1.

NANOMATERIALS

1.1.1. Definitions: nanoscience, nanotechnology and nanomaterials

It is the ability to design and characterize materials at the nanoscale that

distinguishes modern nanotechnology from previous activities in materials science
and chemistry. Although nanotechnology is widely talked about, there is little
consensus about where the nanodomain begins. In the recent report [Nanoscience and
nanotechnologies: opportunities and uncertainties, The Royal Society and the Royal
Academy of Engineering, London, 2004], the definitions of nanosciene and
nanotechnology are presented without the use of dimensions.

Nanoscience is the study of phenomena and manipulation of materials at

atomic, molecular and macromolecular scales, where properties differ significantly
from those at a large scale.

Nanotechnologies are the design, characterization, production, and application

of structures, devices, and systems by controlling shape and size on the nanoscale.

Nanomaterials is the interdisciplinary discipline crossing the boundary between

nanoscience and nanotechnology and link the two areas together.

It is recognized that the size range that provides the greatest potential and,
hence, the greatest interest is that below 100 nm (equivalent to approximately 500
atom diameters), however, there are still many applications for which larger particles
can provide properties of great interest. Nanoparticles can come in a wide range of
morphologies from spheres, through flakes and platelets, to dendritic structures, tubes,
and rods. Furthermore, nanomaterials cover a hugely diverse range of materials:
polymers, metals and ceramics.

1.1.2. Critical dimensions

Not all materials that can be made into very small particles mean they have
practical use. However, the fact that these materials can be made at nanoscale gives
them the potential to have some very interesting properties which sharply differ from
ones characteristic for massive materials.
It is important that materials at the nanoscale between 1 nm and 100 nm lie
between the quantum effects of atoms and molecules and the bulk properties of
materials. It is this scale where many properties of materials are controlled by
phenomena that have their critical dimensions at the nanoscale.
By being able to fabricate and control the structure of nanoparticles, the
designers can influence the resulting properties and, ultimately, design materials to
give desired properties. It is widely known, the electronic properties can be controlled
at this scale. This phenomena forms the basis for modern electronics industry. Recent
investigations have shown that the range of applications where the physical size of the
particle can provide enhanced properties that are of benefit are extremely wide.
 1.1.3. Nanoparticles fabrication

Manufacturing nanoparticles can be achieved through a wide variety of different

routes. In essence, there are four generic routes to make nanoparticles: wet chemical,
mechanical, form-in-place, and gas-phase synthesis.

Wet chemical processes include chemistry, hydrothermal methods, sol-gels, and

other precipitation processes. Essentially, solutions of different ions are mixed in
well-defined quantities and under controlled conditions of heat, temperature and
pressure to promote the formation of insoluble compounds, which precipitate out of
solution. These precipitates are then collected through filtering and/or spray drying to
produce a dry powder.

Mechanical processes include grinding, milling, and mechanical alloying

techniques. Provided that there is a coarse powder, this coarse powder mechanically is
transformed into finer and finer powder. The most common processes are either
planetary or rotating ball mills. The advantages of these techniques are that they are
very simple, require low cost equipment and, provided that a coarse feedstock powder
and be made, the powder can be processed. However, there are difficulties such as
agglomeration of particles, broad particle size distribution, contamination from the
process equipment, and often difficulty in getting to the very fine particle sizes with
viable yield. It is commonly used for metals and inorganics.

Gas phase synthesis includes flame pyrolysis, electro-explosion, laser ablation,

and plasma synthesis techniques. The production of fullerenes and carbon nanotubes
is a specific subset of gas-phase synthesis techniques.

Form-in-place processes vacuum deposition processes such as physical vapour

deposition (PVD) and chemical vapour deposition (CVD), and spray coating. These
processes are focused to the production of nanostructured layers and coatings with
enhanced properties for different applications. These processes are quite inefficient
for the fabrication of powders. Powders can be manufactured by scraping the deposits
from the collector.
The recently gained knowledge on the atomic and molecular level about
macroscopic phenomena (adsorption, bonding, catalysis, oxidation and other surface
reactions, diffusion, desorption, melting and other phase transformations, nucleation,
growth, friction, hardness and lubrication and etc.) has given new understanding about
processes in materials used for different applications in extreme environment
conditions.
Materials used for specified applications can be divided into two groups: (i)
those that utilize external surfaces, and (ii) nanostructured materials where most of
surfaces of nanoparticles composing material resides at interfaces in the volume of
material.

