PHYS350

Introduction to Nanophysics
Topic 4

Nanostructures (Bottom Up): Synthesis

Dr. Dalaver H. Anjum, Assistant Professor

Department of Physics
Khalifa University, Abu Dhabi

Disclaimer: Pictures used in the Lecture are taken from Reference Books and Web
Bottom-Up Approach: Synthesis
• Bottom-up approaches are the production of nanoparticles starting from atoms
using basically the chemical processes based on transformations in gas, or
liquid form.

• The most common techniques include:

• Chemical vapor deposition (CVD)
• Wet Chemical Methods (WCM)
• Chemical vapor condensation (CVC)
• Plasma or flame spraying synthesis
• Laser pyrolysis precipitation
• Sol–gel
• Biomimetics Approaches
Chemical vapor deposition (CVD)

Schematic representation of chemical vapor deposition: (a) thermal and (b) plasma assisted.

• CVD methods of gas-phase synthesis allow an elegant way to control process parameters
in order to be able to produce desired size, shape, and chemical composition-controlled
nanostructures.
• Multicomponent systems are relatively easy to prepare using CVD methods.
• Most of the synthesis routes are based on the production of small clusters that can
aggregate to form nanoparticles (condensation).
• Condensation occurs only when the vapor is supersaturated, and in these processes,
homogeneous nucleation in the gas phase is utilized to form particles.
CVD Reactor Details: Example GaN
Chemical vapor deposition (CVD)

• The process is often used in the semiconductor industry to produce thin

films.

• In typical CVD, the wafer (substrate) is exposed to one or more volatile

precursors.

• Precursors then decompose on the substrate surface to produce the

desired deposit.

• As a result of chemical reactions, volatile by-products are also

produced, which are removed by gas flow through the reaction chamber.

• Microfabrication processes widely use CVD to deposit materials in

various forms including monocrystalline, polycrystalline, amorphous,
and epitaxial.
Primary Nucleation Types

Primary nucleation plays a fundamental role in CVD.

Primary Nucleation Types

• Heterogeneous nucleation is more favored than homogeneous one.

• ΔG is Gibbs Free Energy
Homogeneous Nucleation

and
Heterogeneous Nucleation
Heterogeneous Nucleation

and
Heterogeneous Nucleation
Fully Wetting No Wetting

θ = 0º

Fully wetting of the surface, No wetting of the surface,

and nucleation catalyzed by and thus no catalysis by the
the surface. This means, no surface. This means, the case
barrier at the surface for is falling back into
nucleation homogeneous nucleation
Examples of Materials for CVD
• The following materials (but not limited) include:
• Silicon (Si)
• Carbon fibers, nanofibers, & nanotubes
• Silicon Oxide (SiO2)
• Silicon-germanium (Si-Ge)
• Tungsten (W)
• Silicon carbide (SiC), silicon nitride (SiNx), silicon oxynitride (SiOxNy),
• Titanium nitride (TiN)
• Synthetic diamonds.

• CVD is commonly used to deposit conformal films. A variety of applications

for such film exist.
• Gallium arsenide is used in some ICs and photovoltaic devices.
• Amorphous polysilicon is used in photovoltaic devices.
• Certain carbides and nitrides confer wear-resistance.
1: CVD of polysilicon (p-Si)
• Polycrystalline silicon is deposited from following precursors
• Trichlorosilane (SiHCl3)
• Silane (SiH4)

Chemical Reactions:
SiH3Cl → Si + H2 + HCl
SiH4 → Si + 2H2

• These reactions are usually performed in Low Pressure CVD

(LPCVD) systems with pure precursors carried by inert gases
such as Argon (Ar).

