Self assembly of

Nanoparticles
Self-assembly of nanostructures is a process where atoms, molecules, or
nanoscale building blocks spontaneously organize into ordered
structures or patterns with nanometer features without any human
intervention. It is the most promising, practical, low-cost, and high-
throughput approach for nanofabrication.
 What is self assembly?
• Self assembly is a process in which components, either separately or linked,
spontaneously form stable, well shaped, ordered aggregates.
• Or, Self assembly is a process of spontaneous association of individual units of a
material into highly ordered structures/patterns; transformation of disordered
structure into ordered ones.
• It’s a powerful strategy for controlling the structure and physicochemical properties
of the nanoparticles.
• This shows collective properties that differ from individual nano crystals and bulk
samples.
• The uniqueness is due to the ability to adjust the self assembly process and
interactions among the electronic, magnetic, and optical properties of the single nano
Building unit.
• The hierarchical structures provide new opportunities for optimising, tuning, and/or
enhancing the properties or and performance of these materials.
Assembly of CTAB in water
Surfactant assembly

• Micelles, spherical or
cylindrical, can be obtained at
particular conditions

Phase diagram of CTAB in water

Surfactant-oil-water ternary phase diagram
 Importance of self assembly
• The cell contains different complex assemblies, such as lipid membranes, folded
proteins, structured nucleic acid, protein aggregates, molecular machines, and
many others natural forms by self assembly.
• Self assembly provides routes to a range of materials with regular structures, such
as molecular crystals, liquid crystals, and semi-crystalline and phase-separated
polymers.
• Self assembly occurs widely in systems of components larger than molecules, and
there is great potential for its use in materials (including biomaterials) and
condensed material science.
Importance of self assembly
• Self assembly seem to offer one of the most general strategy that is now available
for generating nanostructures.
• Self assembly produces structures in a bottom-up approach.
• Device fabrication methods are top down and need a large number of steps, and
costly infrastructure
• Feature size of the pattern is restricted by diffraction limits of exposure
wavelength
• Miniaturisation of the electronic devices
 Self assembly
• In SA nano building blocks, forms larger, well
organised patterns, when they interact with one
another through a balance of usually weak and non-
covalent intermolecular forces which facilitates self-
assembly of the units.
• The intermolecular forces are Van der Walls interaction,
hydrogen bonds, static charges, magnetic interaction, et.
• The intermolecular forces helps stabilise the self-
assembled structures under different environmental
conditions.
• The directionality and functionality of self-organised
structures are determined by other functional
interactions or forces.
Mechanism of self-assembly (SA)
• Any system tries to go to the lowest energy state. This is the driving force of SA
• Molecules with definite shape, number of atoms, and size, already in the state of
low energy are good candidates for the SA, as they are held together by stronger
forces.
• The SA depends upon the availability of units of same size and shape
• When these building blocks are available for SA, a state of minimum energy is
attained spontaneously even in the absence of any external force
Types of self assembly
• Static: system that were at global or local equilibrium and do not dissipate energy
• Molecular crystal are formed by static self assembly

• Dynamic: the interaction is responsible for the formation of structures of patterns

