Nanomaterial’s Synthesis Processes…

Nanomaterial Toxicity: Things to remember while working with Nanomaterials

ü Understand the physical characteristics and the chemical composition of a nanomaterial before you begin
to work with nanomaterials--a key element of your risk assessment.

ü Comparison of biological / Toxicological data of similar chemicals –When working with hybrid
materials

ü Characterisation information for engineered nanomaterials should be available from manufacturers or

suppliers along with a safety data sheet –Important to keep this information handy

ü Always cover yourself with PPE (Personal protective equipment’s)—To avoid long term consequences !

ü Do not use any powder, ornament, etc. while working with nanomaterials – To avoid unknown chemical
reaction !
 •SEMICONDUCTOR QUANTUM DOTS

v Semiconductor quantum dots (‘nanocrystals’) shows quantum confinement effects

v Quantum size effects are manifested when the length of the nanocrystal made is comparable to the
exciton radius, ‘a’. Bohr exciton radius of CdSe is ~ 56 Å.

v In semiconductor, due to thermal excitations, an electron−hole pair is created, known as an

‘exciton’, which is delocalized throughout the nanocrystals.

v Exciton Bohr radius can be given as: ‘a’ = 4𝜋𝜀𝜖! ℏ2 / e2[1/me + 1/mh],
All symbols shown here have their usual meaning!
Synthesis of Quantum Dots (QDS)
Synthesis in Con,ined Media: nanoparticles are synthesized in a space that is already available.

• Reverse micelles (water in oil) ::

• zeolites
• porous membranes

Ø In reverse micelles (water in oil) method, oil is the majority phase while water is the minority phase, and nanoscopic
containers are formed by micelles.

Ø The oil/ water ratio and the temperature conditions can be adjusted to obtain suitable particle dimensions.

Ø The medium can have capping agents as a result of which the surface prepared is passivated.

What is capping agents?

Why do we need them?

Capping Agents:
• A capping agent is a molecule that stabilizes nanoparticles during synthesis.
• Capping agents are also known as coating agents or surfactants.
• They are used to prevent nanoparticles from growing too large and aggregating.

Ø Cyclodextrins
Ø Polysaccharides Ø Dendrimers
For ex.: poly(propylene imine) (PPI)

The preparation of nanomaterials by organometallic precursors require a capping agent, which primarily acts
as stabilizing agent and provide colloidal stability along with preventing agglomeration and stopping
uncontrolled growth. Final morphology of nanocrystal largely depends on the type of capping agent which is
adsorbed on the surface of nanocrystal. Thus, capping agents are the keys to obtain the small-sized
nanoparticles and are very frequently used in colloidal synthesis of nanoparticles to avoid its overgrowth.
Synthesis of Quantum Dots (QDS) - Reverse micelles (water in oil)
Chemical Synthesis Using Clusters / Molecular Precursors-

The nanocrystals prepared this way can undergo Ostwald ripening (growth of larger particles at the expense of
smaller ones) as a result of which monodisperse particles can be formed.

The solvent universally chosen for this approach is trioctylphosphine oxide ‘OP(C₈H₁₇)₃’ (known as TOPO), which
has high thermal stability and can co-ordinate with inorganic surfaces [i.e., chemical compounds that contain no
carbon (C)].

Cadmium dithiocarbonates (e.g. Cd(S2CNEt2)2) can produce CdS nanocrystals.

• Zeolites
Ø In confined cages such as those of zeolites, the maximum dimension of the particle formed is fixed (1 – 10Å).

Ø In above approach, the Na+ is exchangeable ions with Cd2+ by washing the zeolite with a Cd2+ solution.

Ø When exposed to H2S gas. Depending on the extent of Cd2+ present in the sample, various nanoparticle (CdS) sizes
are obtained.

