Valence noit c udno C

dna B
decay
Fluorescence Band gap
Absorption

Band
Small Qdots Semiconductors
Molecules
 Size Dependent Absorbance
2 and Emission
1.8
1.6
1.4 5.0 nm
1.2
CdSe
(AU)

1
0.8
0.6
0.4 2.2 nm
0.2
0
CdSe
350 450 550 650
W avelength (nm)

L L

Eg ~ 1/L2
 Ordinary light excites all color quantum
dots.
(Any light source “bluer” than the dot of
interest works.)

Quantum dots change color with size because additional

energy is required to “confine” the semiconductor
excitation to a smaller volume.
 ZnSe CdSe CdTe
Normalized Intensity

350 400 450 500 550 600 650 700 750

Emission Wavelength (nm)
Excitation: ZnSe @ 290 nm, others 365 nm

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
• 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