Carbon, Vol. 33, No. 7, pp.

989-993, 1995
Coovrieht 0 1995 Elsevier Science Ltd
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0008-6223(95)00027-5

ONION-LIKE GRAPHITIC PARTICLES

D. UGARTE
Laboratbrio National de Luz Sincrotron (CNPq/MCT), Cx. Postal 6192,
1308 l-970 Campinas SP, Brazil;
Institut de Physique Experimentale, Ecole Polytechnique Ftderale de Lausanne,
1015 Lausanne, Switzerland

(Received 18 July 1994; accepted 10 February 1995)

Abstract-Nanometric graphitic structures (fullerenes, nanotubes, bucky-onions, etc.) form in different

harsh environments (electric arc, electron irradiation, plasma torch). In particular, the onion-like graphitic
particles may display a wide range of structures, going from polyhedral to nearly spherical. High-resolution
electron microscopy is the primary tool for studying these systems. On the basis of HREM observations,
we discuss the energetics and possible formation mechanism of these multi-shell fullerenes. The better un-
derstanding of the underlying processes would allow the development of an efficient production method.

Key Words-Graphite, fullerenes, HREM, nanostructures, electron irradiation

1. INTRODUCTION large-scale synthesis of nanotubes[4]. The central part

of the deposit consists of a black powder containing
The high melting temperature of carbon materials
a mixture of graphitic nanotubes and nanoparticles.
(~4000°K) has made difficult the preparation and
Although this procedure allows the generation of these
study of carbon clusters. In recent years, the field of
particles in macroscopic quantities, the purification of
nanometric carbon particles has found an unexpected
the different soot components (e.g., nanotubes) has
and overwhelming development. In a first step, the so-
not been easily performed. Centrifugation and filtra-
phisticated laser evaporation source revealed the ex-
tion methods have been unsuccessful, and a rather in-
istence of fullerenes, but with the limitation that their
efficient oxidation procedure (99Vo of the material is
study could only be performed in cluster-beam exper-
lost) has allowed the production of purified nanotubes
iments[l]. Second, in 1990, the current and simple
samples[l2].
electric arc_discharge[2] allowed the synthesis and
The electric arc is a transient phenomenon, where
study of these molecules by a large number of labo-
the region of the electrode producing the arc changes
ratories, generating a burst of revolutionary discov-
permanently all over the surface of contact. The gen-
eries. A wide family of nanometric graphitic systems
erated temperature gradients induce an important
may be synthesized by making slight modifications to
range of conditions for the formation of graphitic
the electric arc experiment (nanotubes[3,4], nanopar-
nanoparticles; this fact leads to wide size and shape
ticles[S71, metal-filled nanoparticles[8-lo], etc.).
distributions (see Fig. la). The particles usually display
High-resolution transmission electron microscopy
a clear polyhedral morphology, and a large inner empty
(HREM) is the technique best suited for the structural
space (3-10 nm in diameter). Macroscopic quantities
characterization of nanometer-sized graphitic parti-
of nanometric graphitic particles may be obtained by
cles. In-situ processing of fullerene-related structures
a thermal treatment of “fullerene black”[ 13,141; this
may be performed, and it has been shown that carbo-
method yields particles with similar structure to those
naceous materials transform themselves into quasi-
ones generated in the arc, but with a narrower size dis-
spherical onion-like graphitic particles under the effect
tribution, in particular located in the 5 10 nm range.
of intense electron irradiation[ 111.
The high-energy electron irradiation of carbona-
In this paper, we analyze the methods of synthesiz-
ceous materials produces remarkably symmetrical and
ing multi-shell fullerene structures and try to gather
spherical onion-like particles[ 1 I] (see Fig. lb, 2). These
some information about their formation mechanism.
particles are very stable under electron bombardment,
We also discuss some particularities of the energetics
even when formed by a small number of shells (2-4)
of onion-like graphitic particles. The understanding of
[ 151. The generation of these quasi-spherical graphitic
the parameters involved would allow the development
systems (nicknamed bucky-onions) is realized in situ in
of efficient production procedures.
an electron microscope. However, the particles are only
formed in minute quantities on an electron microscopy
2. SYNTHESIS OF MULTI-SHELL FULLERENES
grid, and their study may only be performed by trans-
mission electron microscopy-associated techniques.
The electric arc is the easiest and most frequently Two major structural aspects differentiate them from
used experiment to produce onion-like particles. A the graphitic particles discussed previously: (a) the
dc arc-discharge is used to generate a carbon deposit shape of the concentrical arrangement of graphitic lay-
on the negative electrode following the procedure for ers is a nearly perfect sphere, (b) the innermost shell

989
990 D. UGARTE

Fig. 1. High-resolution electron micrographs of graphitic particles: (a) as obtained from the electric arc
deposit, they display a well-defined faceted structure and a large inner hollow space, (b) the same parti-
cles after being subjected to intense electron irradiation (note the remarkable spherical shape and the dis-
appearance of the central empty space); dark lines represent graphitic layers.

