Introduction to Nanoscience

LECTURE 2
INTRODUCTION II

Copyright: CRC Press 2009

 Agenda

• Material Continuum
• Nanotechnology Timetable
• Properties & Phenomena Continued

Copyright: CRC Press 2009

 Material Continuum?

Materials:

Bulk ↔ Micro ↔ Nano ↔ Atoms & Molecules

Physics:

Classical ↔ Small Particles ↔ Quantum

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 Think in terms of
the “integration of everything”
There is a smooth materials continuum—
we just break it up for the sake of convenience !!

Continua Themes:
the Material Continuum
the Electromagnetic Spectrum
the Energy Continuum
the Chemical Bonding Continuum

Others ???

Copyright: CRC Press 2009

 More Nano History

In addition to colored glasses, pigments, carbon

nanotubes there are:
• Catalysis
• Photography
• The Transistor
• Integrated Circuits
• Micro-Electro-Mechanical Systems (MEMS)

Copyright: CRC Press 2009

 The Timeline
2600 YA Kanada Atomism
2600 YA Anaximander The Aeprion
2500 YA. Democritus Atomism
4th Century Lycurgus Cup Colored glass
1st Century Hero Compressibility
500-1450 Cathedrals Stained glasses
1450-1600 Deruta pottery Iridescence/metal clusters
1661 Robert Boyle Minute masses
1805 John Dalton Elements are atoms
1827 Photography Silver nanoparticle
1857 Michael Faraday Colored gold colloids
1908 Gustav Mie Light scattering nanoparticles
1931 Ernst Ruska Electron microscope
1938 Langmuir / Blodgett LB Films
1947 John Bardeen et al The first transistor
1951 Erwin Mueller Ion-field electron microscope
1st one to see atoms

Copyright: CRC Press 2009

 The Timeline (Continued)
1953 Watson and Crick DNA
1958 Leo Esaki Electron tunneling
1959 Richard Feynman “There’s plenty of room …..”
1960’s NASA Ferrofluids
1960 Plank and Rosinski Zeolites and catalysis
1965 Gordon E. Moore Moore’s Law
1970 John Pople Atomistic modeling
1974 Norio Taniguchi The term “nanotechnology”
1974 M. Ratner / Aviram Molecular electronics
1977 Richard P. van Duyne Surface Enhanced Raman (SERS)
1980 Jacob Sagiv Self-assembled monolayers
1981 G. Binnig / H. Rohrer Scanning tunneling microscope
1985 Smalley / Croto / Curl Buckminster fullerenes
1986 G. Binnig / C. Gerber Atomic force microscope
1987 Averin / Likharev Single-electron tunneling transfer
1988 Louis Brus Quantum dots
1990 Donald Eigler et al IBM with Xe atoms

Copyright: CRC Press 2009

 The Timeline (Continued)
1991 Sumio Iijima Multi-wall carbon nanotubes
1993 Iijima / Bethune Single-wall carbon nanotubes
1996 Mirkin / Letsinger SAM of DNA + gold colloids
2000 Hersam / Lyding Feedback control lithography (FCL)
2001 Mihail Roco National Nanotechnology Initiative

There have been, of course, more developments since 2001.

Please keep up with them by subscribing to online nanotech
services and academic and trade journals.

Source: History of nano Timeline, Northwestern University

www.discovernano.northwestern.edu/whatis/History/# Copyright: CRC Press 2009
 Micro Electro Mechanical Systems = MEMS

Source: Sandia National Laboratory, SUMMiT Technologies Copyright: CRC Press 2009
 MEMS
It is from our integrated circuit / transistor technology
and MEMS that top-down fabrication was developed.

NEMS (nano-electro-mechanical systems) is an

evolutionary byproduct of MEMS technology

Is nanotechnology revolutionary? Is it the next Industrial

Revolution?

Decide for yourself after finishing

this course !
 Integrated Circuits and Transistors
MEMS are fabricated from the top-down by techniques such as
lithography. MEMS is a descendent of the integrated circuit
business. The image on the left is actually “old technology”. The
dielectric gate material is 1.2 nm thick.

