Materials Science and Engineering B74 (2000) 206 – 217

www.elsevier.com/locate/mseb

Synthesis, atomic structures and properties of carbon and boron

nitride fullerene materials
Takeo Oku *, Takanori Hirano, Masaki Kuno, Takafumi Kusunose, Koichi Niihara,
Katsuaki Suganuma
Institute of Scientific and Industrial Research, Osaka Uni6ersity, Mihogaoka 8 -1, Ibaraki, Osaka 567 -0047, Japan

Abstract

Carbon (C) and boron nitride (BN) fullerene materials (clusters, onions, intercalation, nanopolyhedra, nanotubes and
nanocapsules) were synthesized by polymer pyrolysis, chemical reaction, arc-melting and electron-beam irradiation. Atomic
structure and formation mechanism were investigated by high-resolution electron microscopy, energy dispersive spectroscopy and
electron energy-loss spectroscopy. Fullerene clusters and atomic clouds (atom hopping) were formed on the surface of the C and
BN fullerene materials. They provided angular and spherical nanocage structures which consist of four-, five-, six-, and
seven-membered ring bonding. Detection possibility of doping atoms in metallofullerene was discussed. Included clusters showed
some crystallographic relationship with {001} layers of C and BN fullerene materials, and a structure model was proposed.
Photoluminescence and magnetic properties of C and BN nanocapsules were measured, which showed higher energy shift of
luminescence and superparamagnetism. The present work indicates that the new C and BN fullerene materials with various atomic
structure and properties can be produced by various synthesis methods, and a guideline for designing the C and BN fullerene
materials is summarized. © 2000 Elsevier Science S.A. All rights reserved.

Keywords: HREM; Fullerene; Carbon; BN; Cluster

1. Introduction blockade, photoluminescence, and superparamag-

Carbon (C) and boron nitride (BN) have various
hollow-cage-structures such as C60, giant fullerenes,
nanocapsules, onions, nanopolyhedra, cones, cubes,
and nanotubes [1 – 7]. These structures show different
physical properties, and have a potential for studying
materials of low dimensionality within an isolated envi-
ronment. Especially, cluster-included fullerene materials
are intriguing for both scientific research and device
applications such as cluster protection, cluster separa-
tion, nano-ball bearings, nano-optical-magnetic devices,
catalysis, and biotechnology [8 – 11]. By controlling the
size, layer numbers, included clusters, helicity and com-
positions, the cluster-included C – B – N nanocage struc-
tures with bandgap energy of 0 – 5 eV and
non-magnetism are expected to show various electronic,
optical and magnetic properties such as Coulomb
* Corresponding author. Tel.: +81-6-6879-8521; fax: + 81-6-6879-
8522.
E-mail address: oku@sanken.osaka-u.ac.jp (T. Oku)
netism. Our recent research on these C and BN
fullerene materials is summarized in Fig. 1.
The purpose of the present work is threefold. First,
to prepare the new C–BN fullerene materials. In the
present work, various clusters with polymer pyrolysis,
chemical reaction, arc-melting and electron-beam irra-
diation technique were selected for the formation of
C–BN fullerene materials. C–BN nanocapsules and
onions are expected to form at low temperatures com-
pared to the ordinary arc-discharge method. SiC, Ag,
FeOx and Pd clusters were selected for nanocapsule
formation. Polyvinyl alcohol is easily decomposed at
elevated temperatures, and produces carbon-based ma-
terials [12,13]. Organic materials of urea (CO(NH2)2)
and boric acid (H3BO3) were selected in the present
work for the formation of BN layers. The mixture is
expected to form BN layers by annealing in hydrogen
gas [14]. SiC is a hard material with a hardness of 30
GPa. If the SiC nanoparticles are combined with slip-
pery graphite, nano-ball bearings and solid-state lubri-
cants can be obtained. Similarity in properties to the

