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GE8073 Unit 2
GE8073 Unit 2
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UNIT - II
General Methods
2 of Preparation
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Bottom - up Synthesis - Top - down Approach : Co-Precipitation, Ultrasonication,
Mechanical Milling, Colloidal routes, Self-assembly, Vapour phase deposition, MOCVD,
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Sputtering, Evaporation, Molecular Beam Epitaxy, Atomic Layer Epitaxy, MOMBE.
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Contents
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2.1 Fabrication Methods - Introduction nee
2.2 Co-Precipitation rin
2.3 Ultrasonication
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2.4
2.5
Mechanical Milling
Colloidal Routes
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2.6 Self Assembly
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Fundamentals of Nanoscience (2 - 2) General Methods of Preparation
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Integrated circuit fabrication is an example for top down nanotechnology. Now it has been
grown to the level of fabricating nano electromechanical systems (NEMS) where tiny
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mechanical components such as levers, springs and fluid channels along with electronic
circuits are embedded to a tiny chip. The starting materials in these fabrications are
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relatively large structures such as silicon crystals. Lithography is the technology which has
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enabled making such tiny chips and there are many types of them such as photo, electron
beam and ion beam lithography.
Bottom - up Approach ngi
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Bottom-up approach in nanotechnology is making larger nanostructures from smaller
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building blocks such as atoms and molecules. Self assembly in which desired nano
structures are self assembled without any external manipulation. When the object size is
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getting smaller in nanofabrication, bottom-up approach is an increasingly important
complement to top-down techniques.
Bottom-up approach nanotechnology can be found from nature, where biological systems
have exploited chemical forces to create structures for cells needed for life. Scientists and
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engineers perform research to imitate this quality of nature to produce small clusters of
specific atoms, which can then self assemble into more complex structures. Manufacturing
of carbon nanotubes using metal catalyzed polymerization method is a good example for
bottom-up approach nanotechnology.
The bottom-up approach first forms the nanostructured building blocks such as atoms and
molecules and assembles them into larger nanostructured material. This is a powerful
approach of creating identical structures with atomic precision.
The top-down approach involves the breaking down of large pieces of bulk material to
generate the required nanostructured material from them. Both approaches can be done in
gas, liquid, solid state or in vacuum.
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(ii) Sputtering
a. DC sputtering
b. RF sputtering
c. Magnetron sputtering
d. Reactive sputtering.
2. Self-assembly
3. Liquid phase processes
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2.2 Co-Precipitation
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Coprecipitation (CPT) or co-precipitation is the carrying down by a precipitate of
substances normally soluble under the conditions employed. Analogously, in medicine,
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coprecipitation is specifically the precipitation of an unbound "antigen along with an
antigen-antibody complex.
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Coprecipitation is an important issue in chemical analysis, where it is often undesirable, but
in some cases it can be exploited. In gravimetric analysis, which consists on precipitating
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the analyte and measuring its mass to determine its concentration or purity, coprecipitation
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is a problem because undesired impurities often coprecipitate with the analyte, resulting in
excess mass. This problem can often be mitigated by "digestion" (waiting for the precipitate
to equilibrate and form larger, purer particles) or by redissolving the sample and
precipitating it again.
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There are three main mechanisms of coprecipitation : Inclusion, occlusion and adsorption.
An inclusion occurs when the impurity occupies a lattice site in the crystal structure of the
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carrier, resulting in a crystallographic defect; this can happen when the ionic radius and
charge of the impurity are similar to those of the carrier.
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An adsorbate is an impurity that is weakly bound (adsorbed) to the surface of the
precipitate.
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An occlusion occurs when an adsorbed impurity gets physically trapped inside the crystal
as it grows.
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Besides its applications in chemical analysis and in radiochemistry, coprecipitation is also
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"potentially important to many environmental issues closely related to water resources,
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including acid mine drainage, radionuclide migration in fouled waste repositories, metal
contaminant transport at industrial and defense sites, metal concentrations in aquatic
systems and wastewater treatment technology".
Coprecipitation is also used as a method of magnetic nanoparticle synthesis.