Encapsulation of Metal Nanoparticle Catalysts Within

Mesoporous Zeolites

High Silica contain – Hydrophobic

Applica'ons of
Semiconductor
quantum dots:
Langmuir−Blodgett (LB) Technique
(Irving Langmuir ‘1917’ monolayer formation and transfer on solid surface)

Step 1: Langmuir film is prepared by spreading amphiphilic molecules on a liquid surface.

Step 2: Considerable order can be achieved in these films by adjusting the ‘pressure’ parameters.
Step 3: Film is then transferred to a solid substrate.

Surfactants
“amphiphilic molecules”
[polar (Hydrophilic) and non-polar
(hydrophobic) regions in same molecules]:

cholesterol, detergents, and

phospholipids.
 • Langmuir−Blodgett (LB) Technique
Minimum colloidal particle size of 700 nm can be easily assembled
Colloids particles are around 700 nm which results in nanostructures of ~200 nm

Parameters:
• Solution concentration
• Monolayer formation pressure
• Pulling rate of substrate
• Substrate Surface properties
• Solution Temperature

Ref.: Samatha B. Ph.D. Thesis 2020

 • Hole-Colloidal Lithography

• Charged colloids are used in HCL process for assembly on the polymer coated substrate.

• Through electrostatic force of attraction between substrate and charged particles,

colloidal assembly is formed.

• The process uses a sacrificial layer combined with a thin film mask with holes and hence
the name Hole colloidal lithography.

• The HCL process does not have limitation on the colloid size and also gives long range
order. The process is applicable on any patterned substrate and it gives good coverage.
 Process flow of HCL method:-

Nanostructure Size ~ 10 nm
Nanostructures development using HCL process:-

*polymethyl methacrylate (PMMA)

*Poly(diallyldimethylammonium chloride) (PDDA)
Self-aligned fabrication
 Self-assembly Monolayer (SAM)

Ø The formation of a self-assembled monolayer does not require the help of an external driving force.

Ø Monolayer is formed when the metal (or any other substrate) surface is exposed to a solution containing the
surfactant (a detergent that, when added to a liquid, reduces its surface tension, thereby increasing its
spreading and we7ng proper8es)

Ø Gold substrate is preferred due to its non-oxidation nature, clean surface, easy to grow thin film (Single-
crystal Au(111) film – Substrate coupled process).

Ø SAMs can be formed on other surfaces such as Cu, Ag, Pt, GaAs, etc. The coverage of molecules on these
surfaces is in the order Cu>Ag>Pt>Au>GaAs, which is a direct consequence of the adsorbate structure.
 • Self-assembly Monolayer (SAM) – Substrate Coupled Process
The process of assembly of monolayers on the surface involves two stages.
• During the first stage, the surfactants are rapidly pinned on the surface, followed by a slow reorganization step
• During the second stage, extending over several hours (12- 14 hours) for complete self-assembly

The structure of alkane thiol monolayers on Au(111) is shown schematically below:

X is a functional group

Monolayer of alkanethiol on Au(111) Assembly of thiolate chains

NOTE: Au-grain size limits the uniform area coverage of thiolate chains on Au-surface.
• Self-assembly Monolayer (SAM) – Substrate Coupled Process

A. Ulman et al. (Chem. Rev. 1996) found that on AgO

surfaces, the carboxylate two oxygen atoms bind to the
surface nearly symmetrically, while on surfaces of CuO
and Al2O3, the carboxylate binds asymmetrically to the
surface displaying tilt angles close to zero.

• AFM image of octa-decane-thiolate on Au(111)

• Self-assembly Monolayer (SAM) – Substrate Coupled Process

• Self-assembly Monolayer (SAM) – Substrate De-coupled Process

For Example: In the substrate decoupled process, such as the

formation of alkylsiloxanes on a hydrated silicon substrate, no
direct interaction between the surface and SAM molecules is
involved, and the monolayer formation process is purely driven
by intermolecular forces.
Types of monolayers:
A. Gibbs Monolayer (Using Surfactants)
B. Langmuir Monolayer (Hydrophilic-tail // Hydrophobic-head)
 Self-assembly Monolayer (SAM): Applications

q Sensors: A variety of metal ion sensors can be made by functionalizing the metal surface with a ligand with high
specificity to a particular ion.
Ø Sensors selective to Cu2+ were made by functionalizing the gold surface with 2,2’-thiobisethyl acetoacetate.

