Template Organization of 1-D

nanostructures

Definition of 1-d nanostructures

Generally defined as chains/wires with nanoparticles or atoms as building blocks.

However this is not adequate. We consider aspect ratio.

In some cases, if the building blocks are rather big (or are very small three-
dimensional particles) or the aspect ratio is not very well expressed, one also
speaks of quasi one-dimensional structures. Therefore, in the following, there
will no longer be a distinction between a truly one-dimensional assembly of
nanoparticles and a merely quasi one-dimensional assembly.

There is a very imp. Diff between 1-d and 2-d nanostructures. 2-d self
assembly can take place without a template

Advantages of template synthesis

Template-directed synthesis represents a convenient and versatile
method for generating 1D nanostructures. In this technique, the
template simply serves as a scaffold against which other kinds of materials
with similar morphologies are synthesized. These templates could be
nanoscale channels within mesoporous materials or porous alumina and
polycarbonate membranes. The nanoscale channels can be filled using
solution, sol-gel or electrochemistry to generate 1D nanoscale
objects. The produced nanowires can then be released from the
templates by selectively removing the host matrix. The template
method has a number of interesting and useful features.
1. First, it seems to be very general. The methodology was pioneered
by Moskovits and Martin [22]. Researchers have now used this
method to prepare nanoscale wires, and tubules made of
electronically conductive polymers, metals, semiconductors,
oxides, carbon, and many other materials.
2. Furthermore, nanostructures with extraordinarily small diameters
can be prepared using this method. For example, Wu and Bein [28]
have recently used this method to prepare conductive polymer
nanofibers with diameters of 3 nm in MCM-41 mesoporous
silica. It is quite difficult to make nanowires with diameters this small
186 H. Yan and P. Yang using lithographic methods.
 3. In addition, because the pores in the porous membranes usually
have monodispersed diameters, analogous monodispersed
nanostructures can be in principle prepared.
4. Finally, the 1D nanostructures synthesized within the pores can
be freed from the template membrane and collected.
Alternatively, an ensemble of 1D nanostructures can be obtained.

Various templates
Nanopores are in principle promising candidates if they can be filled with

nanoparticles in such a way that the resulting composites can be used for
planned

investigations or applications. In this connection, nanoporous alumina

plays a

certain role, since it can easily be prepared as thin films equipped with 109–
1011

pores per cm2, all running parallel through the membrane. These films are

formed by anodic oxidation of aluminum surfaces in polyprotic

aqueous acids, the

applied voltage determining the pore width. The pore length simply
depends on

the anodization time. So, pores from about 10 up to 200 nm in width

and up to

some hundreds of mm in length are available .

Preformed particles can be transferred into the pores from solution by
vacuum induction,

or they can be generated inside the pores by decomposition of

previously

deposited appropriate complexes. Figure 4-35 shows a TEM image of a

sectioned

piece of a membrane filled with gold nanoparticles.

However, as it turned out, these templates did not yet lead to fully
convincing

results, i.e., to the perfect wires of nanoparticles which are necessary

to study

electronic conduction mechanisms, since the lack of only one particle in

a row
would interrupt the electric conductance. Among other causes of this
difficulty, the

main one was the length of the pores. For instance, in a pore of a 1 mm
thick

membrane (a minimum thickness that could still be handled), 500

particles of size

2 nm have to be arranged without defects. This is practically

impossible

Polymer molecules could be promising alternative templates for

assembling
metal nanoparticles on their surfaces. DNA is one of several candidates for
assemblies
of up to several microns.

Examples of DNA as template

• Ligand-protected platinum particles of 2–3nm do in fact add to

natural DNA in buffer solution in a very regular fashion and can
easily be observed by TEM [211]. Figure 4-36 shows an assembly of
DNA strands covered with Pt nanoparticles.
• lamda-DNA has also been used for covering with 3–5 nm Pd
particles [206]. Here,
preformed particles were not used, but were generated on the
DNA surface by
reduction of Pd(CH3COO)2 with a mixture of sodium citrate,
lactic acid, and dimethylamine borane.

