Template-Based Synthesis

Introduction
• used in fabrication of nanorods, nanowires and nanotubules,of polymers,
metals, semiconductors and oxides.
• First,the template materials must be compatible with the
processingconditions. For example, an electrical insulator is required for a
template tobe used in electrochemical deposition. Except for the template
directedsynthesis, template materials should be chemically and thermally
inertduring the synthesis.
• Secondly, depositing materials or solution must wetthe internal pore walls.
• Thirdly, for the synthesis of nanorods or nanowires,the deposition should
start from the bottom or one end of the templatechannels and proceed
from one side to another. However, for the growth ofnanotubules, the
deposition should start from the pore wall and proceed inwardly. Inward
growth may result in the pore blockage, so that should be avoided in the
growth of “solid” nanorods or nanowires.
• Kinetically, enough surface relaxation permits maximal packing density, so
a diffusion limited process is preferred.
• Other considerations include the easiness of release of nanowires or
nanorods from the templates and of handling during the experiments.
 Electrochemical deposition

• also known as electrodeposition,

• only applicable to electrical conductive materials such as metals, alloys, semiconductors and
electrical conductive polymers,
– since after the initial deposition, the electrode is separated from the depositing solution by the
deposit and the electrical current must go through the deposit to allow the deposition process to
continue.
• Electroplating-Electrochemical deposition for making metallic coatings
• When deposition is confined inside the pores of template membranes, nanocomposites are
produced. If the template membrane is removed, nanorods or nanowires are prepared.
• This process involves
– (i) oriented diffusion of charged growth species (typically positively charged cations) through a
solution when an external electric field is applied, and
– (ii) reduction of the charged growth species at the growth or deposition surface which also serves as
an electrode.
• The electrode potential or surface charge density,E, is described by the Nernst equation:

• Eo is the standard electrode potential, or the potential difference between the electrode and
the solution, when the activity,ai, of the ions is unity,F, the Faraday’s constant, R,, the gas
constant and T, temperature.
 Charge transfer
• When the electrode potential is more negative (higher) than the energy level of vacant molecular
orbital in the electrolyte solution, electrons will transfer from the electrode to the solution,
accompanied with dissolution or reduction of electrode as shown in Fig. (a). If the electrode
potential is more positive (lower) than the energy level of the occupied molecular orbital, the
electrons will transfer from the electrolyte solution to the electrode, and the deposition or
oxidation of electrolyte ions on the electrode will proceed simultaneously as illustrated in Fig. (b)
. The reactions stop when equilibrium is achieved.
 Galvanic cell
• When two electrodes of different materials immerse into one electrolyte solution, each electrode
will establish equilibrium with the electrolyte solution. Such equilibrium will be destroyed, if two
electrodes are connected with an external circuit. Since different electrodes have different
electrode potentials, this difference in electrode potential would drive electrons migration from
the electrode with a higher electrode potential to the lower one.
• Let us take the Cu and Zn electrodes immersed in an aqueous solution. Assuming both activities
of copper and zinc ions in the aqueous solution are unity in the beginning, the copper electrode
has a more positive electrode potential (0.34 V) than that of the zinc electrode (-0.76V). In the
external circuit, electrons flow from the more negative electrode (Zn) to the more positive
electrode (Cu). At the zinc solution interface, the following electrochemical reactions take place:

This reaction generates electrons at the interface, which then flow through the external
circuit to another electrode (Cu). At the same time, Zn continues to dissolve from the
electrode into the solution. At the copper-solution interface, a reduction reaction takes place
resulting in deposition of Cu onto the
electrode through the following reduction reaction:

