NANOTECH INSIGHTS

Spotlight
Carbon Nanobuds: Are They Superior to than the conventional emitters due to the presence
CNTs? of atomically sharp tips (higher the number of tips/
curved surfaces, better is the field emission). Recently,
The immense interest in carbon nanotube research led
Samsung has demonstrated its new working e-paper
to the discovery of a novel hybrid carbon material named
display which is the first in the world to use carbon
Carbon NanoBuds (CNB) in the year 2006. Unlike the
nanotubes. The display does not require any backlight
nano peapod structure, where the fullerene molecules
and retains the image for a longer duration. Though
are encapsulated into the hollow space of carbon
FEDs rank first among all the realizable applications
nanotubes, CNB is a novel hybrid carbon nano material
of CNTs, CNBs now offer better field emission (lower
where the fullerene molecules are covalently bonded to
field threshold and higher current density) due to the
the outer wall of single walled carbon nanotubes. The
increase in the number of curved surfaces on CNTs
covalent bonding of reactive fullerenes on inert SWCNT
because of the attached fullerene molecules. (Fig. 2)
walls presents interesting applications. The discovery
of this peculiar hybrid structure was reported in the Composites: The chemically inert surface of SWCNTs
journal Nature Nanotechnology in 2007 by a Finnish (sp2 bonding) makes them slide/debond easily in the
research group lead by Professor Esko Kauppinen. (polymer/metal/ceramic) matrices. This, in turn, is
Similar to the discovery of nano peopod, this too was
discovered accidentally while analyzing the synthesized
SWCNTs by TEM (Fig. 1). When examined with a low
magnification microscope, the SWCNTs seemed to
have a coating of amorphous carbon clusters. However,
a closer examination with a higher resolution electron
microscope revealed that most of the clusters were
actually fullerenes. The observed fullerene coating on
the SWCNTs was a big surprise as the previous attempts
made by other researchers to physically combine CNTs
and fullerenes were unsuccessful.

Nanobuds Provide a Unique Solution

Field emission: It is well known that the carbon Fig. 2: Carbon nanobuds show the lowest turn-on voltage
nanotubes show enhanced field emission properties compared to fullerenes and SWCNTs (1, 2)

(a) (b) (c)

(d)

5nm
50nm

SWNTs seemingly covered Surface of the SWNTs covered by Surface of the SWNTs combined
by amorphous carbon spherical structures with a fullerene

Fig. 1: TEM images of CNB with a) 50 nm, b) 5 nm and c) 2 nm resolutions d) STM topographic image of a
fullerene on the surface of a SWCNT. The fullerene appears as bright area on SWCNT
(Images reprinted with permission from Macmillan Publishers Ltd: [Nat. Nanotechnology, 2, (2007) 156])

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 research s u mmary

reported to bring down the mechanical strength of the and light amplification (5). In addition, the concentration
composites. The challenge of dispersing/ debundling of the fullerene molecules in the nanobuds can be
the CNTs is also well known to researchers working on controlled to limit the output intensity of the device
the development of CNT based composites. Use of or to protect portions of a device from damage due
carbon nanobuds can alleviate these problems due to to excessive electromagnetic energy. This can be
the improved dispersion and higher strength possible, used in the field of communication and measurement
as mentioned below. technology.
• Dispersion: The attached fullerene molecules Recently, the fabrication of carbon nanobud deposit,
weaken the bundling adhesion forces leading to in which the nanobuds are bonded to each other
better dispersion in the composite matrix. through the fullerene molecules has been patented (6).
The deposit or the film can be fabricated by various
• Strengthening: The fullerene bud can act as a
processes and it can be used as an electrical device
molecular anchor and prevent slipping of SWCNTs
like a transistor, field emitter, transparent electrode,
in composites and, thus, can improve the strength
capacitor, solar cell and display element or sensor.
of the composite. The strengthening effect of
CNBs show superior capacitance compared to
carbon nanobuds on the mechanical properties of
other carbon based electrodes, making them ideal
different matrices is yet another interesting study
candidates for the manufacture of super capacitors
that may reveal new strengthening mechanisms and
with greater energy storage capacity (Fig 4)
microstructures.
Fabrication of Devices: The advantages of fabricating
devices with CNBs are illustrated in Fig. 3. Devices
made of CNBs can be manufactured directly, thus
avoiding potential damage to carbon nanostructures
during processing steps like purification and
dispersion. The carbon nanobud molecules provide
an exceptional platform for anisotropically functioning
optical or optoelectronic devices .The fullerene
molecule attached to the tubular carbon molecule
can interact with electromagnetic radiation through
relaxation and/or excitation of carbon nanobud
molecule. This can be used to fabricate a device
for saturable or reverse saturable absorption of Fig. 4: Carbon nanobuds showing superior capacitance
compared to other carbon-based electrode materials.
electromagnetic radiation for polarized optical emission
Adapted from (7) and *(8)