0921-5107/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 9 2 1 - 5 1 0 7 ( 9 9 ) 0 0 5 6 3 - 2
 T. Oku et al. / Materials Science and Engineering B74 (2000) 206–217 207

metal dichalcogenides was produced by Rapoport et al.
[10]. Gold colloids have been used for the formation of
single electron transistors [15,16] because of easy con-
trol of cluster size [17]. In the present work, Ag
nanoparticles with BN sheets were selected, which are
expected as quantum electronic devices. Silver nitrate
was selected for the formation of silver nanoparticles in
the present work. Furthermore, since these precursors
are soluble in solvents, it is possible to mix them
homogeneously in the ionic state. If the FeOx nanopar-
ticles are divided by carbon sheets with thickness less
than 3 nm, superparamagnetism is expected, and they
can be applied to magnetic refrigeration [18].
The second purpose is to understand the formation
mechanism and microstructure of the nanocapsules and
onions from high-resolution electron microscopy
(HREM), which is a powerful method for structural
analysis at the atomic scale [19–23]. Energy dispersive
spectroscopy (EDS) and electron energy-loss spec-
troscopy (EELS) were carried out for composition anal-
ysis and electronic bonding state of the C–BN fullerene
materials. The third purpose is to investigate photolu-
minescence (PL) and magnetic properties of these
fullerene materials. Downsizing of these materials is
expected to show the various properties. These studies
will give us a guideline for design and synthesis of the
C–BN fullerene materials, which are expected to be
used in future nanoscale devices.
2. Experimental procedures
Carbon nanocapsules and clusters were produced by
the following method [12,13]. b-SiC nanoparticles

Fig. 1. Structure and properties of C and BN fullerene materials.