From the Nernst equation, one can see that the copper electrode potential decreases due to a
decrease in copper ion activity in the solution, whereas the zinc electrode potential increases due to
an increased activity of zinc ions in the solution as both electrochemical reactions proceed. This
system is a typical example of galvanic cell, in which chemical potential is converted into electricity.
This process can be altered or even reversed,
when an external electric field is introduced to the system.
 Electrolysis
• When an external electric field is applied to two dissimilar electrodes, electrode potentials can be
changed so that electrochemical reactions at both electrode-solution interfaces are reversed
and the electrons flow from a more positive electrode to a more negative electrode. This process is
called electrolysis, which converts electrical energy to chemical potential, and is a process widely
used for applications of energy storage and materials processing.
• The system used for the electrolysis process is called electrolytic cell; in such a system the
electrode connected to the positive side of the power supply is an anode, at which an oxidation
reaction takes place, whereas the electrode connected to the negative side of the power supply is
a cathode, at which a reduction reaction proceeds, accompanied with deposition. Sometimes,
electrolytic deposition is therefore also called cathode deposition
• In an electrolytic cell, it is not necessary that anode dissolves into the electrolytic solution and
the deposit is the same material as cathode.
• Which electrochemical reaction takes place at an electrode (either anode or cathode) is
determined by the relative electrode potentials of the materials present in the system. Noble
metals are often used as an inert electrode in electrolytic cells.
 Nanowire growth
• A typical electrolytic process composes of a series of steps; each step could be a rate-limiting
process:
– (1) Mass transfer through the solution from one electrode to another.
– (2) Chemical reactions at the interfaces between electrodes-solution.
– (3) Electrons transfer at the electrode surfaces and through the external
– (4) Other surface reactions such as adsorption, desorption or recrystallization
• Electrochemical deposition of conductive materials is a self-propagating process. When little
fluctuation yields the formation of small rods, the growth of rods or wires will continue, since
the electric field and the density of current lines between the tips of nanowires and the
opposing electrode are greater, due to a shorter distance, than that between two electrodes. The
growth species will be more likely deposit onto the tip of nanowires, resulting in continued growth.
it is very difficult, if not impossible, to control the growth. Therefore, templates with desired
channels are used for the growth of nanowires in electrochemical deposition. Figure 4.21
illustrates the common set-up for the template-based growth of
 Difference
• Electroless deposition is actually a chemical deposition and involves the use of a chemical agent
to plate a material from the surrounding phase onto a template surface.
electrochemical electroless

the deposition begins at the bottom electrode
deposited materials must be electrically
conductive
results in the formation of “solid” nanorods
or nanowires of conductive materials,
the length of nanowires or nanorods can be
controlled by the deposition time,
deposition starts from the pore wall and
proceeds inwardly
method does not require the deposited
materials to be electrically conductive
often grows hollow fibrils or nanotubules
the length of the nanotubules is solely
dependent on the length of the deposition
channels or pores, which often
equal to the thickness of membranes

prolonged deposition time does not guarantee
the formation of solid nanorods
Variation of deposition time would result in a
different wall thickness of nanotubules. An
increase in deposition time leads to a thick
wall and a prolonged deposition may form a
solid nanorod.
 Electrophoretic deposition

• film deposition of ceramic and organoceramic materials on cathode from colloidal dispersions.
• First, the deposit by electrophoretic deposition method need not be electrically conductive.
• Secondly, nanosized particles in colloidal dispersions are typically stabilized by electrostatic or
electrosteric mechanisms.
• When dispersed in a polar solvent or an electrolyte solution, the surface of nanoparticles
develops an electrical charge via one or more of the following mechanisms:
– (i) preferential dissolution or
– (ii) deposition of charges or charged species,
– (iii) preferential reduction or (iv) oxidation,and (v) adsorption of charged species such as
polymers.
• Upon application of an external electric field to a colloidal system or a sol, the constituent
charged particles are set in motion in response to the electric field, referred as electrophoresis.
 Zeta potential
• When a charged particle is in motion, some of the solvent or solution surrounding the particle will
move with it, since part of the solvent or solution is tightly bound to the particle.
• The plane that separates the tightly bound liquid layer from the rest of the liquid is called the
slip plane. The electric potential at the slip plane is known as the zeta potential.
• Zeta potential determines the stability of a colloidal dispersion or a sol; a zeta potential larger
than about 25 mV is typically required to stabilize a system.'

Q is the charge on the particle, a is the radius of the particle out to the shear
plane,E, is the relative dielectric constant of the medium, and ni andzi are
the bulk concentration and valence of the ith ion in the system, respectively.
 Zeta potential
• A high concentration of counter ions, however, can result in a zeta potential of the opposite sign.
• The mobility of a nanoparticle in a colloidal dispersion or a sol µ is dependent on the dielectric
constant of the liquid mediumɛr the ze ta p
o ten ti
al oft he n an op a rt
icl
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ɛand t heviscosityo f
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• Electrophoretic deposition simply uses such an oriented motion of charged particles to grow films
or monoliths by enriching the solid particles from a colloidal dispersion or a sol onto the surface
of an electrode.
• If particles are positively charged (more precisely speaking, having a positive zeta potential),
then the deposition of solid particles will occur at the cathode. Otherwise, deposition will be at
the anode.
• At the electrodes, surface electrochemical reactions proceed to generate or receive electrons. The
electrostatic double layers collapse upon deposition on the growth surface, and the particles
coagulate. There is not much information on the deposition behavior of particles at the growth
surface.
• The films or monoliths grown by electrophoretic deposition from colloidal dispersions or sols are
essentially a compaction of nanosized particles. Such films or monoliths are porous, i.e. there are
voids inside.
• Typical packing densities, defined as the fraction of solid (also called green density) are less
than 74%, which is the highest packing density for uniformly sized spherical particles.
• The green density of films or monoliths by electrophoretic deposition is strongly dependent on
the concentration of particles in sols or colloidal dispersions, zeta potential, externally applied
electric field and reaction kinetics between particle surfaces .
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