• Temperatures between 600 and 650 ºC

• Pressures between 25 and 150 Pa typically yield a growth rate

between 10 and 20 nm per minute.
2: CVD of Silicon Dioxide (SiO2)
• Silicon Dioxide (SiO2) is deposited from following Si precursors
• Silane (SiH4) & Oxygen
• Dichlorosilane (SiCl2H2) & Nitrous Oxide (N2O)
• Tetraethylorthosilicate (TEOS; Si(OC2H5)4)

• Chemical Reactions:
SiH4 + O2 → SiO2 + 2H2
SiCl2H2 + 2N2O → SiO2 + 2N2 + 2HCl
Si(OC2H5)4 → SiO2 + by-products

• Substrate temperature for the deposition for:

• Silane between 300 and 500 ºC
• Dichlorosilane at around 900 ºC
• TEOS between 650 ºC
3: CVD of Silicon Nitride (SiNx)
• Silicon Nitride (SiNx) is deposited from following Si precursors
• Silane (SiH4) & Ammonia (NH3) or Nitrogen (N2)
• Dichlorosilane (SiH2Cl2) & Ammonia (NH3 )

• Chemical Reactions:
3SiH4 + 4NH3 → Si3N4 + 12H2
3SiCl2H2 + 4NH3 → Si3N4 + 6HCl + 6H2

• Silicon nitride deposited by LPCVD contains up to 8% hydrogen.

• It also experiences strong tensile stress, which may crack film thicker than
200 nm.
• However, it has higher resistivity and dielectric strength than most
insulators commonly available in microfabrication (i.e. 1016 Ω-cm and 10
MV/cm, respectively)
4: CVD of Metals
• CVD of metals have different precursors. For Example:
• For Tungsten (W) metal, hexafluorid (WF6) & with or without Hydrogen (H2)
• For Aluminum (Al) can be deposited from triisobutylaluminum (TIBAL)
• For Molybdenum (Mo), tantalum (Ta), titanium (Ti), and nickel (Ni) is widely
pentachlorides (MCl5) with Hydrogen (H2). Or, metal carbonyl (M(CO)n)
without Hydrogen (H2)

• Chemical Reactions:
2MCl5 + 5H2 → 2M + 10HCl
M(CO)n → M + nCO
Wet Chemical Methods (WCM)

• Wet chemical methods are the most exploited bottom-up

approach for the synthesis of a variety of nanomaterials.

• Several methods included under this category that can be

discussed including the following:

• Exchange Reactions
• Chemical Reduction Method
WCM: Exchange Reactions
WCM: Exchange Reactions
• The exchange reactions leading to the precipitation of solids from a
solution with metal ions are one of the most common processes to
produce nanomaterials.

• In supersaturated solutions, particles are formed via homogeneous or

heterogeneous nucleation.

• The growth of particles usually occurs via diffusion or Ostwald ripening.

Particle size and particle size distribution, crystallinity, as well as
morphology are controlled by applying the reaction kinetics.

• Important parameters are concentration, temperature, pH of the solution,

order of adding the reactants, and mixing processes.
WCM: Exchange Reactions, examples
1: Synthesis of metal chalcogenides

• Chalcogen is added to the metal precursor solution in a hot

coordinating solvent.

• CdE (E=S, Se or Te) NPs:

• Chalcogen is added to the Cd precursor (dimethyl Cd, Cd oxide,
carbonate, or acetate) in a hot coordinating solvent (e.g., tri-n-
octylphosphine oxide, TOPO).
• High temperature is maintained for fast particle nucleation followed
by lowering the temperature for slow particle growth.

