CHEMICAL VAPOR DEPOSISITON

PHYS 450- Advanced Lab

Thushani De Silva
PHYS 450
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Contents
List of figures ................................................................................................................................... 2
Introduction .................................................................................................................................... 3
Method ........................................................................................................................................... 4
Results, Observations and discussion ............................................................................................. 7
Conclusion ....................................................................................................................................... 9
Bibliography .................................................................................................................................. 10
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List of figures
Figure 1 : CVD system which is used to grow MWCNT ................................................................... 4
Figure 2: The CVD setup .................................................................................................................. 4
Figure 3: a) SiO2 pieces, b) Optimal growth area of MWCNT ......................................................... 5
Figure 4: Chemicals used for the precursor .................................................................................... 5
Figure 5: one hour growth of MWCNT using CVD .......................................................................... 7
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Introduction

With the rapid depletion of natural resources, the world has turned to material science, looking
for solutions to replace conventional methods of energy harvesting and storage mechanisms with
more effective and efficient methods. Pressure from environmental activists, demand for green
energy solutions has further motivated scientists to explore novel materials for the vast variety
of industrial applications.
Due to this increase attention towards materials processing technology, growing solid thin-films
has become popular in materials physics, with the motivation of investigating nanoscale
applications of certain materials. One of the widely used methods for applying solid thin-films
coatings to surfaces is the Chemical Vapor Deposition technique (CVD). This technology is also
used to produce high-purity bulk materials and powders, as well as fabricating composite
materials via infiltration techniques. It has been used to deposit a very wide range of materials
including carbon nanotubes, which itself made a huge uproar since it’s discovery in late the 90s
(Creighton & Ho, 2001) (Instruments, n.d.).
A typical CVD system is functioned by flowing a precursor gas or gasses into a reaction chamber
containing a heated substrate. Once the chemical reactions occur on and near the hot surfaces
of the substrate, a thin film starts to grow on the surface. In the meantime, the by-products are
exhausted out of the chamber along with unreacted precursor vapor by a constant flow of gas.
However due to the diversity of usage of CVD, there are many variants of this technique, such as
CVD done in hot-wall reactors and cold-wall reactors, at sub-torr total pressures to above-
atmospheric pressures, with and without carrier gases, and at temperatures typically ranging
from 200-1600°C. As enhanced CVD systems, the deposition rates can be increased as well as
lower the deposition temperature using plasmas, ions, photons, lasers, hot filaments, or
combustion reactions. There are also many derivatives of the CVD terminology, such as metal-
organic chemical vapor deposition (MOCVD or organo-metallic chemical vapor deposition
(OMCVD) (Creighton & Ho, 2001).
However, the startup cost for CVD procedure could be high for commercial applications. In
comparison there are several other techniques used to deposit metals such as thermal spray
coating using combustion torch, electric arc and plasma sprays and vapor deposition using ion
plating, ion implantation, laser surface alloying, sputtering and sputter deposition. Still, even for
the alternative methods, the startup cost is bit high. Also, commercial availability might be limited
in certain cases (Freeman, 1995).
In this laboratory work, the CVD system that’s being used is located in room 407 which includes
a horizontal tube furnace to grow Multiwalled Carbon Nanotubes (MWCNT) on a silicon dioxide
substrate.
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Method

Pressure
gauge

Tube
furnace

Oven Scale

Figure 1 : CVD system which is used to grow MWCNT

The CVD system described in this experiment is illustrated in figure 1. The glass tube inside the
oven is the tube furnace where the Silicon Dioxide (SiO2) substrate is placed for MWCNT to grow.
The first step is to lightly clean the tube furnace with acetone, to remove the remaining precursor
vapor on the tube wall, from the previous run. However, it’s important to not to remove
amorphous carbon from the tube’s wall since it optimizes the growth of MWCNT. Once the tube
furnace is ready, it is inserted into the oven as showed in figure1.

