Nanotechnology

 one nanometer = 10−9 m

 the two-dimensional material “graphene” and the two-dimensional
sheet of one atomic layer thick.
 As an electrical conductor, it is as good as copper, and as a
conductor of heat, it is superior to most other materials.
 It is almost completely transparent but impervious to penetration
by all gases including the smallest gas-helium atoms.
 Graphene is a single sheet of graphite, and it can be produced by
rubbing a lump of graphite; for example, drawing a line with a
pencil on a hard surface will produce some graphene sheets
 Terminology
 A nanomaterial - a solid material that exists over the scale of 1 to
100nm and exhibits novel properties that are related to its scale.

 Nanoscience is also sometimes restricted to the study of the new

effects that arise only in materials that exist on the nanoscale

 Nanotechnology is similarly restricted to the procedures for

creating new functionalities that are possible only by manipulating
matter on the nanometer scale.
 Metallic nanopigments are now becoming a focal point of
biomedical nanotechnology because they can be used to tag DNA
and other active nanosized particles in silver halide emulsions used
in photography, nanoparticulate TiO2 pigments, and the nanosized
carbon granules in the ‘carbon black’ used for reinforcing tryes and
in printer’s ink.
 Top-down and Bottom-up Approaches

 Top-down Approach
 The first is to take a macroscale (or microscale) object and carve
out nanoscale patterns, methods of this sort are called top-down
approaches.
 Physical interactions are used in top-down fabrication approaches,
such as photolithography, electron-beam (e-beam lithography),
and soft lithography.
 Photolithography is used to fabricate very large-scale integrated
circuits having feature dimensions on the 100 nm scale
 Bottom-up approach
 The second technique is to build larger objects by controlling the
arrangement of their smaller-scale components and methods of
this sort are called bottom-up approaches.
 The bottom-up approaches to nanoscale fabrication focused on the
chemical interactions of atoms and molecules, and their controlled
arrangement, using chemistry, into larger functional structures

 The two basic approaches most widely used to prepare nano-

materials using bottom-up methods are solution and vapour-phase
methods.

 SYNTHESIS OF NANOPARTICLES

Solution Based Synthesis

 Solution-based, bottom-up, synthetic methods are mainly used for
nanoparticle synthesis because they have atomically mixed and
highly mobile reagents.
 The two stages of crystallization from solution are nucleation and
growth.
 The two basic techniques used to generate inorganic solids are
direct-combination methods and solution-based methods.
 The former does not lend itself well to the synthesis of
nanoparticles because the reactants tend to be micrometre size
particles which react over long periods to reach equilibrium.
 the use of elevated temperatures leads to particle growth during
the reaction, resulting in large crystallites, typically of sizes greater
than 1µm
 There are, however, some examples of the use of mechanical ball-
milling at low temperature to break micrometer-sized powders into
nanoparticles; such methods have been used for producing
nanosized particles of metal hydrides important as hydrogen-
storage materials.
 Solution-based methods, however, permit excellent control over
the crystallization of inorganic materials and are widely used in
nanochemistry.
 By fine-tuning the crystallization process from solution, highly
monodispersed, uniformly shaped nanoparticles of a wide range of
compositions can be prepared by appropriate combinations of
elements from throughout the periodic table.
 Because the reactants in solution-based methods are mixed on an
atomic scale and solvated in a liquid medium, diffusion is fast and
diffusion distances are typically small.
 Therefore, reactions can be carried out at low temperature, which
minimizes the thermally driven particle growth process that is
problematic in direct-combination methods.
 the basic stages in solution chemistry are:
1. Salvation of reactant species and additives
2. Formation of stable solid crystallization nuclei from the solution
3. Controlled growth of the solid nuclei to a specific nanoparticle size
through the addition of controlled amounts of reactant species.
The basic aim in solution synthesis is to generate, in a controlled
manner, the simultaneous formation of large numbers of stable
nuclei that undergo little further growth.
If growth is to occur, it should occur independently of the
nucleation step because then all particles have a chance to grown to
similar sizes.
If performed successfully, the particles will be monodispersed- that
is, all of a similar size in the nanometer range.
 The drawback to the solution method is that the particles can
undergo Ostwald ripening, in which smaller particles in the
distribution redissolve and their solvated species subsequently re-
precipitate on to larger particles, so increasing the average particle
size and decreasing the total particle count.
 To prevent this unwanted ripening, stabilizers- surfactant
molecules that help prevent both dissolution and growth of small
particles- are added.

