Techniques for synthesis

of nanomaterials (I)
Lecture
Lecture1110
MTX9100
Nanomaterials

OUTLINE
-What are the possible approaches to making
nanomaterials?
-Which technologies can be used to produce
nanostructures using a top-down approach?
- What is bottom down approach?

How to get at nano scale?

There are two general approaches to the synthesis of
nanomaterials and the fabrication of nanostructures

Bottom-up approach
These approaches include the
miniaturization of materials components
(up to atomic level) with further selfassembly process leading to the formation
of nanostructures.
During self-assembly the physical forces
operating at nanoscale are used to combine
basic units into larger stable structures.
Typical examples are quantum dot
formation during epitaxial growth and
formation of nanoparticles from colloidal
dispersion.
2

Top-down approach
These approaches use larger
(macroscopic) initial structures,
which can be externally-controlled in the
processing of nanostructures.
Typical examples are etching through the
mask, ball milling, and
application of severe plastic deformation.

Top-down vs. bottom-up

Top-down methods
begin with a pattern generated on a larger
scale, then reduced to nanoscale.
By nature, arent cheap and quick to
manufacture
- Slow and not suitable for large scale
production.
Bottom-up methods
start with atoms or molecules and build up to
nanostructures
Fabrication is much less expensive
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Top-Down: lithography
At the moment, the most used top-down approach is photolithography.
It has been used for a while to manufacture computer chips
and produce structures smaller than 100 nm.

Strip resist and do process again and again.

Eventually, a 3-D structure is built up

Typically, an oxidized
silicon (Si) wafer is
coated with a 1m thick
photoresist layer. After
exposure to ultraviolet
(UV) light, the
photoresist undergoes a
photochemical reaction,
which breaks down the
polymer by rupturing the
polymer chains.
Subsequently, when the
wafer is rinsed in a
developing solution, the
exposed areas are
removed.

Basic idea behind lithographic

processing

Coat, protect, expose, etch, repeat

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Result:
Multiple patterned layers of different materials.

Top-Down: photolithography

Ferromagnetic/superconducting
devices (e-beam lithography)

Molecular electronics
(e-beam lithography)

Lithographic processing: Masking and

exposure
Expose resist to UV light through a mask

Mask is aligned to wafer before exposure.

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Lithographic processing: Developing

the pattern

Resist is removed from exposed areas

Remaining resist faithfully reproduces mask pattern
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Lithographic processing:
Etch the material

Resist protects selected regions during etch.

Pattern is transferred to substrate material.

Problems in lithography
Though the concept of photolithography is simple, the
actual implementation is very complex and expensive.
This is because
(1) nanostructures significantly smaller than 100 nm
are difficult to produce due to diffraction effects,
(2) masks need to be perfectly aligned with the pattern
on the wafer,
(3) the density of defects needs to be carefully
controlled, and
(4) photolithographic tools are very costly, ranging in
price from tens to hundreds of millions of dollars.
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Electron-beam lithography
Electron-beam lithography and X-ray lithography techniques
have been developed as alternatives to photolithography.
In the case of electron beam lithography, the pattern is written
in a polymer film with a beam of electrons.
Since diffraction effects are largely reduced due to the
wavelength of electrons, there is no blurring of features, and thus
the resolution is greatly improved.
However, the electron beam technique is very expensive and very
slow.
In the case of X-ray lithography, diffraction effects are also
minimized due to the short wavelength of X-rays, but
conventional lenses are not capable of focusing X-rays and the
radiation damages most of the materials used for masks and
lenses.
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The most recent lithography methods

Printing, stamping, and molding use mechanical processes
instead of photons or electrons.
These methods are normally called soft lithography
methods because they involve the use of polymers.
microcontact printing method

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A chemical precursor to polydimethylfiloxane

(PDMS) is poured over and cured into the rubbery
solid PDMS stamp that reproduces the original
pattern.
The stamp can then be used in various inexpensive
ways to make nanostructures.
The stamp is inked with a solution consisting of
organic molecules and then pressed into a thin film
of gold on a silicon plate.
The organic molecules form a self-assembled
monolayer on the solid surface that reproduces the
pattern with a precision of approximately 50 nm.

