NANOTECHNOLOGY

Nanotubes and Nonowires

Nanotubes and Nanowires present a vast amount of opportunities in basic science

and commercial developments. They are indeed one of the most exciting and promising

material originated with the nano revolution. Synthesis and characterization of nanotubes

and nonowires and constitute an important part of nanoscience . In the present paper the

preparation of aligned C-nanotubes bundles and Y-junction nanotube by the pyrolysis of

appropriate organic precursors has been depicted.

The aligned bundles are useful for field emission display while the Y-junction

nanotube are likely to be useful as nanochips since they exhibit diode properties at the

junction. By making use of C-nanotubes, nanowires of metals, metal oxides, and GaN

have been obtained. Both the GaN nanowires show excellent photoluminescence

characteristics.
Introduction

Soon after the laboratory preparations of C60 and C70 were reported CNT were

discovered as a microscopic wonder. Since then there has been considerable work on CNT’s.

Multiwalled & single walled CNTs have been prepared by variety of methods and several unique

properties as well as applications were discovered.

In this study there are several new routes are involved in the preparation of

CNT’s by using organometallic precursors such as metallocenes. The routes enabled not only the

preparation of MWNT & SWNT but also that of aligned nanotube bundles. The study also

involves the synthesis of y-junction nanotubes, which are expected to be crucial components in

nanoelectronics. The present study involves the synthesis and characterization of aligned

nanotube bundles and y-junction nanotubes.

Carbon nanotubes can be usefully employed for the synthesis of other

nanomaterials. Thus, metal nanowires can be made inside SWNT’s (single walled carbon

nanotubes). To prepare CNT’s and CN wires of several metal oxides as well as that of GaN, The

CNT is used as template. GaN is very important material today.

Experimental preparation of aligned MWCNT bundles by ferrocene

pyrolysis
Experimental set-up is shown in fig.

It consists of stainless steel gas flow lines and a two-stage furnace system fitted

with a quartz tube. The flow rate of the gases was controlled using UNIT mass flow controller.

A known quantity (100-gm.) of ferrocene (presublimed to 99.99% purity) was

taken in a quartz boat and placed at the center of first furnace. The part of the quartz tube

containing the ferrocene was heated by raising the temperature of first furnace to 673 k at

controlled heating rate. Argon (Ar) gas was passed through the same quartz tube at the desired

rate. The ferrocene sublimed and the vapor was carried by argon gas into the second furnace,
maintained at 1373 k, where pyrolysis occurred. Large quantities of carbon deposits accumulated

at the inlet of the second furnace.

The main variables in the experiments were the rate of heating of ferrocene, the

rate of flow of Ar gas and the pyrolysis temperature.

To get aligned carbon nanotube (CNT) bundles, a typical heating rate of 50 k/min

of the first furnace and the Ar flow rate of 1000 standard cubic centimeter per minute (sccm) were

maintained.

To get compact aligned carbon nanotube (CNT) bundles C2H2 (50-100 sccm)

was incorporated during the sublimation of ferrocene. These carbon deposits, mainly containing

carbon nanotubes, were examined by a Lieca S44I scanning electron microscope (SEM) and a

Jeol 3010 transmission electron microscope (TEM).

Pyrolysis apparatus for synthesis of aligned CNT bundles

RESULTS AND DISCUSSION

Aligned carbon nanotubes bundles

In fig. Showing the SEM image of nanotubes obtained by carrying out the

pyrolysis of ferrocene at 1373 k with a fast heating rate of ferrocene (100 k/min) and a high flow

rate of Ar (1000 sccm).

The images in fig, which are recorded in two directions with respect to axis of

nanotubes, clearly reveal the extraordinary alignment.

TEM image of these nanotube reveal that they are multiwalled, some of them

partially filled with metallic iron.

SEM images of aligned nanotubes obtained by the pyrolysis of ferrocene at 1373

K and 1000 sccm Ar:

(a) and (b) shows views of the aligned nanotubes along and perpendicular to the axis of

the nanotubes.
 (c) shows the SEM image of aligned-nanotube bundles obtained under a flow of C2H2(5sccm) and
Ar(1000sccm); and (d) shows the TEM image of densely packed aligned nanotubes obtained in the
presence of a higher proportion of C2H2 (85sccm) in the reaction mixture.