• Doped ZnS NPs:

• ZnS nanophosphors doped with halides
• Cu+ halides, Cu+, Al3+, and Mn2+can be prepared by the colloidal
precipitation method at room temperature.
WCM: Exchange Reactions, examples
2: Preparation of iron oxide NPs by exchange reaction
• In a typical synthesis, a source of iron is prepared by dissolving:
• 0.02 M FeCl3 in 250 ml water
• 0.01 M Fe2SO4 in 250 ml water.
• Appropriate amount of coating material is added to the source of iron
solution.
• The co-precipitation of Superparamagnetic iron oxide nanoparticles
(SPION) was carried out in a reaction with magnetic stirring, by slowly
adding 5 M NaOH until obtaining pH 9–10 at room temperature.
• The resulting solution was kept for 1 h to complete the reaction.
• Then the precipitate was magnetically separated from the supernatant
and washed several times with distilled water, until obtaining pH 7
• During each washing step, samples were separated from the
supernatant using a permanent magnet.
• Thoroughly washed magnetic particles were dried at room temperature,
yielding a fin powder.
WCM: Exchange Reactions, examples
2: Preparation of iron oxide NPs by exchange reaction

Preparation of Fe2O3. Shukla et al. [15] © 2010. With permission of ASPBS.

WCM: Ostwald Ripening Process
WCM: Ostwald Ripening Process
WCM: Ostwald Ripening Process
WCM: Reaction Kinetics
WCM: Reaction Kinetics
WCM: Reaction Kinetics
WCM: Reaction Kinetics
WCM: Reaction Kinetics
WCM: Reaction Kinetics
WCM: Reaction Kinetics
WCM: Reaction Kinetics
WCM: Reaction Kinetics
WCM: Chemical Reduction Methods
The chemical reduction method consists of three
essential stages, namely:
• the reduction of metallic salts by reducing agents

• stabilization of the ionic complexes

• controlling of the size by the capping agent.

Many different types of metallic nanoparticles have been

synthesized using this method.
WCM: Chemical Reduction Methods
Chemical reduction of metal salts is the most common method for the
synthesis of nanoparticles and has the potential to be scaled up even at room
temperature.

Schematic representation of chemical reduction method for nanosynthesis.

WCM: Chemical Reduction Methods

Schematic representation different capping agents (a) polymer; (b) organic

ligand, and (c) micelle.

• Reducing agents:
• ascorbic acid, citric acids, and their salts; alkali hydrides namely
NaBH4, NaB(C2H5)3H, and LiB(C2H5) 3H

• Capping agents:
• polymers, for example, polyvinylpyrrolidone; organic ligand (e.g.
quaternary amines, thiols; and surfactants)
WCM: Chemical Reduction Methods, examples

1: Preparation of silver nanoparticles

• In a typical synthesis, 0.85 g
of AgNO3 (Salt) was
dissolved in 100 ml of
aqueous solution of 0.85
wt% polyethyleneimine
(PEI, Mw 600,000–
1,000,000) (Capping)
• Homogenized by stirring for
2 min.
• It is followed by the addition
of 1 ml of 35% solution of
• formaldehyde (reducing)
and mixing the resultant
solution well.
• Light yellow color appeared
after 2 min, indicating the
nucleation and growth of Ag
NPs
Preparation of Ag NPs by reduction method. Manoth et al. [16] © 2008.
WCM: Chemical Reduction Methods, examples

2: Preparation of gold nanoparticles

• One of the most simple and reproducible methods to synthesize Au nanorods is
the seed-mediated growth method. It consists of a two-step process, that is,
nucleation and then successive growth of the NPs.
Typical preparation I
I step:
A growth solution is prepared by the mild reduction of Au ions (HAuCl4, 0.001 M) with l-
ascorbic acid (0.0778 M) in the presence of AgNO3 (0.04 M), which promotes
anisotropy in the presence of hexadecyltrimethylammonium bromide (CTAB, 0.2 M)
and benzyldimethylhexadecylammonium chloride (BDAC, 0.15 M) as surfactants.

II step:
The seed solution is prepared afterward by the rapid reduction of the Au precursor with
a strong reducing agent (NaBH4, 0.010 M) in the presence of CTAB (0.20 M) as a
surfactant.