Advantages of lithography

Once the master template has

been made, no special equipment

is required.

Soft lithographic methods are
capable of producing
nanostructures in a wide range
of materials and can
print or mold on curved as well as
planar surfaces
Photolithography. A beam of UV light activates
the photoresist, transferring the pattern from
the mask to the sample.
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Nanosphere lithography

14

Micromachining methods

15

Focused ion-beam (FIB) machining

FIB machining offers the greatest
resolution, with the ability to make features as
small as 20 nm, but it is very slow.
In FIB a beam of gallium ions from a
liquid metal ion source is accelerated, filtered,
and focused with electromagnetic
lenses to give a spot size of 58 nm.
The beam is tracked across the surface,
contained in a chamber under high vacuum.
The high-energy ions blast atoms from the
surface, allowing simple cutting of slots and
channels or the creation of more elaborate 3-D
shapes. Secondary electrons are
emitted when the gallium ions displace the
surface atoms. These can be used to image the
surface, allowing observation and control
of the process as it takes place.
Dual-beam FIBs have an additional electron gun
16that is used as an alternative way of imaging. The
precision is extraordinary.

Growth and patterning

(top down and bottom up)

Nano-scale structures and micro-scale structures are readily

formed using top
down and bottom up approaches.
Best chance for integration.
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New Method : Bottom Up + Top Down

Self-assembled block copolymers + Optical lithography

Bottom-up methods
1. High precision actuators
move atoms from place to
place
2. Micro tips emboss or
imprint materials
3. Electron (or ion) beams
are directly moved over a
surface

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1. Chemical reactors create conditions for special growth

2. Biological agents sometimes used to help process
3. Materials are harvested for integration

Bottom-Up: Molecular self-assembly

Nature uses self-assembly in
infinitely subtler ways; indeed,
the whole of the natural world is
self-assembled.
Spontaneous organization of
molecules into stable, structurally
well-defined aggregates
(nanometer length scale).
Polythiophene wires

19

Molecules can be transported to

surfaces through liquids to form
self-assembled monolayers
(SAMs).

Self-assembly examples

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Atomic layer deposition

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Methods for making 0-D Nanomaterials

Nanoclusters are made by either gas-phase or

liquid-phase processes.

The commonest of which are inert-gas
condensation and inert-gas expansion.

Liquid phase processes use surface forces to
create nanoscale particles and structures.
There are broad types of these processes:
ultrasonic dispersion, sol-gel methods, and
methods relying on self-assembly.

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Nanoparticle condensation in inert gas

The inert gas
condensation (IGC)
process is one of
the most known and
simplest technique
for production of
nanoparticles (in
particular, Me
nanopowders)

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An inorganic material is
vaporized inside a
vacuum chamber into
which an inert gas
(typically argon or
helium) is periodically
admitted.
Once the atoms boil off,
they quickly lose their
energy by colliding
with the inert gas.
The vapor cools rapidly
and supersaturates to
form nanoparticles with
sizes in the range 2100
nm that collect
on a finger cooled by
liquid nitrogen.

Nanoparticle condensation in inert gas

A material, often a metal, is evaporated from a
heated metallic source into a chamber which has
been previously evacuated to about 107 torr and
backfilled with inert gas to a low-pressure.
The metal vapor cools througchto sluchilos?
h collisions with the inert gas atoms, becomes
supersaturated and then nucleates
homogeneously; the particle size is usually in the
range 1100 nm and can be controlled by varying
the inert gas pressure.

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Ultimately, the particles are collected and may be

compacted to produce a dense nanomaterial.