Pyrolysis of ferrocene at 1170 k under vacuum also yielded good quantities of

aligned nanotube bundles. When the rate of heating of ferrocene (1 k/min) and the flow rate of Ar

(10sccm) were low, fewer aligned nanotubes were obtained at a pyrolysis temperature of 1373 k.

The pyrolysis of ferrocene with acetylene is carried out by passing a mixture of

argon and acetylene through the quartz tube.

In fig. SEM image of aligned nanotubes obtained by the pyrolysis of mixture of

ferrocene and acetylene (5 sccm) at 1373 k in flowing Ar (1000 sccm). The alignment could be

further improved by increasing the flow rate of acetylene. The SEM image in fig. Shows the

densely packed aligned nanotubes. The TEM image in fig. Reveals how well aligned these

nanotubes are. The nanotubes in the bundles were generally closed and were 5-10 µm in length.

The experimental preparation of Y- junction carbon nanotubes.

It is similar to one describe for the synthesis o aligned nanotube bundles with an

addition thiophene bubbler attached to hydrogen gas line.

A known quantity of metallocenes was sublimed in the first furnace and carried

along with a flow of Argon(Ar) gas to the pyrolysis zone in he second furnace. Simultaneously

hydrogen (H2) was bubbled through thiophene and was mixed with the Argon-metallocenes vapors
at the inlet of the furnace and carried to the pyrolysis zone. Pyrolysing these mixed vapors at 1273

K yielded junction nanotubes. Several experiments were carried out by varying the flow rate of Ar

and H2 between 100-200sccm and 150and 50sccm (sccm = standard cubic centimeter per minute)

resp. The pyrolysis of Ni/Fe phthqalocynanine mixture with thiophene was carried out in a similar

manner taking phthalocyanines instead of metallocenes. Carbon deposits accumulating at the inlet

and outlet of the second furnace were examined by TEM and other technique.
Pyrolysis apparatus for Y-junction nanotubes

Result and Discussion :-

Y- junction carbon nanotubes

Carbon deposits obtained from the pyrolysis of cobaltocene –thiophene

mixtures shoed Y-junction nanotubes both at the inlet and outlet ends of the second furnace. In fig.

It is shown that Y-junction nanotubes obtained when the flow rates of H2 and Ar were 100 sccm

and 150 sccm resp. The diameter of the inner core of the nanotubes is 20 nm and the outer diameter

is 50 nm. Multiple junction are found in the nanotubes at these flow rates. The formation of

multiple junctions suggests the possibility of multiple tunnel devices in a single carbon nanotube.

When the H2 flow rate was increased to more than 200 sccm, there was no significant change in

the features of the nanotubes. At low flow rates of H2 (less than 25 sccm), no junction nanotubes
were found. When Ar was bubbled through thiophene instead of H2, there was a greater proportion

of amorphous carbon and the junctions obtained were not of good quality. The interlayer separation

of the graphitic layer as reveled by HREM as well as electron diffraction (ED) pattern is ~ 3.4 A0.

the graphitic layers are seen parallel to the corners of the junctions although fishbone-type stacking

is also present. The presence of graphite layers parallel to the junction is however noteworthy.

More detailed studies employing HREM as well as chemical analysis are required to understand the

structure and chemical constitution of the junction. Pyrolysis of ferrocene-thiophene mixtures

showed the presence of Y-junction predominantly in the deposits collected at the outlet ends when

the H2 flow rate used was 25 sccm, that of Ar being 225 sccm. The presence of junctions in the

inlet region was rare. The flow rate of H2 was crucial in the formation of junctions. The use of Fe-

and Ni- phthalocyanines instead of metallocenes also yields Y- junctions, with a Ni-

phthalocyanine-thiophene mixture at a H2 flow rate of 50 sccm and that of Ar 200 sccm. when the

flow rate of H2 and Ar were 150 100 sccm resp., multiple junctions formed continuously.