q Biosensors : A biorecognition molecule is the sensor element (form of antibodies, proteins, DNAs, etc), which is
specific to the analyte molecule.
Ø The change in the surface plasmon resonance of a thin film of gold as a result of the biorecognition event is used to
sense the event.
Ø The change in the oscillation frequency of a quartz crystal as a result of the mass accumulation on a gold film
deposited on its surface, is used to sense the biorecognition event.

q Chemical Sensors: One of the most common sensing events is the quantitative detection of transition metal ions,
especially in presence of other ions. The detection of Cu(II) in presence of Fe(III) is an example.
Self-assembly Monolayer (SAM):
Applications in Molecular Electronic Devices
 Metal Nanoparticles
ü Monolayer-Protected Metal Nanoparticles
ü Functionalized Metal-nanoparticles

INTRODUCTION:
In 1857 Faraday made colloidal gold by reducing the aqueous solution (water as solvent !)
of (AuCl4-) with phosphorus in Carbon disulfide (Faraday, M., Phil. Trans., 147 (1857), p.
145).

The most popular one is the citrate reduction method of Turkevitch (Turkevitch, J., Discuss
Faraday Soc., 11 (1951), p. 55). Here a solution of the gold or silver salt (typically 1 mM)
is boiled with a higher concentration (typically 1 M) of sodium citrate for a few minutes.
This results in the formation of metal colloids of 10–50 nm diameter, and the size can be
varied by altering synthetic parameters.

This colloidal solution is stable for several months (the gold colloid is much more stable
than that of silver). Here the stability is due to an electrical double layer surrounding the
metal surface.
 Monolayer-
Method Of Preparation: Reducing agent protected
clusters

AuCl4-was transferred to toluene using tetra octyl ammonium bromide as the phase transfer agent. The phase-
transferred Au 3+ is then reduced in the presence of the surfactant, octadecanethiol using NaBH 4 as the reducing
agent…

Brust, M., M. Walker, D. Bethell, D.J. Schffrin and R.J. Whyman, J. Chem. Soc., Chem. Commun., 801, (1994).
Functionalized Metal(Au)-nanoparticles:
• Functionalization can be either through a ligand exchange reaction or using modified thiol as the capping agent.

• Various photoactive molecules have been attached to the surface of gold using the thiol end group and such
structures are shown below.

Brust, M., M. Walker, D. Bethell, D.J. Schffrin and R.J. Whyman, J. Chem. Soc., Chem. Commun., 801, (1994).
 APPLICATIONS of Functionalized Metal(Au)-nanoparticles:

Ø Gold nanoparticles have very high extinction coefficients (Strong coupling with electromagnetic radiation)

Ø Crown ethers in combination with gold nanoparticles have been used as K+ ion sensor. K+ has the ability to form 1:2
adducts with crown ethers attached to adjacent nanoparticles as shown in Fig. below.

Ø This results in aggregation and the colour changes from dark brown to purple (Lin, S.Y., S.W. Liu, C.M. Lin and C.H.
Chen, Anal. Chem., 74 (2002), p. 330).
 APPLICATIONS of Functionalized Metal(Au)-nanoparticles:
Ø Selective detection of lithium ion by gold nanoparticles

(Lin, S.Y., S.W. Liu, C.M.

Lin and C.H. Chen, Anal.
Chem., 74 (2002), p. 330).

Ø Toxic heavy metal ions such as lead, cadmium and mercury can be detected by using gold nanoparticles. This ion
templated chelation process changes the color of the solution. It also changes the Rayleigh scattering response from the
medium.

Ø Ion‐assisted chelation (bind to metal) for the detection of heavy metals