Example of nanoparticles obtained by

IGC
Decahedral gold nanoparticle generated
from an inert gas aggregation
source using helium and deposited on
amorphous carbon film
[ K. Koga, K. Sugawara, Surf. Sci. 529 (2003) 23]

Icosahedral gold nanoparticles

generated from an inert gas
aggregation source using helium and
deposited on amorphous carbon film
[ K. Koga, K. Sugawara, Surf. Sci. 529 (2003)
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23]

Plasma based synthesis

Vacuum arc deposition is well-established process for producing

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of thin films and nanoparticles. This technique involves the

initiation of an arc by contacting a cathode made of a target
material. An igniter is attached to an anode in order to generate
a low-voltage, high-current self-sustaining arc.
The arc ejects ions and material droplets from a small area on
the cathode. Further, the ions are accelerated towards a
substrate while any large droplets are filtered out before
deposition .

Vapor condensation

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One of the outstanding strides in plasma processing for

nanoparticles synthesis is the developed process of the vapor
condensation.
The precursor material is put into the working chamber with a
stable arc.
The chamber is filled by reactive gas that becomes ionized;
then molecular clusters are formed and cooled to produce
nanoparticles.

Methods for making 1-D and 2-D

nanomaterials

The production route for 1-D rod-like nanomaterials by liquid-

phase methods is similar to that for the production of

nanoparticles.

CVD methods have been adapted to make 1-D nanotubes and
nanowires. Catalyst nanoparticles are used to promote nucleation.

Nanowires of other materials such as silicon (Si) or germanium
(Ge) are grown by vapor-liquid-solid (VLS) methods.

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Molecular Beam Epitaxy (MBE)

A molecular beam
epitaxy (MBE) machine
is essentially an ultrahigh-precision, ultra
clean evaporator,
combined with a set of
in-situ tools, such as
Auger electron
spectroscopy (AES)
and/or reflection highenergy electron
diffraction (RHEED),
for characterization of
the deposited layers
during growth.
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Molecular Beam Epitaxy (MBE)

Schematic diagram of a molecular beam epitaxy thin film deposition

system (adapted from Nanoscale Science and Technology, Eds. R.W. Kelsall, I.W. Hamley, M.

30Geoghegan, John Wiley&Sons Ltd, 2005).

Molecular Beam Epitaxy

In solid-source MBE, ultra-pure elements such
as gallium and arsenic are heated in
separate quasi-Knudsen effusion cells until they
begin to slowly evaporate.
The evaporated elements then condense on the
wafer, where they may react with each other.
In the example of gallium and arsenic, singlecrystal gallium arsenide is formed.
The term beam simply means that evaporated
atoms do not interact with each other or any
other vacuum chamber gases until they reach
the wafer, due to the long mean free paths of
the beams.
The substrate is rotated to ensure even growth
over its surface.
By operating mechanical shutters in front of
the cells, it is possible to control which
semiconductor or metal is deposited.
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MBE principal

Slow but well controlled

deposition rate 1 to 300
nm per minute
For example, opening the Ga and As
cell shuttersresults in the growth
of GaAs. Shutting the Ga cell and
opening the Al cell switches the
growth to AlAs. As the shutters can
be switched rapidly, in comparison
to the rate at which material is
deposited, it is possible to grow
very thin layers exhibiting very
32 sharp interfaces.

The sources can be either solid or gaseous and an

MBE machine will typically have an array of
multiple sources, which can be shuttered to allow
layered, alternating heterostructures to be
produced. Semiconductor quantum wells,
superlattices and quantum wires and metallic or
magnetic multilayers for spin valve structures
are deposited using this technique.

Metal-organic Chemical Vapor

Deposition (MOCVD)
Schematics of the commercial MOCVD
system

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Electrodeposition

Electrodeposition is a long-established

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way to deposit metal layers on a

conducting substrate.

Ions in solution are deposited onto
the negatively charged cathode,
carrying charge at a rate that is
measured as a current in the
external circuit.

The process is relatively cheap and
fast and allows complex shapes.

The layer thickness simply depends on the
current density and the time for which
the current flows.

The deposit can be detached if the
substrate is chosen to be soluble by
dissolving it away.