• Colloidal platinum particles have also been generated on DNA,

starting with
an impregnation step with dichloro(2,20:60,200-
terpyridine)platinum(II) or cis-
Pt(NH3)2Cl2, followed by reduction with NaBH4 [207].

• All these methods give quasi one-dimensional, but more or less

disordered, structures. A rather interesting route to ordered
arrangements of gold nanoparticles in combination with DNA
has recently become known [209]. The method is based on
Coulomb interactions between the negatively charged
phosphate backbone of synthetic and natural DNA and
positively charged 3.5 nm gold nanoparticles prepared from
HAuCl4 and NaBH4 and capped with lysine molecules. TEM
investigations of these hybrid systems indeed prove the formation of
 equidistant rows of nanoparticles between parallel DNA sequences, as
sketched in Figure 4-37.

Polymer as template

Examples

Polymer molecules were used in two cases for decoration with

Au55(PPh3)12Cl6 clusters. Substituted poly(p-
phenyleneethynylenes) turned out to readily chemisorb the clusters,
probably owing to pp interactions between the electron-rich polymer
and the phenyl groups in the clusters’ ligand shells. In the special
case of the I-octyl-substituted derivative (PPEI- oct), small bundles of
polymer molecules can be generated in very dilute solutions [211]. PPE-I-
oct (0.5 mg per liter dichloromethane) forms bundles of diameter
ca. 10–12 nm and length 250 nm. These thin chains of polymers are
able to adsorb the clusters in a truly one-dimensional manner, as
can be seen from Figure 4-40.
More or less all attempts to organize nanoparticles are driven by their
possible
use in future nanoelectronic devices, above all as miniaturized
transistors. This
highly desirable goal can only be reached if we succeed in generating
structures
which are not made by nature, but instead follow complex designs.
The precise
placement of nanoparticles, acting as single electron transistors, is therefore
the
ultimate dream of any research in that field.
The very first attempts have been made. The present state of the art is
based on
the use of appropriately nanostructured surfaces that are chemically
modified in
such a way as to irreversibly bind nanoparticles onto the structure.
One possible
route has been pointed out by J. R. Heath et al. However, it still leads to
rather
broad structures [224]. They used light-controlled arrangement of gold
nanoparticles
on glass and silicon substrates. These are first covered with a
monolayer of
(3-aminopropyl)ethoxydimethylsilane, and this is followed by the
addition of nitroveratryloxycarbonylglycine (NVOC-GLY) to yield a
surface with light-sensitive
NVOC functions. Exposure to UV/Vis light through a mask results in a
pattern of
free and protected amino groups. Gold particles (2.6 nm), protected
by a shell of
1-dodecylamine, are then used for addition to the free amino
groups. Ligand exchange
reactions between the 1-dodecylamine and the free amine groups of the
surface lead to the decoration of the exposed areas with gold nanoparticles.
The
process is illustrated in Scheme 4-1. As can also be seen from this figure,
additional
particles can be placed in successive steps via dithiol ligands removing more
weakly bound amines.

Mesoporous silica as template

Besides porous alumina and polymer membranes, with their high surface
areas and uniform pore sizes, mesoporous silica materials have also
been widely used as host materials for loading catalysts, polymers,
metal and semiconductor nanoparticles that have potential catalytic,
environmental, and optoelectrical applications. Both polymer and
inorganic nanowires have been successfully synthesized using
either MCM-41 or SBA-15 as the templates. A simple chemical
methodology for the formation of uniform Ag nanowires within
mesoporous silica SBA-15 has been developed recently [32]. This process
involves AgNO3 solution impregnation followed by thermal
decomposition. Transmission electron microscopy studies on these
samples show that these continuous Ag nanowires are made of long
polycrystalline domains. They have uniform diameters of 5 - 6 nm, and
large aspect ratios between 100 and 1000. This process represents a
viable approach for synthesizing uniform metallic nanowires (Au, Pt) and
may be applicable for making other inorganic nanowires. For example, Ge
nanowires has been successfully synthesized within the meso-channels of
MCM-41 .