 Gold nanoparticles can be obtained by controlled reduction of

solutions of [AuCl4] ̶ in the presence of stabilizers.
 Metal oxides and semiconductor nanoparticles may be obtained by
controlled precipitation from solution.
 Vapour Phase Synthesis

 Vapour-phase synthetic methods are alternative techniques for

nanoparticle synthesis using solutions or solids.
 The same fundamentals concerning nucleation and growth that are
relevant to solution synthesis is apply to vapour-phase synthesis.
 The vapour phase needs to be supersaturated to the point at
which a high density of homogeneous nucleation events produces
solid particles in one short burst, and growth must be limited and
controlled in a subsequent step, if it is to occur at all.
 There are significant differences between vapour-phase and
solution-based techniques
 Commercially, vapour-phase synthesis is carried out to produce
nanoscale carbon black and fumed silica in large quantities. Metals,
oxides, nitrides, carbides, and chalcogenides can also easily be
formed by using vapour-phase techniques.
 stabilizers can be added in a straightforward and controllable
fashion, and particles remain dispersed and independent of one
another..
 In vapour-phase techniques, surfactants or stabilizers are not easily
added, and, without surface stabilizers, nanoparticles tend to
agglomerate into larger particles. The size dispersion of
nanoparticles tends to be better for solution-based techniques
than for vapour-phase techniques.
 Vapour-phase techniques are classified by the physical state of the
precursor used as a reagent and by the reaction method
 In spray pyrolysis, a solution is directed onto a hot surface that
causes the solvent to evaporate very quickly, leaving the solid
product on the surface
 In flame synthesis or pyrolysis, a liquid or solution is directed into a
flame and thermal decomposition yields a fine particulate of the
product
 Laser pyrolysis uses a direct laser beam to rapidly heat the solution,
causing evaporation of the solvent and decomposition of the
nanoparticulate.
 In chemical vapour deposition (CVD), the vapour is transported to a
substrate where reaction and solid nucleation occurs
 Plasma synthesis can be used to synthesize elemental solids, alloys,
and oxides, as well as core-shell nanoparticles.
  Templated synthesis
 Nanosized reaction vessels:
 By carrying out reactions in nanoscale reaction vessels, the
ultimate dimensions of solid products are confined to the vessel
size; a reverse (inverse) micelle including amphipathic molecule
has an aqueous polar core in which reactions can occur. (e.g., Cu,
Fe, Au, Co, CdS, CdSe, ZrO2, Ferrites, Fe/Au
 Physical vapour deposition:
 In physical vapour deposition methods, atoms, ions, or clusters,
present as a vapour, absorb on to the surface and combine with
other species to create a solid; molecular beam epitaxy is a
technique in which evaporated species from elemental charges
are directed as a beam at a substrate where growth occurs.
Pulsed laser deposition is a versatile technique to synthesize a
wide variety of high-quality thin films
  MICROSCOPY FOR CHARACTERIZATION OF NANOMATERIALS

 The important characterization techniques under the general
umbrella of scanning probe microscopy are dip-pen
nanolithography, AFM ( Atomic Force microscopy) (using ink pen),
 Self-assembled monolayers (SAMs). SAM can be formed through
molecular transport of the nanoink to the solid substrate surface.
ElectronMicroscopy methods have been essential for the
visualization of nanoscale structure.
 TEM – transmission electron microscopy
 SEM – Scanning electron microscopy