Fig. 3: Advantages of fabricating devices with carbon nanobuds instead of nanotubes

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NANOTECH INSIGHTS
Currently, a Finnish nanotechnology-based electronic
component company named Canatu (a spin-off from the
Helsinki University of Technology, Finland) is working on
the development of industrial scale production of high
purity carbon nanobuds and NanoBud thin films tailored
for specific industrial applications.
Synthesis, Characterization and
Applications of Carbon Nanobuds
NanoBuds are synthesized by using in situ generated
catalyst (Ferrocene reactor) and pre-made catalyst
(Hot Wire Generation Method). These two methods
are originally used to synthesize single wall carbon
nanotubes, except for the presence of optimal
concentrations of H2O vapour and CO2, which in
turn along with the reactor temperature control
the density of fullerenes on the nanotubes. Fig. 5
presents the schematic for synthesis of CNBs and the
characterization techniques that are used to study the
properties of CNBs.
Fig. 5: Flow chart for synthesis and characterization of
carbon nanobuds
Appications of CNBs
• Flexible transparent electrodes in touch sensors,
solar cells and displays • Field emission films in
displays • Charge storage layers in supercapacitors
• Saturable absorbers in pulsed lasers • Electron-hole
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generators in solar cells • Semiconductor films in field
effect transistors
Next Generation NanoBuds for Gas Storage
Fig. 6: Structure of periodic graphene nanobuds
(Reprinted with permission from [Nano Lett., 9(1), (2009),
250-256] 2008, American Chemical Society)
Nebraska Center for Materials and Nanoscience, USA
has proposed a new hybrid nano structure called
Periodic Graphene NanoBud (PGNB). PGNB has the
C60 buckyballs covalently attached to a graphene
monolayer forming a periodic lattice on the monolayer
due to which the interlayer distance between the
graphene sheets is enhanced four-fold (12.5 Å). The
covalent bonding between C60 and graphene in PGNB
prevents the aggregation of C60 bucky balls and
allows the network structure to be intact. The very high
surface area and interlayer distance of PGNB structures
studied by computational methods show that PGNB is a
promising carbon material for gas storage.
References:
1. A.G. Nasibulin et al, “A Novel Hybrid Carbon
material” Nature Nanotechnol. 2, (2007) 156
2. H. Mizukami et al, “Fabrication and Field Emission
Properties of C60 Nanorod Formed by Spin-Cast
Treatment”, Japanese Journal of Applied Physics,
44 (2005) L851-L853 
3. Y. Zhang et al, “Progress of Electrochemical
capacitor Electrode materials: A review” International
Journal of Hydrogen Energy, 34 (2009) 4889–4899
4. X. Wu et al, “Periodic Graphene Nanobuds” Nano
Letters, 9, 1, (2009) 250–256
5. D. Brown,” Uses Of Carbon Nanobud
Molecule And Devices Compromising The
Same”,WO2009/156596 A1(2009)
6. A. Roos, “A Deposit And Electrical Devices
Comprising The Same”, WO2009/056686 A1(2009)
7. D. Brown, Canatu, “Energy, Electronics and Beyond”
(2009), www.canatu.com
8. Y. Wang et al, “Supercapacitor Devices Based on
Graphene Materials”, Journal of Physical Chemistry.
C .113 (2009), 13103-13107
Contributed by I. Sophia Rani, CKMNT