CH7101-Nanotechnology and its applications

Textbook: Introduction to Nanoscience, Gabor L.

Hornyak et al., CRC press.
Reference: Nanostructures & nanomaterials
synthesis, properties & applications. Guozhong Cao

A/P Xu Rong A/P Wang Xin

Office: N1.2-B1-10 Office: N1.2-B1-15
Email: Email:
RXu@ntu.edu.sg WangXin@ntu.edu.sg
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Course contents
 Introduction of nanotechnology
 Physical chemistry of solid surfaces
 Preparation of nanomaterial
 Characterization techniques of nanomaterial
 Size dependent properties and special
nanomaterials
Assessment:
 Project <=30%
 Final exam >=70%
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 Course Project

•Topic: one type of selected nanostructured

materials/nanotechnology and its applications.

•At the end of the project, students should have a

comprehensive understanding of the selected
nanostructured material: its methods of synthesis,
characterization and properties, applications.

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 Course Project

•Extensive search of information from the web is

expected, particularly on research or commercial
developments. The reports must be properly
referenced (use common scientific journal format),
credits acknowledged and not to exceed 6000
words.

•Every one requires the submission of one report.

•Online submission to NTULearn -> Assignment

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I. Introduction of nanotechnology
Overview
 History of nanotechnology.
 What makes the ‘nanoscale’ so special.
 How nanomaterials are made and
characterized
 Examples of nanomaterials and
nanotechnology .
 What nanotechnology can offer now and
in the future.

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 Electron microscopy enters the picometer
scale

Juelich, Germany ferroelectric

PbZr0.2Ti0.8O3

Studying Atomic Structures by Aberration-Corrected Transmission

Electron Microscopy, Knut W. Urban
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Science 25 July 2008: 506-510
1. History of nanotechnology

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Prof. Norio Taniguchi:
Nano-technology mainly consists of the processing of,
separation, consolidation, and deformation of materials by one
atom or one molecule。

• Dr. K.E. Drexler promoted the concept in his book:

– 1986: Engines of Creation: The Coming Era of
Nanotechnology
Molecular Nanotechnology
Most methods arrange atoms crudely; even the finest
commercial microchips are grossly irregular at the atomic
scale.
Like Biology, cells contain molecular machines that
read digital genetic data to guide the assembly of
large molecules (proteins) that serve as parts of
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molecular machines.
Factory of nanomachine
By holding and positioning molecules,
nanomachines will control how the
molecules react, building up complex
structures with atomically precise
control.

―Nanotechnology is the principle of atom manipulation atom by atom,

through control of the structure of matter at the molecular level. It
entails the ability to build molecular systems with atom by atom
precision, yielding a variety of nanomachines.‖

As such, nanotechnology does not yet exist

according to Drexler’s definition

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 Nanoelectromechanical systems --
CNT based motor

* A. Barreiro, et al. subnanometer motion of cargoes driven by thermal

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gradients along carbon nanotubes, Science, 320 (2008) 775.
 Scanning Probe Patterning: When
Probe Size Does Not Matter

scan speed: 5 micron/s

Line width: 28nm

Thermochemical Nanopatterning of Organic Semiconductors

Nat. Nanotechnol. 2009, 4, 664–668
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In recent years,
Nanotechnology: Making/Measuring/Manipulating
matter at a scale of 1 to 100 nanometers.

―Nanotechnology is the creation of functional

materials, devices, and systems through control of
matter on the nanometer length scale, exploiting
novel phenomena and properties (physical,
chemical, biological) present only at that length
scale.‖ Federal Government of USA

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New Journals dedicated: Nano Letters, ACS Nano, Small,
Nanotechnology, Nanoscale, Nano Research, Nano
Energy… 15
Nanotechnology is hot and multidisciplinary:

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2. What makes the ‘nanoscale’ so special

 At the nanometer scale, properties

become size-dependent.
 We can arrange molecules in a way that
they do not normally occur in nature (e.g.
defect free nanotube – electron moves
ballistically)
 The material strength, electronic, magnetic
and optical properties of materials can all
be altered using nanotechnology.
New properties enables new applications.
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New properties at nanoscale

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(I) Thermal properties

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 The melting point change is inversely
proportional to the radius of the nanoparticle, r.

The shape also affect the melting point.