• By introducing some modification in experimental conditions (e.g., solution

temperature, stirring rate, ratio of seed to metal salt), it is possible to obtain a define
aspect ratio of the Au nanorods.
WCM: Chemical Reduction Methods, examples

2: Preparation of gold nanoparticles

Typical preparation II
Step I:
• Aqueous solution of Au (HAuCl4, 0.001 M) is mixed with
mercaptosuccinic acid (MSA, 0.005 M in methanol) to give a transparent
solution.
Step II:
• Freshly prepared aqueous solution of sodium borohydride (NaBH4,
0.010 M) is then added under vigorous stirring conditions.
• The solution will turn dark brown immediately but remain transparent
(which indicates that the nanoparticles have not yet formed) until
enough reductant was added till a flocculen dark brown precipitate is
generated.
• The pH of the solution increases gradually with the addition of reactant,
and finall the pH of the solution is brought to 8.6.
• The solvent was removed by decantation after the centrifugation. The
precipitate is washed, suspended in ethanol, and dried by rotary
evaporation.
WCM: Chemical Reduction Methods, examples

3: Iron–cobalt (FeCo) nanoparticles

Synthesis of core–shell metal alloy nanoparticles:
• first step involves the synthesis of nanocomposites of mixed metal oxide (FeCo)
at the room temperature in the copolymer matrix of aniline formaldehyde
• second step involves the pyrolysis of as-prepared nanocomposite under inert
atmosphere
Sol–Gel Method: Introduction
• A “sol” is a type of colloid in which a dispersed solid phase is mixed in a
homogeneous liquid medium.

• As the name suggests, the sol–gel process involves the evolution of

networks through the formation of a colloidal suspension (sol) and
gelation of the sol to form a network in a continuous liquid phase (gel).

• The sol–gel technique is a long-established industrial process for the generation

of colloidal nanoparticles from liquid phase that has been further developed in
previous years to produce advanced nanomaterials and coatings.

• Sol–gel processes are well adapted for oxide nanoparticles and composites
nanopowders synthesis.

• The main advantages of sol–gel techniques for the preparation of materials are
low temperature of processing, versatility, and flexible rheology allowing easy
shaping and embedding.

• They offer unique opportunities for access to organic–inorganic materials

Sol–Gel Method: Precursors
• The precursors are usually ions of a metal.
• Metal alkoxide and alkoxysilane are the most popular since they
react readily with water (hydrolysis).

• The most widely used alkoxysilanes are tetramethoxysilane

(TMOS) and tetraethoxysilane (TEOS), which form silica gels
Alkoxides such as aluminates, titanates, and borates are also used,
often mixed with TMOS or TEOS.

• In addition, since alkoxides and water are immiscible, a mutual

solvent is used such as an alcohol.
Sol–Gel Method: Process
• The sol–gel process involves the evolution of inorganic networks through the
formation of a colloidal suspension (sol) and gelation of the sol to form a
network in a continuous liquid phase (gel).

• The precursors for synthesizing these colloids consist usually of a metal or

metalloid element surrounded by various reactive ligands.

• The starting material is processed to form a dispersible oxide and forms a sol in
contact with water or dilute acid. Removal of the liquid from the sol yields the
gel, and the sol–gel transition controls the particle size and shape.

• Calcination of the gel produces the oxide. Sol–gel processing refers to the
hydrolysis and condensation of alkoxide-based precursors such as Si(OEt)4
(tetraethyl orthosilicate).

• The reactions involved in the sol–gel chemistry based on the hydrolysis and
condensation of metal alkoxides M(OR)z can be described as follows:
MOR + H2O → MOH + ROH (hydrolysis)
MOH + ROM → M − O − M + ROH (condensation)
Sol–Gel Method: Hydrolysis
Sol–Gel Method: 4 Steps-Involved
1. Formation of stable solutions (sol) of alkoxide or solvated metal
precursor by hydrolysis reaction, in which the –OR group is replaced with
an –OH group. The hydrolysis reaction can occur without a catalyst but is
more rapid and complete when catalysts (e.g., base NaOH, NH3 or acid
HF,CH3COOH) are used.