between components only occur if the system is dissipating energy
• The patterns formed by competition between reaction and diffusion in oscillating
chemical reactions
Mechanism of self assembly
• SA may occur in the presence of an external driving
force like temperature, pressure, magnetic field, etc.
• Assembly in the absence and presence of an external
driving force are known as static and dynamic
assemblies, respectively.
• In static assembly, the system achieves minimum
energy state in the absence of any external forces,
example formation of ordered crystalline structure from
a melt.
• In dynamic assembly, constant influence of external
force from the ambient.
• If the energy intake from the ambient stops, the SA can
leave the state of organised structure and deassemble.
 • Hierarchical SA is a multilevel organisation
Hierarchial and co-assembly process.
• Assembles elementary molecular units into
ordered secondary structures via non-covalent
interactions.
• Act as the building blocks to form more complex,
multifunctional superstructures.
• In directed SA, Building blocks occupy the pre-
designed places like lithographically patterned
substrate, pores in membranes, or spaces between
ordered particles.
• Directionality is controlled either by changing the
energy or entropy landscapes or applying external
fields
• Co assembly can be formed with two or more
types of blocks which can fit into each other
• Forms of more complex, hierarchal, colloidal
superstructures observed.
Hierarchical self-assembly
• In hierarchical self-assembly, structuration of the building blocks occurs over
multiple length scales. Initially, at the smallest length scale, self-assembly of the
original building blocks takes place.
• The assemblages that grow out of the first level of assembly form the building
blocks for the second stage.
• This hierarchy of self-assembled building blocks continues at multiple levels,
which span multiple length scales.
 Eg. Hierarchical self assembly process
• At thermodynamic equilibrium interactions between the nano particles reduces the
systems free energy.
• This exhibits unique physical and chemical properties
Directed self-assembly
• In the directed self-assembly an external stimulus is used to drive the assembly in
a desired direction. One way to direct the self-assembly is to provide a
lithographic template, and use the template to guide colloidal particles or
nanoparticles in a solution to self-assemble on the template surface.
• Directed self-assembly can further be divided to static and dynamic self-assembly.
In static self-assembly, the external forces drive the system to an equilibrium state.
The system dissipates energy as it moves towards a static equilibrium. At this
equilibrium, the self-assembled structure will retain its configuration there after
even if the external stimuli are removed; hence called static self-assembly.
• Dynamic self-assembly generates stable assemblages, which may not be at
thermodynamic equilibrium. These stable configurations persist as long as the
external stimuli are present and the system dissipates energy. These configurations
can also be manipulated by rectifying the external forces. As soon as external
forces are removed, the system will disassemble, and return to a thermodynamic
equilibrium.
Self organisation of nanocrystals generates a variety of
structures, including

Self assembled anti-cancer drug conjugate

nano structure that can be administered
directly to kill cancer cells, without the need
for additional carriers or delivery vehicles
• Self assembled nano and
micro structures (fibres,
tubes, rings, cages,
polyhedrons, and more
complex structures)
consisting of peptides and
proteins, of formed based on
the formation of secondary
structures and specific
interactions.
 Nano composite self assembly
• Nanocomposite is multiphase, solid material or structure, having nanoscale repeat
distance between the different phases that make up the material
• Organic matrix serves as template on which specific mineral (in organic material)
is formed
• Arrangement of the bio minerals is controlled by the surface tension between the
cells, vesicles and the growing mineral
 Synthesis of Pt-around-Au nanocomposite electrostatic self-
assembly oppositely charged NPs
• Pt NPs (+) prepared in PDDA solution (polydiallyldimethylammonium chloride)
• Au NPs (-) synthesis in sodium citrate solution
• Once these two solutions are mixed, the positively charged Pt NPs interact with
the negatively charged Au NPs, and Pt-around-Au nanocomposite particles are
obtained.
Self assembly of Nanoparticles via organic molecules
• Performed inorganic nano
particles. Example CdS
nano particles
functionalised with
carboxylic group can be
transferred to aluminium
thin films.
• Dithiols adsorbed on metal
surfaces also could adsorb
CDS nano particles to form
layers of them.
Self assembly of Nanoparticles

Ag NPs are adsorbed on

oxidised aluminium layers using
through carboxylic group and
thinly attaches.

• Here, chemical reaction takes place in an aqueous medium.

• Colloidal Ag NPs are then transferred into an organic solvent and drop casted on
an aluminium oxide layer.
• After the evaporation of organic solvent, self assembled Ag NPs layer is left on
the metal oxide layer
Self assembled silica particles on glass slide
• Silica particles are formed by a sol-gel Route
• Particles synthesised in Aqueous medium are
simply allowed to evaporate from the solution
drop placed on a glass substrate
• After sometime, the particles self assemble due
to weak Van der walls interaction amongst the
particles.
• Driving force is the capillary force
• Surface energy is minimised by forming
hexagon L network
• Size uniformity of the particles lead to make
an ordered 2-D network of particles
Applications
Self assembly affected by….
• External forces
• Gravitational attraction
• External electromagnetic fields
• Magnetic
• capillary
• And entropic interactions
Biological assembly
• The association of weak, reversible interactions for thermodynamically,
favourable State.
• Assembly is different from binding (lock and key mechanism)
• Cooperative
• Complimentary in molecular shape.
Factors affecting self assembly
• Balance between Brownian
motion and intermolecular forces.
• Brownian motion control the
location of the molecules where
intermolecular forces hold the
molecules at the particular
position.
• Brownian motion takes care of the
incorrect assemblies of the
molecules
Examples of static self assembly