1.1.4. External surface

The concentration of atoms or molecules at the surface of a solid or liquid can

be estimated from the bulk density. For a bulk density of 1 g/cm3 (such as ice or
water), the molecular density ρ – in units of molecules per cm3 is ≈ 5⋅1022. The
surface concentration of molecules σ (molecules/cm2) is proportional to σ2/3,
assuming cube like packing, and on the order of 1015 molecules/cm2. Because the
densities of most solids or liquids are within a factor of 10 or so of each other, 1015
molecules/cm2 is a good order-of-magnitude estimate of the surface concentration of
atoms or molecules fro most solids or liquids. Of course, surface atom concentration
of crystalline solids may vary by a factor of two or three, depending on the type of
packing of atoms at a particular crystal face.
Thin films are of great importance to many real-world problems. Their material
costs are very little as compared to the bulk material, and they perform the same
function in surface processes. For example, a monolayer of rhodium, a very expensive
metal, which contains only about 1015 metal atoms per cm2, can catalyze the reduction
of NO to N2 by its reaction with CO in the catalytic converter of an automobile, or it
can catalyze the conversion of methanol to acetic acid by the insertion of a CO
molecule.

1.1.5. Dispersed materials

Dispersed materials are constructed from clusters and small particles. Their
properties depend on the size of clusters. Let us introduce quantitative characteristic
of individual clusters and particles.
Dispersion D

Number of atoms in the cluster n

Fig. 1. Clusters of atoms with cubic packing having 8, 27, 64, 125, and 216 atoms. Whereas in an eight
atom cluster all of the atoms are on the surface, the dispersion rapidly declines with increasing cluster
size, as shown in the lower part of the figure [1]

All of the atoms in a three- or four-atom cluster are by necessity “surface

atoms”. As a cluster grows in size, some atoms may become completely surrounded
by neighboring atoms and are thus no longer on the “surface” (Fig. 1). A particle of
finite size is frequently described by its dispersion D, where D is the ratio of the
number of surface atoms to the total number of atoms

number of surface atoms

D= (1)
total number of atoms

For very small particles, D is unity. As the particle grows and some atoms become
surrounded by their neighbors, the dispersion decreases (Fig. 1). Of course, D also
depends somewhat on the shape of the particles and how the atoms are packed. The
dispersion is already as low as 10-3 for particles of 10 nm (100 Å) radius. Many
chemical reactions are facilitated by surface atoms. Consider a monolayer of gold
atoms (a layer of gold one-atom thick) deposited on iron. This film has a dispersion of
unity since all the gold atoms are on the surface. About 50 layers of gold atoms (D =
1/50) are needed to obtain the optical properties that impart the familiar yellow color
characteristic of bulk gold.

Often the surface of a material is roughened deliberately. Automobile brake

pads are designed to optimize the desired mechanical properties of surfaces in this
way, as is the corrugated design of rubber soles of tennis shoes. The large number of
folds of the human brain helps to maximize the number of surface sites, which also
facilitate charge transport of molecules. These are some of the examples that show
how external surfaces are frequently used in nature. External surfaces are a key
element of technology, ranging from catalysts and passivating coatings, to computer-
integrated circuitry and the storage and retrieval of information.

1.1.6. Internal surface

Nanostructured thin films-materials full of nanocrystallites (nanoparticles) have

very large internal interface surface areas. Many thin films that are nanostructured
accommodate atoms and molecules at the interface between nanograins where atoms
and molecules can adsorb or undergo chemical reactions. These materials adsorb
preferentially certain atoms and molecules according to their size and/or
polarizability. This properties is of great commercial importance and may be used to
store gases in thin film materials, to separate mixtures of gases (selective membranes),
or to carry out selective chemical reactions.
The properties of the internal surfaces in nanostructured materials are under
intensive investigations. These studies will result in rapid developments in molecular
studies of phenomena at the buried interfaces including electrochemistry, tribology,
and biology and will lead to rapid developments of new nanotechnologies.
In the following Chapters, the basic knowledge about thin film growth kinetics
using physical vapour deposition technology, and the evolution of film microstructure
is presented.