2. After hydrolysis, the sol starts to condense and polymerize (gel). This
leads to a growth of particles to dimensions of a few nanometers.
Gelation resulting from the formation of an oxide- or alcohol- bridged
networks by a polycondensation reaction results in a dramatic increase in
the viscosity of the solution.
Sol–Gel Method: 4 Steps-Involved
1. Syneresis, the aging of the gel during which the polycondensation
reactions continue until the gel transforms into a solid mass, is
accompanied by the contraction of the gel network and expulsion of the
solvent from gel pores. Ostwald ripening (also referred to as coarsening
is the phenomenon by which smaller particles are consumed by larger
particles during the growth process) and phase transformations may
occur concurrently with syneresis. The aging process of gels can exceed
7 days and is critical to the prevention of cracks in gels.

2. Drying of the gel, when water and other volatile liquids are removed from
the gel network. If the solvent (such as water) is extracted under
supercritical or near supercritical conditions, the product is an aerogel.
Gels are stabilized by dehydration, during which surface-bound M-OH
groups are removed. This is usually achieved by calcining the monolith
at temperatures up to 800 ∘C.

Syneresis or weeping is the process in which gel shrinks and looses the
entire liquid present inside it after standing for a long time.
Sol–Gel Method: Schematic

Schematic representation of sol–gel process for the synthesis of a variety of nanostructures.

Hench and West [19] © 1990.
Biomimetic Approaches
• The limitation of bottom-up approach for nanosynthesis is the lack of a
general scheme for the creation and assembly of nanomaterials.
• On the other hand, through millions of years of evolution, Nature has
selected organisms that can create diversifie inorganic material
structures in nano- or microscale, which is known as biomineralization.
• Examples include calcification and silificatio found in diatoms, and the
formation of magnetite crystals in magnetotactic bacteria, as shown in
Figure a.
• These organisms are capable of organizing nanoscale building blocks
into large-scale hierarchical structures (Figure b) to form hard tissues
serving different functions such as mechanical support, filtration light
harvesting, gravity sensing, and locomotion.

Scanning electron micrograph (SEM): (a)

magnetotactic bacteria (Magnetospirillum
gryphiswaldense) cell; (b) magnetite crystals
observed at the ends of the chain in
magnetotactic bacteria. Bazylinski and Frankel
[23] © 2004
Extracellular Bionanosynthesis of Nanoparticles
Extracellular Bionanosynthesis of Nanoparticles
Extracellular Bionanosynthesis of Nanoparticles
Extracellular Bionanosynthesis of Nanoparticles
Extracellular Bionanosynthesis of Nanoparticles
An Example
• Bacteria Microorganisms are considered as a potential biofactory for
the synthesis of nanoparticles such as gold, silver, and cadmium
sulfide.

• Some well-known examples of bacteria synthesizing inorganic

materials include magnetotactic bacteria (synthesizing magnetic
nanoparticles) and S-layer bacteria that produce gypsum and calcium
carbonate layers.

• The mechanisms involve efflux systems, alteration of solubility, and

toxicity via reduction or oxidation, biosorption, bioaccumulation,
extracellular complexation or precipitation of metals, and lack of specifi
metal transport systems.

• For example, Pseudomonas stutzeri AG 259 isolated from silver mines

has been shown to produce silver nanoparticles.
Assignment
Q1: What is plasma-enhanced CVD and how it is different from thermal CVD?
Q2: How does liquid-phase synthesis differs from gas-phase synthesis for the
production of nanoparticles?
Q3: How can you obtain stable gold nanoparticles without adding any stabilizers
or surfactants?
Q4: Enumerate various steps involved in the chemical reduction method for the
synthesis of nanomaterials with suitable example
Q5: Suggest a suitable method for preparing Iron Oxide nanoparticles? Given
reasons for your choice.