Electrodeposition - basics

Icosahedral microparticles, pentagonal microtubes and whiskers obtained in

the process of copper electrodeposition [ after A.A. Vikarchuk]

The principle of electrodeposition is inducing chemical reactions in

an aqueous electrolyte solution with the help of applied voltage, e.g.
this is the process of using electrical current to coat an
electrically conductive object with a relatively thin layer of metal.
This method is relevant to deposition of nanostructured materials
include metal oxides and chalcogenides.
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Electrodeposition - features
Electrodeposition is relatively cheap and can be performed at low
temperatures which will minimize interdiffusion of materials in the
case of a multilayered thin film preparation.
The film thickness can be controlled by monitoring the amount of
charge delivered, whereas the deposition rate can be followed by the
variation of the current with time.
The composition and defect chemistry can be controlled by the
magnitude of the applied potential, which can be used to deposit nonequilibrium phases. Pulsing or cycling the applied current or potential in
a solution containing a mixture of precursors allows the production of a
multilayered material.
The potential during the pulse will determine the species deposited
whilst the thickness of individual layers is determined by the charge
passed. Alternatively, the substrate can be transferred periodically
from one electrolytic cell to another.
The final films can range in thickness from a few nanometers to tens
of microns and can be deposited onto large specimen areas of complex
shape, making the process highly suitable for industrial use.
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Electrodeposition and microelectronics

Electrochemically fabricated flip-chip

interconnects

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Electrodeposition (ED)
is being exploited now to make
complex 3D electrical
interconnects in computer
chips. The key concept is that
electrodeposited materials
grow from the conductive
substrate outward, and the
geometry of the growth can be
controlled using an insulating
mask (so-called through mask
electrodeposition).

Electrodeposition in
microelectronics
The insulating mask need not have
a straight line-of-sight path
between the substrate and the
electrolyte; even tortuous masks
can be filled with materials, so
long as the whole path through
the mask is wetted with the ED
electrolyte.
The resulting deposit is a high
fidelity negative replica of the
A ten level copper on-chip interconnect
mask itself. Through-mask ED has
scheme of 90 nm CMOS node fabricated in
been used extensively to pattern
low dielectric constant material.
metals, semiconductors, and
polymers on conductive
substrates.
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Electrodeposition and
nanobiosystems

As a water-based process, it is
often more environmentally
friendly than deposition
methods that require hazardous
solvents and reactive precursor
chemicals (like organometallic
compounds, for instance).

Biological fabrication.

Nanometer-scale cuprous oxide (colorized

red) can be electrodeposited through the openings in
the hexagonally packed intermediate layer protein
(white regions) from the bacterium Deinococcus
radiodurans. Purified crystalline protein sheets are
first adsorbed to a conductive substrate, and then
electrodeposition is carried out to fill the nanometerscale pores in the protein.

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Proteins are responsible for the nucleation,

growth, composition, and shape of functional
biological structures like bones, teeth, and
shells. Using proteins to control the growth of
ED materials is truly a frontier area where
biology meets nanotechnology.
One way that proteins are being used in
electrochemical nanotechnology is as masks for
through mask electrodeposition.
Proteins can self-organize into complex
structures representing all possible twodimensional (2D) space groups built from chiral
molecules. Moreover, they are readily
engineered through molecular biology, providing
an attractive foundation for nanotechnology.

Why electrodeposition?
Electrodeposition has three main
attributes that make it so well
suited for
nano-, bio- and microtechnologies.
It can be used to grow functional
material through complex 3D masks.

Miniature copper mask from the site of

Loma Negra on the far north coast of Peru, ca.
200 C.E. Removal of the green copper corrosion products
reveals a bright gold surface.The extremely thin layer of
gold was applied to the sheet copper by electrochemical
replacement plating.
[Heather Lechtman, Sci. Amer., 250(6), 56 (1984).]

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It can be performed near room

temperature from water-based
electrolytes.
It can be scaled down to the
deposition of a few atoms or up to
large dimensions.