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(II)

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 (III) Optical property Localized surface
Transmission, reflection, emission color plasmon resonance

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Emission color for the semiconductors

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 Photoluminescence

Quantum dot
quantum of light (―photon‖)
with λ= hc/ΔE
• Smaller particle (larger ΔE)
implies shorter wavelength
(―blue shifted‖)

Decrease particle size 25

 Structural color
wing material is brownish

the nanostructures on the

butterfly’s wings are about
the same size as the
wavelength of visible light
and because of the multiple
layers in these structures,
optical interferences are
created
There is constructive interference for a given wavelength
(around 450nm for this case) and destructive interferences
for the other wavelengths
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 Light scattering in the atmosphere

Rayleigh scattering vs Mie scattering

• the elastic scattering of • For particle sizes larger
light by particles/molecules than light wavelength
much smaller than the • not strongly wavelength
wavelength of the light. dependent

Rayleigh scattering intensity  -4

Why is the sky blue and is the sun

red during sunset/sunrise?
Why is the cloud white?
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(IV)

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The wavefunction of the electron does not decay abruptly to zero but
decays exponentially. If the gap (s) is thin enough there is a probability
that the electron may be found on the other side of the barrier. This
allows the electron to move (or tunnel) through the barrier rather than
over it

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Generic (and idealistic) current–potential relationships
are shown for a bulk metal (left) and a material capable
of single-electron transport (right)—like a gold cluster.

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 (V) Magnetic properties

• Electron orbiting nucleus

Magnetization
• Electron spin
source for material:
• Nuclear spin (negligible)

Three common types of magnetism:

• Diamagnetism

•Paramagnetism

• Ferromagnetism
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 Magnetization

Diamagnetic substance: no unpaired electrons

• Acquisition of SMALL induced magnetization OPPOSITE to
the applied field.

• The magnetization depends linearly on the applied field and

reduces to zero on removal of the field.

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Paramagnetic substance:  with unpaired electrons

•Acquisition of SMALL induced magnetization ALONG the applied

field.
• The magnetization depends linearly on the applied field and
reduces to zero on removal of the field.
•Due to the alignment of unpaired spins of electrons

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 Ferromagnetic substance:  unpaired electrons
 Long range order
• The path of the magnetization as a function of the applied
field is non-linear and is called hysteresis loop.

• Magnetization that can be orders of magnitude larger than

B
the paramagnetic solids.
When T>Curie Temperature,
Lose ferromagnetic property.
remanence
H
Coercivity

This is how the harddisk can store information.36

When ferromagnetic particles become smaller,

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 Giant Magnetoresistance

Nanometer thick films of

magnetic and electrically
conductive materials
experience large
variations in electrical
resistance in the
presence of a magnetic
field.

This phenomenon is
used to read bits in
hard disks

2007 Nobel Prize in physics was awarded to the European Albert 38

Fert and Peter Grünberg for the discovery of GMR.
 (VI) Redox property
As a result of size confinement,
the band gap increases and the
band edges shift to yield larger
redox potentials.

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3. How are nanomaterials made/characterized
The techniques can be classified into two groups:

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Top down approach
•Milling
•Attrition
•lithography
(light, e-beam,
x-ray…)

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Drawbacks of top-down approach
Imperfection of surface structure -- defect,
contamination and internal stress

Reduced conductivity and generation of excess

heat due to inelastic scattering
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 Bottom up approach
Nothing new for material synthesis
•crystal growth
•polymer synthesis

When structures fall into a nanometer scale, there is

little choice for top down approach.

Promise a better chance to obtain nanostructures

with less defects, more homogeneous composition
and better short and long range order. – driven by the
reduction of Gibbs free energy.

But difficult to make complex structure. 44

Another way to group the synthesis techniques

(1)Zero dimensional nanostructure

Nanoparticles by means of colloidal
processing, flame combustion and phase
segregation.
(2) One-dimensional nanostructure
Nanorods or nanowires by template-based
electroplating, solution-liquid-solid growth
(SLS), and spontaneous anisotropic growth.
(3) Two-dimensional nanostructure
Thin films by molecular beam epitaxy (MBE)
and atomic layer deposition (ALD).
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Investigative Tools –
(1). Modeling and Simulation

Computational chemistry
• Ab initio method schrodinger equation
(handle up to a few hundred atoms)
• Molecular mechanics and dynamics method
(able to handle 107 atoms)
• Monte Carlo method – based on statistical
mechanics
• Finite element analysis (treat material as
continuum with consistent properties when
stretched, bent, or perturbed in other ways.) 46
Investigative Tools –
(2). Experimental methods

View and probe:

• Electron Microscopy (SEM,TEM)
• Scanning Probe Microscopes (STM,AFM)
• Spectroscopy
(X-Ray Spectroscopy, UV-Vis, IR, Raman, XPS,
SERS)