Source: Courtesy of George Thompson, Intel Corporation Copyright: CRC Press 2009
Moore’s Law

Copyright: CRC Press 2009

More Properties & Phenomena
 The Damascus Sword
• The Damascus Sword (ca. 10th to 18th centuries) ….. a
composite metal and the first technological (and unwitting)
use of carbon nanotubes, other carbon materials,
cementite nanowires and glasses
• The Damascus sword was strong, hard, flexible and very
sharp– due to its laminar structure, the result of its special
forging process
• Carbon nanotubes were formed from a special iron
(steel) made in India called “Wootz steel”, a high carbon
and pure steel.

Copyright: CRC Press 2009

 7th Nano-Phenomenon
Strongest Materials
• Tensile strength is not a nanophenomenon per se
but the strongest materials known to science and
technology are carbon nanotubes.
• Young’s modulus of carbon nanotubes show that
they are the strongest and stiffest materials
• The carbon–carbon bond is one of the strongest.
This in itself is not a nanophenomenon.
• However, when such C–C bonds exist in a material
formed in a tube that is 1 nm in diameter and
structured like graphite and is relatively pure, then
you have a nanophenomenon.

Copyright: CRC Press 2009

Carbon Nanotubes
 Example 2.1
Q: The energy stored in a C–C bond is 348 kJ·mol-1 and its
length is 0.154 nm. Assume that the bond stretches twice
its equilibrium length before rupture. What is the lifting capacity
of a single C–C bond? Calculate its tensile strength.

0.154 nm Tensile Load

Covalent Radius of Carbon = 0.077 nm

 Example 2.1 (Continued)
A: We need to calculate the force required to rupture the
bond: F = Ebond ÷ xstretch and F = m·a and a = g where
g = 9.81 m·s-2. First we need to convert energy into force.
The distance xstretch = 2·(0.154 nm) - 0.154 nm. The mass
required to rupture the C–C bond needs to be greater than m:

Ebond  348 kJ   mol  1000 J 

EC –C = = ⋅  ⋅   = 5.78x10 −19
J C–C
N 23
 mol   6.022x10   kJ 

EC –C 5.78x10−19 JC–C  
−9 J
Fstretch = = = 3.73x10   = 3.73x10−9
N
€ xstretch 0.154x10 m
−9
 m

FC –C 3.73x10−9 N 1000g  109 ng 

m= = = 3.82x10 kg ⋅ 
−10
⋅  = 383 ng C–C
€ g 9.81m⋅ s−2
 kg   g 

€
 Example 2.1 (Continued)
Proportion of lifting capacity to the mass of 2 C’s:
M  12.01g ⋅ mol−1  -23
 109 ng  -14
m2C = 2⋅  = 2⋅ −1 
= 3.99x10 g ⋅   = 3.98x10 ng
N 
23
 6.022x10 ⋅ mol   g 

m 383 ng 15 14th
Proportion = = = 9.62x10 → 10
€ m2C 3.98x10−14 ng

The carbon–carbon bond is capable of lifting 1014 times

€ the mass of the two carbon atoms making the bond. The
tensile strength is the force divided by its cylindrical area:
2
2 2  1m 
Axs−C = π ⋅ rCovalent = π ⋅ (0.077nm) = 0.0186 nm2 ⋅  9  = 1.86x10−20 m2
10 nm 
N 3.73x10−9 N 11
 1 GPa 
τ C –C = 2 = = 2.00x10 Pa ⋅  9  = 200 GPa
m 1.86x10−20 m2  10 Pa 
€

€
 Example 2.1 (Continued)
Procedure Question: In reality, the energy of the carbon–
carbon bond is not constant as we assumed. The bond energy
was averaged over the distance xstretch in Example 2.1. The break
point (at x or r) of a bond corresponds roughly to its potential
energy at Ebond = 0 J. Looking at a typical E vs. r curve:

The vertical axis is potential energy and the

horizontal axis is inter atomic radius. The top
curve represents a repulsive potential while
the bottom curve represents an attractive
potential.
 Example 2.2
Q: Taking the C–C bond force from the previous problem,
calculate how many (12,0) zigzag nanotubes are required to
lift an average person (wt. = 150 pounds). There are 12
carbon-carbon bonds aligned vertically along the long axis of
the nanotube and the diameter of this carbon nanotube is
0.953 nm. What is the diameter of the cable? Assume that
there is tight packing (i.e. tubes are touching with packing
efficiency in two-dimensions of 0.91). The tensile strength?

