MSE 318 Nano Materials

Homework 4

Daniel Corzo
134001

Exercise 5.6 - Why does nitric acid preferentially open the end of a closed carbon
nanotube? How would you make use of this knowledge to make (a) a carbon
nanotube pH meter (b) a vanadium oxide nanowire?
A carbon nanotube has two different structural regions, the sidewalls and the end
caps, both with different chemical reactivity. The curvature in the fullerence area is
much greater than that of the side walls and therefore more strained, making the
carbon-carbon bonds are more reactive on the end caps than those in the sidewalls.
When CNTs are treated with an oxidation acid (like nitric acid), carbolixyc groups (COOH) are formed almost exclusively at the end caps, and on defects on the side
walls.
HNO3 needs a long time refluxing in order to have an effect on the tubes, and it
cannot generate defect sites on the 6-6 ring boundaries, this limiting its effect only
for large strain sites and reducing groups, such as the end caps. The following
figure shows the effect of a H2SO4:HNO3 solution on a carbon nanotube, the open
ends being the effect of the nitric acid, while the sidewall defects are the effect of
the H2SO4.

a) On the Fabrication of a CNT pH meter

When the SWCTs are washed with a strong acid such as HNO3, they show carboxylic
groups near or on the ends, as well as on defects. These carbon nanotubes are
immobilized between a source and a drain on top of an APS sol-gel layer as shown

MSE 318 Nano Materials

Homework 4

Daniel Corzo
134001

in the picture below in order to create a p-type FET.

A CNT FET device such as the one shown above, when induced with a gate voltage,
shows increased or decreased current when dropping various pH solutions on the
glass substrate. This is due to the acceptance of electrons from the carbon
nanotubes by the protons in the drops, therefore inducing a positive hole in the ptype carbon nanotubes and contributing to increasing the current. This behavior is
the effect of the carboxylic groups on the surface of the CNTs induced by the
washing process (with acids such as HNO3).
The image below shows the different currents associated to different pH. Being able
to measure the current when a droplet of a certain pH is placed on top of the
device, would led to the measurement of its pH.

b) On the Fabrication of a Vanadium Oxide Nanowire

When the CNTs are functionalized with a mixture of H2SO4 and HNO3, carboxylic
and hydroxyl groups are formed mostly in the ends (therefore opening them) and on

MSE 318 Nano Materials

Homework 4

Daniel Corzo
134001

the defects along the walls of the nanotube, as we have discussed above. These
functional groups facilitate the dispersion of the carbon nanotubes and also serve as
centers of polymerization and condensation of vanadium oxy-tripropoxide.
The mechanism relies on the diffusion of atoms and/or ions at the interphase
between the reactants, the growth of vanadium oxide can go two ways: rolling
mechanism ad attaching oriented attachment growth mechanism.
The rolling mechanism involves three steps: 1) The vanadium-trihydroxide is
attached to the functional groups on the CNT and undergoes coordination expansion
due to nucleophilic reactions. 2) The condensation process continues and it results
in more ordered lamellar assemblies. 3) The lamellar sheets become loose at the
edges, and then roll themselves into nanotubes.
The attaching oriented attachment growth mechanism involves 2 steps: 1)
vanadium-trihydroxide condensation occurs at the functional groups on the surface
of the carbon nanotubes in a horizontal manner 2) the vanadium oxide grains are
extend the structure and crystallize, then forming a belt-like structure. These belts
then superimpose on top of each other in order to form VONRs.
Both of these mechanisms are shown in the images below, rolling mechanism on
the left, and the attachment oriented growth mechanism on the right.

Exercise 5.29 - Describe strategies that would allow you to place VLS active
catalytic nanoclusters at specific locations down the length of a semiconductor
nanowire to direct site-selective VLS growth of nanowire branches at the points that
you designated on the body of the nanowire.

MSE 318 Nano Materials

Homework 4

Daniel Corzo
134001

Exercise 7.9 - Devise a synthetic method for storing and retrieving information in a
colloidal crystal array?
By synthetizing monodisperse binary or tertiary microspheres in which each of the
components is associated to a different dye. The close-packed microspheres are
crystallized in a well arranged colloidal lattice, in which each of the spheres is able
to store and encrypt information in color code, and can then be deciphered as
needed.
In order for the system to work, the dyes in the different regions of the multilayered
spheres must be fluorescent and reachable by light of different wavelengths, so that
the color of a sphere in a particular plane can be read with a laser coupled to a
fluorescence confocal microscope.
One centimeter cube of the colloidal microspheres lattice can store up to 10 12 bits of
data. This storage medium can even be scaled up depending on the number of
readable colors in each one of the spheres in the lattice, therefore having a huge
potential in information technology.
Choosing polymer anchored dye combinations what ensure theres almost to none
energy transfer between the dyes and the stability of the dyes to the laser and
visible light are key requirements in order for the system to function properly.
The figure below shows two letters built through this process, both of them are in
the same position in the colloidal crystal, but have different dyes incorporated into
the different components of the microspheres.

MSE 318 Nano Materials

Homework 4

Daniel Corzo
134001

References
Farhad Forohar, C. W. W. M. K., 2010. Method of making functionalized carbon
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Kimberly A. Worsley, I. K. E. B. a. R. C. H., 2009. Functionalization and Dissolution of
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Seiji Takeda, 2007. A pH sensor based on electric properties of nanotubes on a
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Ying Wang, K. T. H. S. a. G. C., 2005. Synthesis and Electrochemical Properties of
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Zhaolong Li, X. Z. J. X. S. H. Q. Z., 2013. Carbon nanotube-induced formation of
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