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2.3 Ultrasonication
Sonication is the act of applying sound energy to agitate particles in a sample, for various
purposes such as the extraction of multiple compounds from plants, microalgae and
seaweeds.
Ultrasonic frequencies (> 20 kHz) are usually used, leading to the process also being
known as ultrasonication or ultra-sonication.
In the laboratory, it is usually applied using an ultrasonic bath or an ultrasonic probe,
colloquially known as a sonicator. In a paper machine, an ultrasonic foil can distribute
cellulose fibres more uniformly and strengthen the paper. www.EasyEngineering.net
Sonication has numerous effects, both chemical and physical. The chemical effects of
ultrasound are concerned with understanding the effect of sonic waves on chemical
systems, this is called sonochemistry. The chemical effects of ultrasound do not come from
a direct interaction with molecular species. Studies have shown that no direct coupling of
the acoustic field with chemical species on a molecular level can account for sonochemistry
or sonoluminescence. Instead, in sonochemistry the sound waves migrate through a
medium, inducing pressure variations and cavitations that grow and collapse, transforming
the sound waves into mechanical energy.
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employed in the production of nanocrystals and/or nanoparticles from all material classes.
The powder materials are crushed mechanically in the rotating drum by the hard balls. This
repeated deformation can cause large reductions in grain size to form nanoparticles.
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The fundamental principle of size reduction in mechanical attrition devices lies in the
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energy imparted to the sample during impacts between the milling media.
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Useful for ceramic processing and powder metallurgy industries objectives of milling,
o Include particle size reduction(grinding);
o Amorphization; particle size growth; rin
o Shape changing (flaking);agglomeration;
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o Solid-state blending (incomplete alloying);
o Modifying, changing, or altering properties of a material (Density, flow ability, or work
hardening);and
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o Mixing or blending of two or more materials or mixed phases.
o “Mechanical alloying.” Mechanical Alloying (MA) is a powder technique that allows
production of homogeneous materials from blended elemental powder mixtures.
Types of Milling
Different types of milling equipment are available for mechanical alloying and nanoparticle
formation. They differ in their capacity, efficiency of milling and additional arrangements
for heat transfer and particle removal.
1. Shaker milling - 10-20 gm
2. Planetary ball milling - few 100 gm
3. Attritor milling - 0.5 to 40 kg www.EasyEngineering.net
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materials, however, was not a matter of detailed investigations in the field of sol-gel
chemistry. However, recent investigations including microwave and hydrothermal
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processing have been used for nanoparticle systems. One of the serious problems is the
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strong aggregation during processing from sols to gels. This is shown in Fig. 2.5.1, where
the formation of low-density aggregates is demonstrated.
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Fig. 2.5.1 : Scheme of the formation of agglomerates from colloidal sols
(Sol-gel transition)
The exciting perspective, however, is that through simple precipitation processes a wide
variety of composition is available, ranging from simple oxides to chalcogenides or even
metals. For these reasons, a precipitation route under a growth-controlling condition has
been developed. This process is based on the hypothesis that molecules able to interact with
the particle surface are influencing nucleation and growth through the interfacial free
energy. It could be shown that the growth reaction follows rather simple rules. It also could
be shown that by use of surface-controlling agents, very www.EasyEngineering.net
uniform particle sizes in the
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Fundamentals of Nanoscience (2 - 8) General Methods of Preparation
nanometer range could be obtained. Various types of component can be used as growth and
size-controlling agents, e.g.complex-forming agents as diketones, which are very useful for
oxides, other complex ligands, like amines or chelating agents, which have shown their
usefulness for metals or sulfides in the case of chalcogenides like CdS2. It is postulated that
these components control the surface free energy during the nucleation and growth process
in a way that very uniform particle size distributions are obtained. This can be explained by
assuming that an optimal coverage of the surface with the surface modifier exists that is
specific for a given system (Leading to a free energy minimum) and that an exchange of
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ions or molecules between the particle can take place. In this case, the particle size can be
tailored by the feed-to-ligand (Surface-controlling agent, SCA) ratio. Based on these
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considerations, a generalizable process has been developed for the fabrication of
nanoparticles that is shown schematically in Fig. 2.5.2 and described indetail.