TEM image of Y-junction nanotubes obtained by the pyrolysis of cobaltocene-

thiophene mixtures under flow of H2 (100 sccm) and Ar (150 sccm) (a), and by the pyrolysis

of thiophene over the Ni/Sio2 catalyst under flow of H2 (50 sccm) and Ar (200 sccm) (b).
 The pyrolysis of thiophene was carried out over Ni/sio2 prepared by the following

procedure—

About 2.4 g Nickel acetate (corresponding to 0.01mol ) was dissolved in 5ml of

acidified ethanol followed by the addition of 2ml of tetraethyl orthosilicate (TEOS) and stirred for

5 min. To this homogeneous solution, 1.5 ml of HF (38% ) was added dropwise. And the resultant

mixture was stirred at 323K for 24 hr. , calcined at 623 K for 2hr and reduced in H2 and reduced in

H2 atmosphere for 2hr . The temperature was subsequently raised to 1273K and thiophene vapors

were passed over the catalyst for 20 min , by bubbling H2 (50 sccm) through the thiophene. The

sample collected from the boat was observed under the microscope, similar experiments were also

carried out with a Fe/SiO2 catalyst.

Preparation of metal nanowires

Metal nanowires were produced by two different methods. In the first method

the pyrolysis of metallocenes (e.g. ferrocene) at 1173 K under vacuum (10 –5 torr) to yield carbon

coated metal (e.g. iron) nanowires. In the second method., there is production of nanowires of Au,

Ag, Pt and Pd (1.0-1.4 nm dia) in the capillaries of SWNTs were produced by the DC arc discharge

method using a composite graphite rod containing Y2O3 (1 at %) and Ni (4.2 at %) as the anode

and a graphite rod as the cathode, under a helium pressure of 660 torr with a current of 100 A and

30 V. The web produced from the Arc- discharge predominantly contained SWNT bundles and

amorphous carbon, along with metal encapsulated carbon particles. Purification of the Web to

produce highly pure SWNT’s was carried out as follows. The as-produced web containing SWNT’s

was heat treated at 573 K in air for 24 h to remove the amorphous carbonaceous materials . The

heat treated material was stirred with concentrated nitric acid at 333k for about 12 h and washe3d

with distilled water to remove the dissolved metal particles. The SWNT material so obtained was

suspended in ethanol by using an ultrasonicator and filtered through a micropore filter paper (0.3

micro m) from Millipore to remove the polyhedral carbon particles present. The product was dried
at 423K for about 12 h. Purified SWNT samples so obtained were3 heat treated at 623 K for 30 min

to remove the acid sites on the surface of the tubes. this treatment is known to open the nanotubes.

High resolution electron microscopic (HREM) observations were carried out to confirm these are

indeed purified SWNT samples.

In order to prepare gold nanowires, 5 mg of purified SWNT’s was

mixed with ~10mg of Haucl4.xH2o and mixture dried in a 10 mm diameter quartz tube at 373 K

for 2h under vacuum (10 –3 torr) . The quartz tube was sealed under vacuum and heated at 673 K

for 20 hours. In order to prepare platinum nanowires a mixture of SWNT’s (5 mg) with

H2PtCl6.6H2O (10 mg) was dried at 393 K for 2 h under vacuum and the sealed quartz containing

the mixture heated in a furnace at 773 K (M.P. of H2PtCl6.6H2O is 333 K) for 20 h. In a similar

manner , PdCl2 (10 mg) was mixed with the SWNT’s (5mg) and heated at 373 K under vacuum.

The sealed tube was maintained at 873 K (decomposition temp of PdCl2 is 773 K) for 20 h. In all

sealed tube reactions, temperature was maintained at ~ 100 K above the decomposition or melting

point of the respective metal salt. After treatment with metal salts, the sealed tubes were broken

open and the product treated with hydrogen at 723 K for one h to reduce the metal salt present. The

hydrogen treatment was not found to be essential in the case of gold nanowires. In order to prepare

Pt. Nanowires it was employed a simple solution method as well. The mixture of SWNT’s (5 mg),

H2PtCl6.6H2O (10 mg) was refluxed in concentrated HCl or HNO3 (2 ml) for 1 h. It was also

attempted to prepare metal nanowires by sonochemical means, wherein SWNT’s in AgNO3

solution were sonicated (35 MHz ultrasound treatment ) for few hours in a hydrogen atmosphere. It

should be noted that SWNTs generally get filled by the metal salt/metal through the open ends.

The products obtained from the various processes discussed above were dispersed in carbon

tetrachloride and deposited onto holey carbon copper grids for transmission electron microscope

(TEM) observations. Plasmon absorption bands of the dispersions of the nanowires in alcohol

were recorded using a Hitachi U3400 spectrometer.