is always very small, displaying a size very close to in the 0.2-I pm range, (b) small particles (<0.2 pm)
C6e (20.7-l nm) (see Fig. 2). also spherical in shape, but formed by concentric gra-
Onion-like graphitic clusters have also been gener- phitic layers. Unfortunately, no detailed HREM study
ated by other methods: (a) shock-wave treatment of of these particles was undertaken, but an apparent
carbon soot[l6]; (b) carbon deposits generated in a size effect connecting diamond and graphitic particles
plasma torch[l7], (c) laser melting of carbon within was insinuated. Recently, an interesting experiment
a high-pressure cell (50-300 kbar)[ 181. For these three also revealed a relation between ultradispersed dia-
cases, the reported graphitic particles display a sphe- monds (3-6 nm in diameter) and onion-like graphitic
roidal shape. particles. The nanometer diamond sample was obtained
In particular, the laser melting experiment produced by a chemical purification of detonation soot. The an-
two well-differentiated populations of carbon clusters: nealing treatment (1100-l 500°C) of nanodiamonds
(a) spheroidal diamond particles with a radial texture generates onion-like graphitic particles with a remark-
 Onion-like graphitic particles 991

is an example of the graphitization of a “hard carbon”

(when subjected to heat treatment, it yields irregularly
shaped pores or particles instead of extended flat gra-
phitic planes)[ 14,211.
In the case of carbon melting experiments[l6] and
electric arc[5,6], it has been suggested that the onion-
like particles are generated by the graphitization of a
liquid carbon drop. The growth of graphite layers is
supposed to begin at the surface and progress toward
the center (see Fig. 3a-d). Saito et al.[7] has suggested
a similar mechanism but, instead of liquid carbon,
they considered a certain carbon volume on the elec-
trode surface, which possesses a high degree of struc-
tural fluidity due to the He ion bombardment.
The progressive ordering from the surface to the
center has been experimentally observed in the case of
the electron irradiation-induced formation of the
quasi-spherical onion-like particles[25]. In this case,
the large inner hollow space is unstable under electron
Fig. 2. HREM image of a quasi-spherical onion-like graphitic bombardment, and a compact particle (innermost shell
particles generated by electron irradiation (dark lines repre- =C,,) is the final result of the graphitization of the
sent graphitic shells, and distance between layers is 0.34 nm).
carbon volume (see Fig. 3e-h).
The large inner hollow space observed in polyhe-
dral particles is supposed to be due to the fact that
able spheroidal shape[l9], and a compact structure the initial density of the carbon volume (drop) is lower
very similar to the bucky-onions generated by electron than graphite[7]. Then, in order to prepare more
irradiation[ 111. compact graphitic particles (smaller inner shell), the
starting carbon phase should have a density closer
to graphite (2.25 gr/cm2). This basic hypothesis has
3. FORMATION MECHANISM
been confirmed by subjecting nanodiamonds to a
In the preceding section, we have described differ- high-temperature treatment (diamond is much denser
ent experiments generating graphitic nanoparticles. As than graphite, 3.56 gr/cm’)[19]. Experimentally, it
for the case of fullerene synthesis, the procedures are has been observed that the formation of graphitic
rather violent (electric arc, plasma torch, shock waves, layers begins at the (111) diamond facets, then gener-
high-temperature treatment, electron irradiation, etc.) ates closed-surface graphitic layers, and subsequently
and clearly display the present incapacity of generat- follows the formation of concentric shells epitaxially
ing nanometric curved and closed graphitic systems by towards the center. At an intermediate stage, the onion-
standard chemical techniques. For the synthesis of like graphitic particles contain a tiny diamond core
CbO, it has been found that a temperature on the or- (see Fig. 2 in ref. [19]). This process yields carbon on-
der of or higher than 1200°C are necessary to anneal
the carbon clusters in the gas phase and efficiently
form Cm molecules[20]. In the case of the graphitiza-
tion process, the dewrinkling and elimination of de-
fects in graphitic layers begins at 2OOO”C[21]. The
extremely stable carbon-carbon bonds are responsible
for the high-energetic process necessary to anneal gra-
phitic structures. I a b d I
The formation mechanism of fullerenes and related
structures is not well understood. The fascinating high
t tet
1 1 tett t let t t let t
aspect ratio of nanotubes is associated to the electric ~~~~
field of the arc[7,22], but this fact has not yet been
confirmed and/or been applied to control their growth.
Moreover, the arc process generates simultaneously a
large quantity of polyhedral graphic particles. The for- Fig. 3. Schematic illustration of the growth process of a
mation of multi-shell graphitic particles from the gas graphitic particle: (a)-(d) polyhedral particle formed on the
phase by a spiral growth mechanism has also been sug- electric arc; (d)-(h) transformation of a polyhedra1 particle
gested[23,24], but no convincing experimental data of into a quasi-spherical onion-like particle under the effect of
high-energy electron irradiation; in (f) the particle collapses
a spiral structure has been reported. and eliminates the inner empty space(251. In both schemes,
The thermal treatment of fullerene black generates the formation of graphite layers begins at the surface and
nanometric polyhedral particles[ 131. This experiment progresses towards the center.
992 D. UGARTE