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Fig. 2.5.2 : General scheme of a chemical route to nanoparticles
`In this process, liquid precursors are used, which, as a rule, react with water in the
presence of H+ or OH– and a specific SCA to the corresponding precipitates. For multi-
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component systems, diphasic systems, e.g. micro-emulsions, are preferred. After
precipitation, separation processes like centrifugation or filtration follow, after changing the
zeta-potential to obtain weak and reversible aggregation. After precipitation, a composition
like Y–ZrO2 is only poorly crystallized. By employing the hydro - or solvo - thermal
process fully crystallized nano-particles of about 10 nm in diameter are obtained. The
surface modifiers fulfill several requirements : They not only control nucleation and growth,
they also prevent the agglomeration and they provide a desired surface chemistry for further
processing. Diketones are suitable for surface modification. The surface chemistry
employed is basically not different from the well-known chemistry taking place on all types
of solid surface with reactive molecules.
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consisting of a well-ordered core, a less ordered shell and an organic thin cover layer. The
coatings made from these particles show very interesting properties with respect to
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densification. The ‘construction principle’ of this type of new material is shown in
Fig. 2.5.3.
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Fig. 2.5.3 : Structural model of a nanomer type of inorganic - organic nanocomposite
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The assumption is made that the organic layer is able to reduce the particle to particle
interaction and to allow a ‘gliding’ of one particle on the others surface. It is expected that a
denser packing than with uncoated particles is obtained. Gels or layers prepared from
unmodified sols, in general, are porous due to the brittleness of the structure. In addition to
the surface chemistry, the surface modifiers also may be used to tailor the surface charge of
the particles. In this case, the modifiers have to be ionic, e.g.by use of amino groupings.
The surface charges are, for example, measured by acoustophoretic measurement, which is
a very fast analytical method monitoring the surface charge. Since the surface charge, in
general, is dependent on pH, the zeta potential (indicating the quantity of surface charges),
as a rule, is measured as a function of the pH. www.EasyEngineering.net
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and the ability to prepare them would open a route to structures comparable in size (and
perhaps complementary in function) to those that can be prepared by microlithography and
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other techniques of microfabrication.
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The four strategies now followed in the synthesis of large molecules and assemblies :
(i) Controlled formation of covalent bonds, (ii) Covalent polymerization, (iii) Self-
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organization and (iv) Molecular self-assembly. The fourth strategy used in synthesis and
the one most relevant to nanostructures, is molecular self-assembly: that is, the spontaneous
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assembly of molecules into structured, stable, non-covalently joined aggregates. Molecular
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self-assembly combines features of each of the preceding strategies to make large,
structurally well-defined assemblies of atoms: (i) Formation of well-defined molecules of
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intermediate structural complexity through sequential covalent synthesis; (ii) Formation of
large, stable structurally defined aggregates of these molecules through hydrogen bonds,
van der Waals interactions, or other non-covalent links; and (iii) Use of multiple copies of
one or several of the constituent molecules, or of a polymer, to simplify the synthetic task.
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The key to this type of synthesis is to understand and control the non-covalent connections
between molecules and to understand and overcome the intrinsically unfavorable entropy
involved in bringing many molecules together in a single aggregate. For the final assembly
to be stable and to have well-defined shape, the non-covalent connections between
molecules must collectively be stable. The strengths (30) of individual van der Waals
interactions and hydrogen bonds are weak (0.1 to 5 kcal/mol) relative to typical covalent
bonds (40 to 100 kcal/mol) and comparable to thermal energies (RT = 0.6 kcal/mol at
300 K). Thus, to achieve acceptable stability, molecules in self-assembled aggregates must
be joined by many of these weak non-covalent interactions (that is, large complementary
areas of molecular surface in interacting pairs of molecules must be in van der Waals
contact) or by multiple hydrogen bonds, or both. Moreover, these interactions between
molecules or parts of molecules must be more favorable www.EasyEngineering.net
energetically than competing
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Fundamentals of Nanoscience (2 - 11) General Methods of Preparation
interactions with solvent and must be able to overwhelm the entropic advantages of
disintegration of the ordered aggregate into a disordered or dissociated state. Biology is
replete with examples of complex, nanoscale structures formed by self-assembly and living
systems have mastered the art of summing many weak interactions between chemical
entities to make large ones. Chemists are just beginning to learn this art.