 Results & Discussion

In fig it was showed a TEM image which reveals the presence of large number of

gold nanowires obtained from the sealed tube reaction. The image clearly shows extensive filling of

SWNT tubes. The length of the gold nanowires is in the range of 15-70 nm and the diameters in the

range 1.0-1.4 nm. Detailed Tem observations show that the extent of filling of Au nanowires inside

the SWNTs is in excess of 50 %. Selected area electron diffraction (SAED) patterns taken from the

region of nanowires (see inset fig ) shows diffuse rings due to small polycrystalline metal particles.

The diffraction rings corresponds to the (111) and (002) reflections of gold. In some nanowires,

however it was found that the metal to be single crystalline as shown in the HREM image of fig.

This image reveals the resolved lattice of gold with a spacing of ~ 0.23 nm, corresponding to the

(111) planes. Polycrystalline Au aggregates could be transformed into the single crystalline formed

by suitable annealing. Platinum nanowires obtained by the sealed tube reaction are ~ 90 nm long

and ~ 1 nm is diameter. Long nanowires of Pt (~70 nm long and ~ 1 nm diameter) were obtained by

the solution method as well. Palladium nanowires could also be obtained by the sealed tube

reaction, but these were not as long as those of gold or platinum. Silver nanowires could be

obtained by heating the SWNT’s obtained after sonnication in AgNO3 solution at 623 K for 1 h, in

a Ar-H2 atmosphere.
 (a) TEM image of Au nanowires inside SWNTs obtained by he sealed-tube

reaction and (b) HREM image showing the single crystalline nature of some of the Au

nanowires. Inset in (b) shows an SAED pattern of the nanowires.

It was recorded the electronic absorption spectra of dispersions of gold nanowires

in ethanol. The spectra show transverse and longitudinal plasmon absorption bands. While the

transverse absorption band (~ 520 nm) does not vary with the aspect ratio of Au nanowires, the

position of the longitudinal absorption band varies markedly with the aspect ratio and medium

dielectric constant.

Discomposition of the observed band envelopes indicates that the dispersions of Au nanowires

are characterized by the bands around 670, 860 and 1150 nm due to the longitudinal absorption.

These bands indicate that there is a distribution of aspect ratios in a nanowires dispersion, with

the aspect ratio corresponding to the longest wavelength being rather large. It was estimated that

the range of aspect ratios in the nanowire dispersions examined to be 3-6. Clearly, more detailed

studies of the plasmon bands of metal nanowires would be of value.

 Conclusion

Nanotubes and nanowires present a vast amount of opportunities in

basic science and commercial developments. They are, indeed one of the most exciting and

promising materials originated with the nanorevolution. However, there are still some problems to

tackle, among them the need for improvements in synthesis techniques so that nanotube production

may be scaled upto tones per day.

The synthesis method has the benefit of giving less graphitic carbon in

the product and thus being a much cleaner method for synthesizing smaller quantities of nanotubes.

For the study and characterization of nanotubes nanoscopic

techniques capable of imaging materials with a resolution are used successfully with desired

results. These include SEM,TEM,HRTEM etc.

References:

Journals :-

1. Journal of Chemical Science

Solid State and Material Chemistry

Vol. 113 No. 5 and 6 , Oct. –Dec. 2001.

2. Nandini Chemical Journal

Vol. 7, issue 12, Sept.,2000

Vol. 8, issue 1, Oct., 2000

Vol. 8, issue 2,Nov.,2000

Papers:-

1. Carbon Nanotubes- A Brief Review

Pedro M.F.J. Da Costa, Malcolm L.h. Green

Inorg. Chemistry Laboratory, Uni. Of Oxford.

2. Synthesis of Carbvon Nanotubes Into Large Scale Functional Devices

 Hongjie Dai, Calvin Quate, Charles Marcus, Thomas Kenny Stanford

University.

3. Physical properties of CNT

Davids Tomanek, Thomas A. Adams

4. Nanotubes and Nanowires

5. Dr. C.N.R. Rao and A. Govindaraj

6. Solid state and structural Chemistry Unit, IISc . Bangalore. India.

5. Production of Single WCN in reduced Gravity Environment

6. 1999, Project Final Report Edward A. Vancise.

Websites from Internate.