Figure 2: The CVD setup

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After the tube furnace is inserted into the oven, the gas inlet is connected to the furnace and
position it in such a way, that the end of the gas inlet tube is 5cm away from the oven entrance.
Next, the boat containing the cleaned SiO2 pieces (using acetone) is placed in the reaction zone,
where the MWCNT growth is optimum.

Optimal growth area

a b
Figure 3: a) SiO2 pieces, b) Optimal growth area of MWCNT

Then the gas outlet is plugged into the furnace, isolating the chamber from the external
environment. After the system has been setup similar to figure 2, the reaction chamber is
pressurized by flushing it with Argon (Ar) for 5 minutes at 100sccm (the brown tank). This is to
remove the atmosphere in the reaction chamber and create an inert atmosphere to heat it. After
5min, the oven is turned on and let the temperature rise to 7900C. Once it has reached the
desired temperature, the chamber is flushed with Ar for 45min at 25-30sccm.
After 45min has passed, a glass syringe, containing the precursor is placed on the delivery system
and connected to the carbon source feed of the chamber (capillary tube next to the gas inlet).
The precursor that is being used is a mixture of Ferrocene/ Xylene with the concentration of
0.01gml-1.

Xylene
Ferrocene

precursor

Figure 4: Chemicals used for the precursor

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Once the syringe is connected to the source feed of the reaction chamber, Ar is turned off and
then a mixture of Ar/H2 (85 % Ar) is turned on at 25-30sccm (the green tank) as well as the tank
with air (yellow tank), which is kept at 2.5sccm.
After the gas has been changed, the precursor is advanced towards the inlet of the chamber and
leave the system for about 10min. Then the delivery system is turned on and allow it to pump
the precursor into the reaction chamber. The system pumps the solution at a rate of 12mlhr -1.
Once the precursor reaches the end of the capillary tube, the timer is switched on to keep a track
of the growth time. In this experiment, the growth time of MWCNT sample was 1hr.
After the growth is complete for the desired reaction time, the precursor is removed from the
capillary tube. Then the syringe is removed from the carbon source feed of the chamber the end
is sealed with a rubber knob as it was before. Next step is to turn off the oven and leave the
chamber to cool down. The gas flow needs to be changed back by turning off both air and the
Ar/H2 mixture and turning on the Ar tank at 25-30sccm. Once the temperature reaches 2000C, Ar
gas supply can be turned off completely and let the system cool further.
After the chamber has cooled down to the room temperature, the MWCNT sample can be taken
out from the furnace.
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Results, Observations and discussion