Some principles of self-assembly : The single feature common to all of the biological
structures is the reliance upon non-covalent self-assembly of preformed and well-defined
subassemblies to obtain the final structure, rather than the creation of a single, large,
covalently linked structure. Biological self-assembly can thus be described by a series of
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principles that are often (but not always) obeyed :
1) Self-assembly involves association by many weak, reversible interactions to obtain a
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final structure that represents a thermodynamic minimum. In correct structural units are
rejected in the dynamic, equilibrium assembly. This equilibration allows high fidelity in
the process.
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2) Self-assembly occurs by a modular process. The formation of stable subassemblies by
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sequential covalent processes precedes their assembly into the final structure. This
mechanism allows for efficient assembly from the preformed units [a "convergent
synthesis," in the terms of organic chemistry].
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3) Only a small number of types of molecules are normally involved in modular self-
assembly. Consequently, a limited set of binding interactions is required to cause the
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final structure to form. This principle minimize the amount of information required for a
particular structure.
4) Self-assembly often displays positive cooperativity.
5) Complementarity in molecular shape provides the foundation for the association
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between components. Shape-dependent association based on van der Waals and
hydrophobic interactions can be made more specific and stronger by hydrogen bonding
and electrostatic interactions.
To summarize these observations, biological self-assembly requires only the information
embodied in the shape, surface properties and deformability of a limited number of
molecular precursors. The association between these precursor molecules involves non-
covalent interactions and generates a structure that is a thermodynamic minimum. This
aggregate of molecules is stabilized by contacts between molecular surfaces of
complementary shape; the stabilizing interactions are distributed over a large number of
individually weak interactions, rather than concentrated in a small number of strong
covalent bonds. www.EasyEngineering.net
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o Glass slide surface modification
o DNA and oligonucleotide adhesion
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o Vapor vs wet deposition.
Vapor phase deposition has supplanted outdated wet methods of coating surfaces with
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silanes. While surface modification with silanes is an important surface functionalization
method due to the range of functional groups introduced through these reagents, the wet
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process is often difficult to control and results are inconsistent. The main problem with wet
processing, or solution phase deposition, is this process typically uses water. Use of water
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causes slow condensation (polymerization) of silane molecules, so the deposition solution
is constantly changing. This creates a challenge for process control.
The Vapor Phase Deposition Process
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In recent years, vapor deposition has become the preferred method for coating surfaces with
silanes. YES coating systems like the VertaCoat and EcoCoat control the functionalization
process so results are precisely reproducible, run-to-run.
Complete dehydration followed by vapor deposition coating provides a superior
silane/substrate bond that is stable after exposure to atmospheric moisture, extending the
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time available between process steps. Chemical usage for the vapor deposition process is
dramatically less than the amount needed for wet application processes, significantly
reducing waste and chemical costs.
Whether you need a slick surface for coating microelectromechanical systems (MEMS) or a
sticky surface for semiconductor fabrication, chemical vapor deposition will provide the
desired surface modification.
2.7.1 MOCVD
Metalorganicvapour-phase epitaxy (MOVPE), also known as organometallic vapour -
phase epitaxy (OMVPE) or metalorganic chemical vapour deposition (MOCVD), is a
chemical vapour deposition method used to produce single - or polycrystalline thin films. It
is a process for growing crystalline layers to create complex semiconductor multilayer
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areas are used for these device applications, deposition techniques are industrially
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employed which ensure a high throughput. The MOVPE meets these needs and is therefore
the preferred deposition technique for industry.
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Accurate control of flow rate, pressure and temperature can ensure stability and
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repeatability.
2. Carrier gas
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“Inert” carrier gas constitutes about 90 % of the gas phase Stringent purity
requirements
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H2 traditionally used, simple to purify by being passed through a palladium foil heated
to 400 C. Problem : H2 is highly explosive in contact with O2 High safety costs.
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Alternative precursor : N2 : safer, recently with similar purity, more effective in cracking
precursor molecules (Heavier).