Unfolded nanotube showing C–C bonds under tension

Bundled (12,0) single-walled carbon nanotubes

 Example 2.2 (Continued)
A: To find the newtons for a (12,0) zigzag tube, we multiply the
FC–C by 12:
N(12,0) = 12 ⋅ 3.73x10 N = 4.48x10 N
−9 −8

The cross sectional area of a nanotube is:

€  d (12,0) 2  0.953x10−9 m 2 2
Axs = π ⋅   = π ⋅  = 7.13x10 m
−19

 2   2 

The number of nanotubes required to lift 150 lbs is:

€ lbs ⋅  N  = 667 N 667 N
150 and N (12,0) = = 1.49x10 10
Nanotubes
 0.225 lbs  4.48x10−8 N

Diameter of the nanotube cable:

€ €⋅A
d cable = 2 ⋅
(N (12,0) xs ) = 2⋅ 1.49x1010 ⋅ 7.13x10−19
= 122 µm
π ⋅ PE π ⋅ 0.91

Which is a little thicker than a human hair!

€
 Example 2.2 (Continued)

The lifting force capability of a (12,0) nanotube is:

FNanotube) = 12 ⋅ FC −C = 12 ⋅ 3.73x10−9 N = 4.48x10−8 N

The tensile strength of a (12,0) zigzag tube is spread over the

€cross sectional area of the tube:

FNanotube 4.48x10−8 N 10
 GPa 
τ (12,0) = = −19 2
= 6.28x10 Pa ⋅  9  = 62 GPa
Axs-(12,0) 7.13x10 m 10 Pa 

This value is “coincidentally” within the range of published

€
values of tensile strength for single-walled carbon nanotubes
 Example 2.2 (Continued)
Procedural Questions:

1. Can we calculate tensile strength of the nanotube by smearing

Fnanotube over its cross sectional area? or should it be calculated
over its annular area— the area the carbon actually occupies?

or ?

2. We started with the energy of a C–C bond. In actuality, a

carbon nanotube does not have pure C–C sp3 bonds but
rather a mixture of sp3 and sp2. Will this be a stronger or
weaker bond? How will the parameters calculated in these
problems vary?
 8th Nano-Phenomenon
Collective Surface Area

As materials get smaller and smaller…. their collective

surface area gets larger and larger.

Collective surface area:

Acollective = ∑ Aparticles

€
Copyright: CRC Press 2009
 Collective Surface Area
Each time the material is divided, the surface area increases
geometrically.

Copyright: CRC Press 2009

 Example 2.3
Q: How many 10 nm nanocubes are required to produce the
same surface area as a one cubic meter cube? How much
volume do they occupy?

A: The surface area of a cubic meter is 6 m2. The surface area

of this single nanocube is 600 nm2.
2
6m2  9
10 nm  16
N nc = 2   = 1x10 nanocubes
600 nm  m 

The volume occupied by this number of nanocubes is:

€  3  3 3

Vnc = 1x1016 nanocubes ⋅ 

(10 nm)  ⋅ m = 1x10−8 m3 100cm = 0.01cm3
   
 nanocube  109 nm  
 m 

 

1/100th of a cc !! THE POWER OF NANO

Copyright: CRC Press 2009
 9th Nano-Phenomenon
Singular Surface Area and
the Surface-to-Volume Ratio
When we refer to singular surface area, we refer to the
surface area of a single nanoparticle.
Area is a function of a dimension squared, e.g. d2, x2 or r2.
Volume is a function of that dimension cubed, e.g. d3, x3 or
r3.
Surface-to-volume ratio (d2 / d3) scales as the inverse of the
dimension: e.g. d-1. In other words, as the dimension
approaches smaller and smaller limits, the surface-to-
volume ratio scales as the inverse of the dimension.