(A) Crystal structure of a ribosome . (B)

Self-assembled peptide-amphiphile
nanofibers. (C) An array of millimetre-
sized polymeric plates assembled at a
water/perfluorodecalin interface by
capillary interactions. (D) Thin film of a
nematic liquid crystal on an isotropic
substrate. (E) Micrometer-sized metallic
polyhedra folded from planar substrates.
(F) A three-dimensional aggregate of
micrometer plates assembled by capillary
forces.
Examples of dynamic self assembly
(A) An optical micrograph of a cell with
fluorescently labelled cytoskeleton and
nucleus; microtubules (~24 nm in diameter)
are coloured red. (B) Reaction-diffusion
waves in a Belousov-Zabatinski reaction in
a 3.5-inch Petri dish. (C) A simple aggregate
of three millimetre-sized, rotating,
magnetized disks interacting with one
another via vortex-vortex interactions. (D) A
school of fish. (E) Concentric rings formed
by charged metallic beads 1 mm in diameter
rolling in circular paths on a dielectric
support. (F) Convection cells formed above
a micropatterned metallic support. The
distance between the centres of the cells is
~2 mm.
Advantages of self-assembly
Self-assembly has a wide range of potential applications, from drug delivery and
tissue engineering to electronics and energy storage. Here are several key
advantages that make it an attractive option for researchers and manufacturers alike:

1. Cost-Effectiveness
• Self-assembly is a highly cost-effective method of fabrication as it relies on
natural interactions between components rather than expensive machinery or
specialized equipment.
• Self-assembly can be performed in solution, which means that large quantities of
material can be produced at once making it an ideal method for industrial-scale
production.
2. Scalability and Flexibility
• Self-assembly can be used to create structures on a wide range of scales - from the
nanoscale to the macroscale - it has the potential to be applied to many different
types of materials and devices making it a highly versatile method tailored to suit a
wide range of applications.
• Self-assembly can be performed under a variety of different conditions, including in
solution, on surfaces, and in the gas phase, and also in a wide range of
environments, including in the human body.

3. Enhanced Precision and Control

• By carefully designing the interactions between components, researchers can create
highly ordered and uniform structures with a high degree of accuracy. This can be
especially useful for applications such as electronics or biomedical engineering,
where precise control over the properties and behavior of materials is crucial.
• Self-assembly can be used to create structures with highly specific properties, such
as porosity, conductivity, or magnetism.
4. Environmental Sustainability
• Because self-assembly does not rely on harsh chemicals or other toxic agents, it
can be a greener alternative to traditional manufacturing methods that may
produce harmful waste products or emissions.
• In addition, self-assembly can be used to create materials with unique properties
that may have environmental benefits. For example, self-assembled materials can
be used to create highly efficient solar cells or to capture and store carbon dioxide
from the atmosphere.
Challenges and Limitations of Self-Assembly
There are several challenges and limitations associated with this method of
fabrication that researchers and manufacturers need to be aware of:

1. Technical Difficulties and Complexities

• Because it relies on natural interactions between components, it can sometimes be
difficult to control or predict the final outcome. Also, the process can be highly
sensitive to factors such as temperature, pH, or the presence of other molecules,
making it a potentially difficult process to reproduce on a large scale.
2. Reliability and Quality Control
• Another challenge with self-assembly is ensuring reliable and consistent results.
Because the process can be highly sensitive to small changes or variations, it can
be difficult to ensure that every assembly is identical and performs as expected.

3.Safety and Ethical Considerations

• Because the components used in self-assembly can be highly complex and novel,
it can be difficult to predict their long-term effects on human health or the
environment. Additionally, there may be ethical concerns associated with the
creation of new materials or devices that have the potential to disrupt existing
social or economic structures.