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High flux Fast change of vapor phase composition. Regulation : Mass flow controller
P ~ 5- 800 mbar mass flow controllers.
3. Material sources et
Volatile precursor molecules transported by the carrier gas
Growth of III-V semiconductors :
Group III : Generally metalorganic molecules (Trimethyl- or triethyl- species)
Group V : Generally toxic hydrides (AsH3; PH3 flammable as well); alternative : Alkyls
(TBAs, TBP).
4. Hydrides and dopants
Form : Gases from high pressure cylinders
Mixed into the carrier gas line
Flow control : Valve + Mass Flow Controller (MFC)
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Fig. 2.7.2
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5. Metalorganics
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Liquid (or finely divided solid – TMIn) contained in a stainless steel bubbler.
Vapor pressure fixed by constant temperature in a thermal bath; T – 20 C 40 C;
DT = 1 C.
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Controlled H2 flow through the bubbler saturated stream; composition depends on H2
flow rate adjustment through MFC.
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Pressure Controller (PC) to keep a fixed pressure in the bubbler and throttles the
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resulting mixture of H2 and MO down to the reactor pressure. PC MFC valve NC valve
NO H2, N2 to reactor bubbler thermal bath bubblers.
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Fig. 2.7.3
6. Metalorganic compounds
Optimal thermal decomposition temperature between 300 and 500 C Availability of
transported reactant at the substrate surface.
The vapor pressure of the MO source is an important consideration in MOCVD, since it
determines the concentration of source material in the reactor and the deposition rate.
Too low a vapor pressure makes it difficult to transport the source into the deposition
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zone and to achieve reasonable growth rates. Too high a vapor pressure may raise safety
concerns if the compound is toxic.
Vapor pressures of Metalorganic compounds are calculated in terms of the expression
Log(p) = B – A / T.
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Evaporation and sputtering.
2.8.1 Evaporation
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In evaporation, the source is placed in a small container with tapered walls, called a
crucible and heated up to a temperature at which evaporation occurs. Various techniques
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are utilized to reach the high temperatures needed, including the induction of high currents
with coils wound around the crucible and the bombardment of the material surface with an
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electron beam (e-beam evaporators). This process is mainly used to deposit metals,
although dielectrics can also be evaporated. In a typical system, the crucible is located at
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the bottom of a vacuum chamber, whereas the wafers are placed lining the dome-shaped
ceiling of the chamber, Fig. 2.8.1 (a). The main characteristic of this process is very poor
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step coverage, including shadow effects, as illustrated in Fig. 2.8.1 (b). As will be explained
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in subsequent sections, some micro fabrication techniques utilize these effects to pattern the
deposited layer. One way to improve the step coverage is by rotating and/or heating the
wafers during the deposition.
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Fig. 2.8.1 (a) : Schematic representation of an electron-beam deposition system
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Fundamentals of Nanoscience (2 - 17) General Methods of Preparation
Fig. 2.8.1 (b) : Shadow effects observed in evaporated films. Arrows show the trajectory
of the material atoms being deposited
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2.8.2 Sputtering
Sputtering is a process whereby atoms are ejected from a solid target material due to
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bombardment of the target by energetic particles. It only happens when the kinetic energy
of the incoming particles is much higher than conventional thermal energies (≫ 1 eV).
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Fig. 2.8.2
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Both evaporation and sputtering systems are often capable of depositing more than one
material simultaneously or sequentially. This capability is very useful in obtaining alloys
and multilayers (e.g., multilayer magnetic recording heads are sputtered). For certain low
reactivity metals such as Au and Pt, the previous deposition of a thin layer of another metal
is needed to improve the adhesion. Ti and Cr are two frequently used adhesion promoters.
Stress in evaporated or sputtered layers is typically tensile. The deposition rates are much
higher than most CVD techniques. However, due to stress accumulation and cracking, a
thickness beyond 2 m is rarely deposited with these processes. For thicker depositions a
technique described in the next section is sometimes used.
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Fig. 2.8.3 : Typical cross section evolution of a trench while being filled with sputter
deposition
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Types of sputtering
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DC sputtering,
Radio frequency sputtering magnetron sputtering
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High pressure oxygen sputtering facing target sputtering.