Manipulate:
• Computer-controlled SPM (Nanomanipulators)
• Optical tweezers

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 Measurement:
• Size (direct observation, light scattering)
• Surface area and porosity (BET, BJH
method by gas adsorption, mercury
porosimetry)
•Weight (Quartz Crystal Microbalance)
• Others
Stokes-Einstein Eq. k T
r B
6 D
Sauerbrey Eq.  6 2 m
f  2.26  10 f 0
A
oscillation frequency of a piezoelectric crystal 48
4. Examples of nanomaterials and
naotechnologies
Carbon in the macro

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 Carbon in the nano

graphene

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A few interesting techniques to manipulate
nanomaterial

•Manipulation of atoms/molecules by
scanning tunneling microscope (STM)

•Nano-tweezer

•Dip Pen Nanolithography (DPN)

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STM

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STM was first invented by Gerd Binning and
Hienrich Rohrer in 1981 at IBM Laboratories. They
could get images that were ten angstroms square!

Gerd Binning Hienrich Rohrer

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Gerd Binning and Hienrich Rohrer were
awarded Nobel prize in physics in 1986 due to
their great contribution in developing STM.

Noble Prize in Physics in 1986

 ½ Nobel prize to Dr. Ernest Ruska: electron

optics and electron microscopy
 ¼ Nobel prize to Dr. Gerd Binning: STM
 ¼ Nobel prize to Dr. Hienrich Rohrer: STM

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•The tunnelling current depends so
strongly on the distance that it is
dominated by the contribution flowing
between the last atom of the tip and
the nearest atom in the specimen ---
single-atom imaging

•For Φ =4 eV, the tunnelling current

reduces by a factor 10 for every 0.1nm
increase in d. This is what makes the
STM so sensitive.

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Manipulation of atoms by STM

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Three steps to move an atom by STM
1) vertically approaching the tip towards the
manipulated atom to increase the tip-atom
interaction.
2) scanning the tip parallel to the surface where
the atom moves under the influence of the tip.
3) retracting the tip back to the normal image-
height thereby the atom is left at the final
location on the surface.
Three modes

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Pushing mode
• Repulsive forces between the tip and the adatom.
• The periodicity d0 of the current signal I reflects the
periodicity of the surface.
• Typically, d0 is equal to the lattice constant if the motion
is parallel to an atomic row of the substrate.

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Pulling mode
• Attractive forces between the tip and the adatom.
• This is again (equivalent to the "Pushing" mode) a
discontinuous ("hopping") motion.

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Sliding mode
• The tip is much closer to the surface.
• When the tip approaches the surface, the adatom hops
onto the tip, but is not chemically bound to it.
• When the tip is withdrawn, the adatom returns to the
surface.

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0.1 nm lateral resolution and 0.01 nm depth resolution
The resolution of an image is limited by the radius
of curvature of the scanning tip of the STM
W (electrochemical etching)
Tip: Pt-Ir (mechanical shearing)
CNTs
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 Nano-tweezer

• STM and AFM have the capability of working at

length scales as small as atoms
• However, single tip limits their ability to manipulate
objects and measure physical properties such as:
• one tip cannot grasp an object
• electrical measurement cannot made without
second contact to the object

Two probes in the form of tweezers can overcome

these limitations and might enable new types of
fabrication and easy electrical measurements on
nanostructures
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Fabrication of first CNT nanotweezers
Philip Kim & Charles M. Lieber, Harvard University

Schematic illustrating the

deposition of two independent
metal electrodes and
subsequent attachment of
carbon nanotubes to these
electrodes

SCIENCE 286 (5447): 2148-2150 DEC 10 1999

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P. Boggild, T.M. Hansen and F Grey, C. Tanasa
Technical University of Denmark MIT

(a) By focusing an electron beam on the end of the

micro-cantilever,a narrow C tip grows in the direction
of the beam.
(b) The growth proceeds in smaller and smaller steps
until the gap is 100–400 nm.

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(c) Secondary parallel tips can be deposited by short
(20–100 s) depositions to facilitate holding of
elongated objects such as wires.
(d) A close up of the nanotweezer, showing tip length
alignment within 10 nm.

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Dip Pen Nanolithography (DPN)

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5. What nanotechnology offers now
and in the future.

Google: smart contact lens to monitor blood

glucose levels

Single atom catalyst with remarkable performance

for water gas shift reaction

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Nanotechnology consumer projects and products

http://www.nanotechproject.org/index.php?id=44

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With the number of nanotechnology-enabled
products entering the market expected to
grow dramatically—from $30 billion in 2005 to
$2.6 trillion in global manufactured goods
using nanotechnology by 2014—―numerous
uncertainties exist regarding possible impacts
on the environment and human health‖

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Prediction is very difficult, Especially of the future ”
attributed to Niels Bohr

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