Self-Assembly

A wet chemical route to the synthesis of thin films, mostly organic or

inorganic-organic hybrid films-

 Self-assembled monolayers (SAMs)

 Electrostatic self-assembly
 Self-organization in block copolymers

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 Self-Assembled Monolayers (SAMs)
 Molecular assemblies that are formed spontaneously by the immersion
of an appropriate substrate into a solution of an active surfactant in an
organic solvent-
 The formation of monolayers by spontaneous chemisorption of long-
chain amphiphilic molecules (that have both hydrophilic and
hydrophobic functionalities) at surfaces is an excellent example of how
self-assembly can create long- range order.

 Factors that contribute to the usefulness of various types of SAMs for

application purposes are stability, functional group versatility, and
substrate/monolayer composition.

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 SAMs have been exploited for applications of surface chemistry
modification, introduction of functional groups on the surface, construction of
multilayer structures.

 Used to enhance the adhesion at the surfaces.

 Used in the synthesis and fabrication of core-shell nanostructures with

silane groups linking to oxides and amines linking to metals.

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3-mercaptopropionic acid
(MPA) 1-tetradecanethiol (TDT)

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SEM images of (a) bare gold electrode (b) AuNP-modified electrode.
 Monolayers of organosilicon or alkylsilane derivatives

 Monolayers of organothiol on flate gold surfaces

 Monolayers of organothiol on faceted metal clusters

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 Organosilicon Monolayers
 SAMs are created from chemisorption of alkylsilanes ( or where R is an
alkyl chain and X is chloride or hydroxyl- terminated alkyl chain) to
hydroxylated silica surfaces

 Monolayer self-assembly can be carried out in solution or the vapor phase

 Organosilicon monolayers are extremely robust due to the network of strong

Si–O–Si bonds

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Fabrication of silica-gold core-shell nanostructures
Organosilicon with amine as a functional group is used to form a
monolayer on the surface of silica nanoparticles by self- assembly. The
surface amine groups then attract gold nanoclusters in the solution, which
result in the formation of a gold shell.

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Fabrication of
SA multilayer structure
Organothiol monolayers on flat gold surfaces
 Affinity of sulfur towards gold, silver, copper, platinum

 Long-chain alkanethiolates (SH group at the end of an alkane chain) on

gold surfaces

 Monolayer self-assembly can be carried out in solution or the vapor

phase

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The sulfur group links the molecule to the gold surface. The
1. AFM
head group can be designed to provide virtually any surface
2. STM
chemistry, binding capacity, or property.

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Gold SAMs – tools for studying molecular-based electronics and creating
nanostructured materials and patterned surfaces

Molecular Junction
Molecules as electronic components!

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Molecular Junction - Molecules as electronic components!
 Organothiol monolayers on faceted metal clusters
 Monolayer Protected Clusters (MPCs)‚ commonly referred to simply as nanoparticles

 Alkanethiolate-stabilized gold cluster synthesized by solution-phase methods

 SAMs assembled on MPCs are quite different than SAMs on flat gold surfaces

 Nanoparticle surface is highly faceted and hence contains many defect sites such as
edges and vertices

 Nanoparticle SAMs radiate outward from the core

 The monolayer structure exhibits both pseudo-crystalline internal regions (providing

long-term stability against agglomeration both in air and in solution) and fluid-like
packing at the periphery

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The SAM shields gold core from agglomeration during nanoparticle formation

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 Among the metals, gold clusters, especially the alkanethiolate monolayer
protected clusters (MPCs), have been extensively investigated during the past
decades. In recent years, silver and copper nanoclusters have also attracted
enormous interest mainly due to their excellent photoluminescent properties.

Meanwhile, more structural characteristics, particular optical, catalytic,

electronic and magnetic properties and the related technical applications of
the metal nanoclusters have been discovered in recent years.

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