ions with a very small inner empty space, which con- 5 hexagons (non-planar structure with a bowl shape)
trasts with the polyhedral particles prepared by heat is a very floppy structure. This molecule is the basic
treatment of fullerene black[ 131. unit of CGO, and also the atomic arrangement present
at the corners of faceted giant fullerenes. It has been
observed by NMR that, at room temperature, it spon-
4. ENERGETIC!3
taneously presents a bowl inversion transition, with an
The elimination of the energetic dangling bonds energy barrier of only 440 meV[32]. Then, we may use
present at the edges of a tiny graphite sheet is supposed this value to get a bare estimation of the energy nec-
to be the driving force to induce curvature and closure essary to crash the 12 corners of a polyhedral graphitic
in fullerenes; this phenomenon is also associated with cage (containing the corannulene configuration) into
the formation of larger systems, such as nanotubes a spherical one, and it turns out to be of the same
and graphitic particles. order of magnitude that the gain in van der Waals
The remarkable stability of onion-like particles[l5] energy mentioned previously (~5 eV). This fact in-
suggests that single-shell graphitic molecules (giant ful- dicates that a global evaluation of multi-shell struc-
lerenes) containing thousands of atoms are unstable tures should be performed to answer the question of
and would collapse to form multi-layer particles; in the minimal energy structure of onion-like graphitic
this way the system is stabilized by the energy gain particles.
from the van der Waals interaction between shells From a different point of view, the sphericity of the
[15,26,27]. irradiation generated onion-like particles have also
Graphite is the most stable form of carbon at am- been attributed to imperfect shells with a large num-
bient conditions, and it is formed by the stacking of ber of defects[33].
planar layers. The extreme robustness of the concen- Concerning the possible arrangement of concentric
tric arrangement of spherical fullerenes led to the hy- defect-free graphitic cages, a polyhedral graphitic par-
pothesis that the quasi-spherical onion-like graphitic ticle has all the shells in the same orientation, so that
particles are the most stable form of carbon parti- all the corners (pentagons) are perfectly superimposed
cles[ 151. This controversy between planar configura- (see Fig. 4a). If the pentagons of the concentric shells
tion of the sp2 bonding in macroscopic graphite and are not aligned, the final shape of graphitic particles
the apparent spherical shape in nanometric system, has should be much closer to a sphere. In the spherical
attracted a great deal of interest[28]. Calculations of particles, an interesting issue is the fact that the shells
the structure of giant fullerenes are not able to give a may be rotating relative to each other[lS]. This behav-
definitive answer: (a) models based on elastic or em- ior has been predicted for C6,, in C240[30] and for
pirical potentials predict that the minimal energy struc- multi-shell tubes[34].
ture is a slightly relaxed icosahedron with planar
facets, the curvature being concentrated at the corner
5. SUMMARY AND PERSPECTIVES
of the polyhedron (pentagons)[26,29,30]; (b) ab ini-
tio calculations predict two local energy minima for The multi-shell fullerenes constitute the transition
C 240. One represents a faceted icosahedron, and the from fullerenes to macroscopic graphite. They present
second, a nearly spherical structure distributing the both the closed graphitic surface of fullerenes and the
strain over all atoms, is slightly more stable (binding stacked layers interacting by van der Waals forces, as
energy per atom -7.00 and -7.07 eV for polyhedral in graphite.
and spherical fullerenes)[3 I]. One of the main scientific issues of the discovery
When using these theoretical results to analyze of the bucky-onions is the unresolved question of min-
onion-like particles, we must take into account that imal energy configuration of carbon clusters (onion-
calculations are performed for single graphitic shells,
which are subsequently arranged concentrically and,
then, conclusions are obtained about the minimal en-
ergy configuration. This fact arises from the limited
number of atoms that may be included in a calcula-
tion due to present computational capabilities (the
smallest onion-like particles are formed by C,, in a
C,,, and this system represents 300 atoms).
The inter-layer interaction (EvdW, van der Waals
energy) is usually added at the end, and then it does
not participate in the energy minimization. Evaluating
inter-shell interaction by a simple Lennard-Jones pair
potential shows that concentrical spherical shells are
more stable than icosahedral ones (Ebdw between C240
and C540 is -17.7 and -12.3 eV for spherical and
Fig. 4. Onion-like graphitic particles formed by three con-
icosahedral shells, respectively). An interesting com- centric layers (C,,, Cz4,,, C&: polyhedral (marked P) and
parison may be performed by considering that coran- spherical (marked S) structures. For clarity, only a half part
nulene C,,H,o, which is a pentagon surrounded by of each shell is shown.
 Onion-like graphitic particles 993

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