Magnetron sputtering
Magnetron sputtering involves the creation of a plasma by the application of a large DC
potential between two parallel plates (Fig. 2.8.4). A static magnetic field is applied near a
sputtering target and confines the plasma to the vicinity of the target. Ions from the high-
density plasma sputter material, predominantly in the form of neutral atoms, from the target
onto a substrate. A further benefit of the magnetic field is that it prevents secondary
electrons produced by the target from impinging on the substrate and causing heating or
damage. The deposition rates produced by magnetrons are high enough (1 mm/min) to be
industrially viable; multiple targets can be rotated so as to produce a multilayered coating
on the substrate. www.EasyEngineering.net
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Fig. 2.8.4 : Schematic diagram of a DC glow discharge apparatus in which gas atoms
are ionized by an electron filament and either deposit on a substrate or cause sputtering
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Fig. 2.8.5 : Schematic diagram of a magnetron sputtering that uses a magnetic field to
contain ionized gas molecules close to a sputtering target, giving large deposition rates et
Ions and their interaction with matter :
In comparison with electrons, ions are relatively heavy, negatively or positively charged
particles and various effects occur upon their interaction with matter. These include ion
backscattering (Rutherford backscattering spectrometry), the excitation of electrons and
photons, X-ray Bremsstrahlung, the displacement of atoms and sputtering, as well as the
possible implantation of ions within the surface of the material. The latter is extensively
used for doping semiconductors.
Advantages :
No container contamination will occur.
It is also possible to deposit alloy films which retain the composition of the parent target
material. www.EasyEngineering.net
Uses of Sputtering :
Sputtering is used extensively in the semiconductor industry to deposit thin films of
various materials in integrated circuit processing.
Thin antireflection coatings on glass for optical applications.
Ideal method to deposit contact metals for thin-film transistors because of the low
substrate temperatures used.
Low-emissivity coatings on glass, used in double-pane window assemblies. The coating
wwis a multilayer containing silver and metal oxides such as zinc oxide, tinoxide, or
titanium dioxide.
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A large industry has developed around tool bit coating using sputtered nitrides, such as
titanium nitride, creating the familiar gold colored hardcoat.
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Sputtering is also used as the process to deposit the metal (e.g. aluminium) layer during
the fabrication of CDs and DVDs.
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Hard disk surfaces use sputtered CrOx and other sputtered materials.
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Sputtering is one of the main processes of manufacturing optical waveguides and is
another way for making efficient photovoltaic solar cells.
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Fig. 2.9.1 : Schematic of an MBE chamber
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magnetic manipulator which can be rotated during growth. K-cells are attached to the
bottom of the chamber, pointing towards the substrate. Selective opening of shutters on
each K-cell ensures the growth using only specific elements. Characterization of substrate
and the thin-film is continuously monitored during growth and is performed by RHEED.
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Molecular Beam Epitaxy (MBE) is an experimental technique utilized for layer-by-layer
growth of thin films of various quantum materials. Out of the variety of thin film growth
techniques available, MBE is considered to be one of the cleanest, but also one of the most
technically challenging and demanding, as MBE growth takes place in ultra-high vacuum
(UHV) environment.
Typical MBE experimental setup consists of two or more Knudsen effusion cells (K-cells),
located at the bottom of a UHV chamber and aligned towards the center of the chamber
where a sample holder with a substrate is located (Fig. 2.9.1). Each individual K-cell
contains a different element in ultra pure solid form (i.e. elemental 99.999 % Selenium,
Bismuth, etc.) which can be used in the thin film synthesis. The process of MBE growth
starts by heating the K-cells to appropriate temperatures until the elements in each cell
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reach a sublimation point. Then, the shutters are opened and physical vapor from each K-
cell diffuses though the chamber until it reaches the substrate where it gets deposited and
the thin film gets formed. The final composition and stoichiometry of the film will depend
on the temperature and surface atomic structure of the substrate, as well as the flux ratios of
individual components reaching the substrate. For more uniform growth, substrate can be
continuously rotated at low rotation speeds (~1-2 rotations per minute) by utilizing a
stepper motor attached to the magnetic manipulator.