208 T. Oku et al. / Materials Science and Engineering B74 (2000) 206–217
(Sumitomo Cement Co. Ltd.), were dispersed in deion-
ized water with polyvinyl alcohol (PVA-706, Kuraray
Co., Ltd.) at 60°C. This polymer is a copolymer of
polyvinyl alcohol and polyvinyl acetate. The solution
with clusters and polyvinyl alcohol was dried in a
drying oven prior to loading into the vacuum chamber.
The annealing chamber was first evacuated to 1 × 10 − 6
Pa, and the samples were annealed at 400 – 800°C for 30
min in an Ar gas atmosphere of 0.12 MPa.
The BN nanocapsules were prepared by two meth-
ods. Boric acid, urea, and silver nitrate were completely
dissolved in deionized water, and this solution was
dried in a rotating vacuum drier. The dried mixtures
were reduced at 300 and 700°C in hydrogen gas for 7 h.
After the annealing, the samples were obtained [24].
The second method is by arc melting in a nitrogen gas
atmosphere using tungsten electrode and boron-based
mixture powder [25]. Boron particles (99%, 40 mm, 1 g,
Niraco Co. Ltd.) were mixed with gold particles
(99.5%, 0.5 mm, 4.56 g, Niraco Co. Ltd.) and iron oxide
particles (10 nm, 1.85 g, ULVAC Co. Ltd.). Atomic
ratios of B/Au and B/Fe3O4 were 8:2. The mixture
powder was pressed at 15 kg mm − 2 into pellets with a
size of 1 mm thick and 20 mm in diameter. The green
compacts were set on copper mold in electric-arc fur-
nace, and were evacuated down to 1×10 − 3 Pa. After
introducing a mixed gas of Ar (0.06 MPa) and N2 (0.06
MPa), arc melting was applied to the samples at the
accelerating voltage of 60 V and an arc current of 200
A for a few minutes. Arc melting was performed with a
vacuum arc-melting furnace (ACM-01, Daia Vacuum
Engineering Co. Ltd.). After the arc melting, a white or
gray powder was obtained around the pellets.
Samples for HREM observation were prepared by
dispersing the materials on perforated carbon grids.
HREM observation was performed with 200, 300 and
1250 kV electron microscopes (JEM-2010, 3000F and
ARM-1250) having a point-to-point resolution of 0.194
and 0.12 nm, respectively. The electron microscope is
equipped with an imaging-plate system (PIXsysTEM),
and the imaging plates with the benefit of a large
detection area of digital data were used to record the
observed images. The detection area of the IP is 102 ×
77 mm with a pixel size of 25 ×25 mm and an image
depth of 0–16 383 gray scale. The digital data were
saved in digital data storage (DDS) by Digital Micro-
Luminography (Fuji Film Co. Ltd.). The electron mi-
croscope is equipped with an EDS system (EDAX) and
EELS system (676 PEELS, Gatan Inc.). For image
processing and analysis of the observed HREM images,
the Image Gauge, L Process (Fuji Film Co. Ltd.),
Digital Micrograph (Gatan Inc.), CRISP (Calidris
Corp., Stockholm, Sweden) and Adobe Photoshop soft-
ware were used. To compare observed images with
calculated ones, HREM images were produced by the
multi-slice method [26] using the MacTempas software
(Total Resolution, CA). The parameters used in the
calculations are as follows: accelerating voltage, 1250
kV; radius of the objective aperture, 8.8 nm − 1; spheri-
cal aberration Cs, 2.28 mm; spread of focus D, 15 nm;
semi-angle of divergence a, 0.85 mrad; defocus values
Df, −49 nm, and crystal thickness t, 2 nm.
Atomic structures of the cluster were optimized by
MOPAC software (Fujitsu Co. Ltd.), and electronic
state of the cluster was calculated by DV-Xa. Photolu-
minescence spectra were measured by fluorescence pho-
tospectrometer (Hitachi, F-4500) at room temperature.
Magnetization measurements were carried out at low
temperatures down to 4.2 K.
3. Fullerene clusters and metallofullerenes
Hollow carbon clusters with diameters in the range
of 0.7–1.0 nm are often on the carbon nanocapsules.
Two of the carbon clusters are shown in Fig. 2(a,b).
The size of the carbon cluster in Fig. 2(a) is in the range
of 0.5–0.7 nm, which corresponds to that of C36,
discovered and studied recently [27,28]. The high-reso-
lution image of Fig. 2(b) also shows a carbon cluster
with the size of 0.7–0.8 nm, and the number of carbon
atoms would be  70 (C70) [1], which could be esti-
mated from the size of the cluster. In addition, dark
contrast is observed inside the cluster, which would
indicate the existence of several atoms inside the carbon
cluster. The carbon cluster is directly connected at the
step edge of the graphite sheets, which results in the
stabilization of the carbon cluster. These C36 and C70
carbon clusters have elliptical structures [1,27,28],
which agrees well with the present high-resolution
observation.
BN clusters are also often observed as shown in Fig.
2(c). The cluster structures were calculated theoreti-
cally, and the present BN cluster would be B36N36 as
shown in Fig. 2(d). The cluster consists of six four-
membered rings and 24 six-membered rings, and struc-
ture was optimized by molecular orbital method using
MOPAC software (Fujitsu Co. Ltd.). The electronic
structure was calculated by DV-Xa, and the energy gap
is  4 eV, which is close to the bulk BN materials. BN
clusters were theoretically calculated, and various BN
clusters are predicted [29]. However, the new stable BN
cluster is found in the present work.
The possibility of direct detection of doping atoms in
C60 solid clusters by high-resolution electron mi-
croscopy (HREM) was investigated using calculated
residual indices (RHREM) and difference images
[19,22,23,30]. The light element nitrogen (Z=7) and
heavy element rubidium (Z= 37) were selected as dop-
ing atoms in the present work. It was reported that
nitrogen atoms were included at the center of the C60
clusters [31], which was detected by electron paramag-
 T. Oku et al. / Materials Science and Engineering B74 (2000) 206–217 209

Fig. 2. HREM images of (a) C36, (b) C70 and (c) BN clusters. Proposed structural model of B36N36.

Fig. 3. Structural models of C60, N@C60 and RbC60 and HREM simulated images.