Figure 5: one-hour growth of MWCNT using CVD

Figure 5 shows the resulted 1-hour growth of vertically aligned MWCNT using the CVD system
which has a thickness close to 1.5cm. Carbon nanotubes (CNT) can be deposited on various
substrates namely quartz, Fe-deposited silicon and quartz, silicon nitride-deposited silicon,
copper foil, and stainless steel mesh using thermal chemical vapor deposition technique
(Handuja, et al., 2010). Since contact with a substrate can modify the nanotube properties, the
choice of a substrate is important (Soares & Jorio, 2011). The substrate we have used for our
experiment is SiO2. We were able to observe layers of MWCNT, where ever the chemical was
able to access SiO2 substrate, even around the sides and underneath the SiO2 pieces. Since carbon
nanotubes (CNT) do not grow on Si, it’s possible to pattern the substrate surface with SiO2 and Si
(Y., et al., 2003). It’s also important to clean the SiO2 pieces with acetone before placing them
inside (Freeman, 1995).
Most commonly used CNT precursors are methane, ethylene, acetylene, benzene, xylene and
carbon monoxide. The molecular structure of the precursor has a detrimental effect on the
morphology of the CNTs grown. Apart from the popular hydrocarbons mentioned above, CNTs
have also been synthesized from many other organic compounds, especially from polymers
(Kumar, 2011). The precursor we have used for this experiment is a mixture of Ferrocene/ Xylene
with the concentration of 0.01gml-1. The concentration is one of the important facts that
determine the growth of MWCNT since changing the concentration also changes the growing
conditions. Also, lower catalyst concentrations exhibited SWCNT growth (at 850 C and above),
whereas higher concentrations favor MWCNT growth (Kumar, 2011). For the above-mentioned
concentration of Ferrocene/ Xylene, the optimal temperature for the MWCNT synthesis is 7900C
and the optimal area is as illustrated in figure 3 b). Ferrocene is a good source to provide Iron as
the catalyst and xylene is the carbon source. Since the system incorporated an air assisted vapor
phase catalyst delivery CVD method, the growth rate has enhanced (Kharlamova, 2017).
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Once the system was cooled down and the MWCNT sample was taken out from the tube, it was
possible to observe that several layers of amorphous carbon, on the wall of the furnace. The
presence of amorphous carbon is beneficial for the growth of MWCNT (even though it might
contaminate the sample a bit, it’s possible to remove amorphous carbon using heat treatments
and/or acid treatments). In fact, an amorphous carbon film can be used as a catalyst layer to
grow metal-free CNTs (Seo, et al., 2010).
Temperature is another important factor for synthesizing CNTs since the reaction does not occur
at low temperatures. It has been noticed that camphor did not decompose below 5000C. Even at
5000C, the CNT growth is quite low. Also at higher temperatures, the metal particles were
gradually pronounced in the samples, preferably encapsulated at the CNT tips (Kumar, 2011).
For controlled growth of CNTs by CVD, the vapor pressure of the hydrocarbon in the reaction
zone is another important parameter. For gaseous hydrocarbons, a desired vapor pressure in the
CVD reactor can be maintained by limited gas-flow rate (Kumar, 2011). Also after the synthesis
of MWCNT, it’s important to keep a constant gas flow of Ar (at a rate of 25-30sccm in our
scenario) to make sure that any other reaction would not occur during the cooling down and to
remove the by-products of the MWCNT synthesis.
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Conclusion
Once the initial setup is built, CVD procedure is a much convenient technique for growing solid
thin-films compared to conventional methods such as plating, cladding and anodizing. This
method is also low risky in terms of environmental, health, and safety (Freeman, 1995).
In this lab-work, we were able to achieve a 1-hour growth of MWCNT sample. The thickness of
the sample is closed to 1.5cm. CVD system is a better technique to produce high quality, high-
performance, solid materials both for research and industry applications.
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Bibliography
Creighton, J. R. & Ho, P., 2001. Chemical Vapor Deposition. s.l.:ASM Internationa.
Freeman, H. J., 1995. Industrial Pollution Prevention Handbook. s.l.:McGraw Hill, Inc..
Handuja, S., Srivastava, P. & VD, V., 2010. On the Growth and Microstructure of Carbon
Nanotubes Grown by Thermal Chemical Vapor Deposition. Nanoscale Research Letters, pp.
1211,1216.
Instruments, N. S., n.d. Nano Science Instruments. [Online]
Available at: https://www.nanoscience.com/applications/education/overview/cnt-technology-
overview/
[Accessed February 2018].
Kharlamova, M. V., 2017. Investigation of growth dynamics of carbon nanotubes. Beilstein
Journal of Nanotechnol., Volume 8, p. 826–856.
Kumar, M., 2011. Carbon Nanotube Synthesis and Growth Mechanism. s.l.:s.n.
Seo, J. K., Ko, K.-h. & Kim, J., 2010. Growth of metal-free carbon nanotubes with amorphous
carbon catalyst layer on glass substrates by microwave plasma enhanced chemical vapor
deposition. Hong Kong, China, IEEE.
Soares, J. S. & Jorio, A., 2011. Study of Carbon Nanotube-Substrate Interaction. Journal of
Nanotechnology, Volume 2012.
Y., J. J., R., V. & P., M. A., 2003. Mechanism of Selective Growth of Carbon Nanotubes on SiO2/Si
Patterns. Nano Letters, 2003, p. 561–564.