To characterize the samples in-situ during growth, we use Reflection High-Energy Electron
Diffraction (RHEED). Electrons emitted from the RHEED gun (Fig. 2.9.1) incident at a
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very low angle with respect to the sample surface are diffracted and the resulting diffraction
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pattern is observed on the screen. This pattern can reveal : (1) Quality of the film surface
and (2) Film thickness down to a single monolayer.
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Advantages and disadvantages
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Why use MBE rather than some other method making a crystal ?
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It's particularly good for making high-quality (Low-defect, highly uniform) semiconductor
crystals from compounds or from a number of different elements, instead of from a single
element.
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It also allows extremely thin films to be fabricated in a very precise, carefully controlled
way. rin
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Unfortunately, it does have some drawbacks too. It's a slow and laborious method (Crystal
growth rate is typically a few microns per hour), which means it's more suited for scientific
research laboratories than high-volume production and the equipment involved is complex
and very expensive (partly because of the difficulty of achieving such clean, high-vacuum
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conditions).
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Fig. 2.10.1
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Compared to basic chemical vapour deposition, in ALE (ALD), chemical reactants are
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pulsed alternatively in a reaction chamber and then chemisorb in a saturating manner on the
surface of the substrate, forming a chemisorbed monolayer.
o ALD (Atomic Layer Deposition) g.n
o Deposition method by which precursor gases or vapors are alternately pulsed on to the
substrate surface.
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o Precursor gases introduced on to the substrate surface will chemisorb or surface reaction
takes place at the surface
o Surface reactions on ALD are complementarity and self-limiting
MOMBE :
Epitaxial growth of Hg-based semiconductors by Molecular Beam Epitaxy (MBE) and
Metalorganic MBE (MOMBE) has progressed sufficiently to shift emphasis to the control
of factors limiting the yield of both materials and devices. This paper reports on an ex-situ
study to evaluate the suitability of reflectance and photoreflectance (PR) as in-situ
characterization techniques for the growth of CdTe and HgCdTe. Photoreflectance yields
information about CdTe layers, with largest utility for doped and multi-layer structures.
However, caution must be taken in interpretation of the spectra since the near-bandedge PR
spectra consists of multiple transitions and the E1 transition energy is very sensitive to the
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sample history. Photoreflectance appears to be of limited utility for HgCdTe single layer
growth with x < 0.4. However, reflectance measurements of the E1 peak can be used to
determine composition in HgCdTe single layers with an accuracy x = 0.01, which can be
useful for growth control. A tight binding model was used to calculate the E1 peak energy
as a function of bandgap for HgCdTe and HgTe/CdTe super lattices. Comparisons are made
with experimental observations. Surface inter diffusion in HgTe-CdTesuperlattices was
probed using reflectance measurements.
MOMBE system the growth experiments of nitride semiconductors were carried out in a
compact MOMBE system, originally designed for growth of III-V semiconductor
compounds like InGaAs, InGaAsP, etc. Fig. 2.10.2 presents a schematic view of the growth
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chamber. For the growth of nitride based semiconductors a number of modifications to the
original system have been performed of which two were critical in obtaining a reliable
operation.
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Fig. 2.10.2 : Schematic view of the MOMBE growth chamber
The sample heater is one of those critical components because of the high temperature
required in nitride growth that can reach 950 C for relatively long periods of time. Priority
has been given to the replacement of Mo fixture parts with more reliable ones that would
sustain high temperature operation without generating contamination problems. At the same
time they had to allow repeated assembly-disassembly operations associated with the heater
maintenance. Heater energy exchange with the base plate and the surroundings had been
reduced by the use of layered thermal insulators and by providing adequate shielding.
Ultimately, the heating element itself has been designed and redesigned until the reliability
issues have been resolved.
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important methods for the synthesis of composites containing two or more kinds of metal
elements
Q.2
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Define sputtering and list its types.
Ans. : Sputtering (sputter deposition) is a method used to create thin films and is a type
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of physical vapor deposition. Unlike some other vapor deposition methods, the material does
not melt. Instead, atoms from the source material (target) are ejected by momentum transfer
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from a bombarding particle, typically a gaseous ion.