Copyright: CRC Press 2009

 The Simple Cube
Dimension Area in m2 Volume in m3 S/V Ratio

1m 6 1 6

0.1 m 6 x 10-2 6 x10-3 60

0.01 m 6 x 10-4 6 x10-3 600

0.001 m 6 x 10-6 6 x10-9 6,000

1 x 10-6 m 6 x 10-12 6 x10-18 6 x 106

1 x10-9 m 6 x 10-18 6 x10-27 6 x 109

Why is this important? It means that the the surface becomes

more important as a material becomes smaller and that there
can be a lot of surface if required (e.g. catalysis).

Copyright: CRC Press 2009

 10th Nano-Phenomenon
Surface Atom to Volume Atom Ratios
This phenomenon should be a corollary of the 9th one, but we
shall give it its own category. It is due to the surface atoms that
nanomaterials display “remarkable phenomena”.

The surface is important at any size

domain. The surface is where just
about everything occurs. In bulk
materials, most of the atoms or
molecules are contained within the
volume of the material.
In nanomaterials, the proportion of
surface atoms increases dramatically
as diameter is decreased.

Copyright: CRC Press 2009

 Example 2.4
Q: Calculate the ratio of surface atoms to volume atoms by a
simple procedure for a R = 10 nm gold colloid. Assume that the
surface atoms occupy a thickness of one atomic diameter
(dgold = 0.288 nm) and that the packing fraction for gold is at a
volume efficiency of 0.740 and surface efficiency of 0.91.
d

1. Calculate the volume of the surface layer:Thickness = d

3 3  3 3
VSurface = πR − π ( R − d )
4
3
4
3
= π 10 − (10 − 0.288)  = 352 nm3
4
3  

Copyright: CRC Press 2009

€
2. Calculate the number of gold atoms in the surface layer:
Volume available for gold atoms = 0.91·Vlayer = 320 nm2
3 3
 d   0.288nm  3
VAtom = 34 π   = 34 π   = 0.0125 nm
2  2 

VSurface 320 nm3

Ns-gold is: N S −Gold = = 3
= 28,200 gold atoms
VAtom 0.0125 nm
€

3. Calculate the number of gold atoms in the volume of the

colloid: 3 3
= 0.740 ⋅ π R = 0.740 ⋅ π 10 = 3,100 nm3
€ V Volulme
4
3
4
( ) 3 ( )
VVolume 3,100 nm3
Nv-gold is: NV −gold =
VAtom
= 3
= 248,000 gold atoms
0.0125 nm
€
Surface atom to volume atom ratio is:

€ S Atoms N S -Gold 28,200

= = = 0.113 = 11.3%
VAtoms NV -Gold 248,000
Copyright: CRC Press 2009
 11th Nano-Phenomenon
Electron (and single electron) Tunneling
If a metal is coated with an oxide a few nm in thickness, the
electrons of the metal are trapped within a potential
barrier— according to classical physics. In order to
surpass the barrier, the electron must gain kinetic energy
such that KEe > Ubarrierl
However, quantum mechanics tells
us that the electron has the ability
to get through the barrier by a
phenomenon called tunneling– at
energy less than the potential
energy of the barrier.

Nanomaterials are able to express

this phenomenon— in particular,
thin films.
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 12th Nano-Phenomenon
Coulomb Blockades & Staircases
This phenomenon relates to the transfer of single electrons
across a nano-barrier. Appropriate for nanomaterials < 30
nm— that occur at metal-insulator-metal junctions, quantum
dots and large molecules with conducting cores.

A Coulomb blockade
suppresses tunneling
voltages:
e
V <
C

€
Copyright: CRC Press 2009
 Nano Phenomena Summary

1. Constructive - Destructive interference by thin films

2. Non-Reflective Surfaces
3. Super-Hydro-Phobicity
4. Self-Cleaning
5. Particulate Dichroism
6. Localized Surface Plasmons
7. Strongest Materials
8. Collective Surface Area
9. Enhanced Surface-to-Volume Ratio
10. Surface Atom Effects
11. Electron Tunneling
12. Coulomb Blockade & Staircase

Copyright: CRC Press 2009

 Keep these phenomena
in mind as we
navigate through this course.

They will emerge—

time and time again and more
will be added for sure.