DC diode sputtering.
RF sputtering nee
DC triode sputtering
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Reactive sputtering
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Q.3
Ans. :
What do you meant by Ultra sonication ?
Ultra sonication is a well-established mechanical technology for sludge
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disintegration. Ultrasound waves cause the periodical compression and rarefaction when
propagating through the medium. The micro bubbles formed during this process violently
collapse within a few microseconds after reaching a critical size, inducing the occurrence of
cavitation. The sudden and violent collapse leads to extreme conditions (a local temperature
of around 5000 K and a pressure above 500 bars) and initiates powerful hydro-mechanical
shear forces and highly reactive radicals (Hand OH). Both the hydro mechanical shear forces
and the oxidizing effect of H and OH contribute to the break-up of sludge flocs and the
liberation of intercellular material. In comparison, hydro-mechanical shear forces,
nonetheless, are stronger in sludge rupture than radicals.
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Ans. : Carbon nanotubes mainly classified into two types. They are,
1. Single walled nanotubes
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2. Multi walled nanotubes other related structures :
Torus
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Graphenated carbon nanotubes (G-CNTS)
Nitrogen doped carbon nanotubes (n-CNTS)
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Q.6 Differentiate carbon nanotubes from bucky balls. rin
Ans. :
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Fullerene - It has all the 3 dimensions in nanoscale range and has a soccer ball like
shape. It is also called Bucky ball. et
Carbon nanotubes - It is a hollow cynlindrical structure whose only 1 dimension is in
nanometer range which is its diameter. Other dimensions are in micrometers.
Q.7 Give a brief note on applications of nanoclays.
Ans. : Nanoclay is used in the ink formulation :
It helps to adjust the consistency of printing inks to the desired value, avoiding pigment
sedimentation, providing good colour distribution, obtaining desired film thickness,
etc. by incorporation of small amount of organically modified layered silicate.
Thickening lubricating oils with nanoclays can produce especially high temperature
resistant lubricating greases.
The performance of cosmetics is enhanced by the use of nanoclays and they allow
good colour retention and coverage for nail lacquers, lipsticks and eye shadows.
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Waste water treatment : The use of nanoclays in wastewater treatment has become
common in industry today. Nanoclays exhibit a synergistic effect with many
commonly utilized water treatment unit processes including granular-activated
charcoal, reverse osmosis, and air strippers. Granular-activated carbon is particularly
effective at removing a large range of organic molecules from water, however, is very
poor for removing large molecules such as humic acid and wastewaters containing
emulsified oil and grease. Nanoclays have proven to be the technology of choice for
treating oily wastewaters
Nanoclay as drug vehicle : Nanoclays as drug vehicle for controlled release of drug is
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one of the born age area in medicinal application, nanoclays have great potential as
compared to polymer and carbon nanotubes for drug delivery applications.
Q.8
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List the application of self-assembly materials.
Ans. : A variety of applications where the self-assembly of nanoparticles might be
useful :
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1. Building sensors or computer chips
2. Nano electronics and bioelectronics
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Q.9
3. Biological applications - drug delivery
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Examine various polymeric materials in nano precipitation.
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Ans. : Polymeric nanoparticles are nanosized solid particles that consist of natural or
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synthetic polymers. Two types of nanoparticles can be distinguished: (1) nanospheres, which
are matrix systems where the drug is uniformly dispersed; and (2) nanocapsules, which are
reservoir systems where the drug is located in the core surrounded by a polymer membrane.
Depending on the method of preparation, the drugs are either physically entrapped within
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the nanoparticles or covalently conjugated or adsorbed to the constitutive polymers of the
polymer matrix.
Q.10 Explain the use of ball milling in nanotechnology.
Ans. :
1. Ball milling is a method of production of nano materials.
2. This process is used in producing metallic and ceramic nano materials.
3. These mills are equipped with grinding media composed of wolfram carbide or steel.
4. Ball mills rotate around a horizontal axis, partially filled with the material to be ground
plus the grinding medium.
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Q.5 Write in detail about the sputtering and its types. (Refer section 2.8)
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