netic resonance [32]. It was also reported that Rb atoms
were doped at the octahedral sites of C60 solid clusters,
which were determined by X-ray diffraction [33]. Based
on the crystal structure of C60 solid clusters, difference
images between C60 and doped C60 (C60/doped C60)
were calculated for image analysis using residual in-
dices. HREM images of C60 doped with nitrogen and
rubidium atoms were calculated as functions of acceler-
ating voltage of microscope, crystal thickness and defo-
cus values. The structure models and calculated images
are shown in Fig. 3. Difference images of N@C60/C60
and RbC60/C60 showed N and Rb atomic positions
clearly at high accelerating voltage and large crystal
thickness. RHREM values of RbC60 are strongly depen-
dent on accelerating voltage and crystal thickness,
which would be due to the dynamical diffraction effect
of Rb atoms. Defocus values also influence the RHREM
values, and the Scherzer defocus would be the best for
atomic detection. The present work indicates that the
doping atoms at the inside and interstitial site of C60
210 T. Oku et al. / Materials Science and Engineering B74 (2000) 206–217
solid clusters could be detected by HREM with differ-
ence images and RHREM values.
4. Onions, intercalation, nanocages and nanotubes
Carbon was formed from polyvinyl alcohol after
annealing at 400°C in Ar, and the carbon matrix is
found to have an amorphous structure from the
HREM image. The amorphous carbon was irradiated
by an electron beam for 30 min under a beam current
of 100 mA cm − 2 at 1250 kV. This beam current is 20
times higher compared to that of ordinary observation
by the electron microscope. Graphitization of amor-
phous carbon is observed, which is confirmed by the
lattice fringes of carbon layers with a spacing of 0.34
nm, as shown in Fig. 4(a). Fig. 4(a) is a six-layered
onion structure, and the outside is calculated to be
C2160 from the equation 60n 2 (n is the number of the
shell). The lattice fringes of the carbon {002} planes are
smeared at the edges of the onions with pentagonal
carbon bonding, as indicated by arrows. ‘Atom clouds’
Fig. 4. (a) HREM images of onion structures. (b) Six-layered carbon onion; 60 s after (a). (c) Seven-layered tetrahedral onion. (d) Onion with Pd
clusters.
[34,35], which have vague contrast, are also observed at
the vertices of onion edges as indicated by arrows. The
carbon ‘vibration’ was also observed at the surface of
the onions. The shell structure is not perfect, but has
some defects. The same onion after 60 s is shown in
Fig. 4(b). Change of the vertices into spherical structure
is observed on the onion surface. At the center of the
onion, there would be a C28 cluster from the size of
 0.4 nm. Although this structure would be unstable,
the C28 cluster would be stabilized by compressive
tension of outer onion. Carbon onions with tetrahedral
structure are also formed as shown in Fig. 4(c). At the
center of the onion, there would be a tetrahedral car-
bon cluster, but the detailed structure is unknown.
The formation of onion structure had been reported
and discussed intensively. Ugarte reported that the
onions had a spherical shape [3], and Ru et al. reported
that the onions had some vertices and 10-fold (icosahe-
dral) symmetry [36]. From the theoretical calculation of
the giant fullerene (onion structure), icosahedral sym-
metry with fivefold axes is stable [37], and the icosahe-
dral symmetry also has threefold axes (with sixfold
 T. Oku et al. / Materials Science and Engineering B74 (2000) 206–217 211

Fig. 5. (a) Processed experimental HREM image of Pd intercalated onion together with original image (lower left). (b) Fourier transform of (a)
structure model. (c) Projected structural models of Pd-intercalated graphite along [100]. (d) Perspective structural models of (c).

shape). The projected models are shown in Fig. 4(c,d).
In the present work, eightfold symmetry was observed,
which was also observed by Iijima [38]. It is believed
that the present onion would be observed along the
threefold axis, and that these onions have some defect
structure. Electron-beam irradiation leads to disconnec-
tion of the carbon bonding (knocking-on carbon
atoms), which results in structural flexibility and the
formation of the spherical structure by surface tension.
The replacement of hexagons by heptagon/pentagon
pairs, which increases sphericity at the expense of
faceting, would be introduced to stabilize the onion
structure [37].
In the present work, atom clouds and the vibration
of facets were also observed at the surface of the onion
as shown in Fig. 4(a), which would be due to the
electron-beam irradiation. ‘Atom clouds’ with vague
contrast at the onion vertices indicates the hopping of
carbon atoms from the onion surface. It is believed that
the pentagonal bonding would be weaker compared to
the hexagonal bonding, which results in the hopping of
carbon atoms at the onion vertices. The carbon ‘vibra-
tion’ was also observed at the surface of the onions.
These atom clouds form carbon vacancies at the onion
surface, which indicates that carbon diffusion in the
onion could be described by the vacancy mechanism.
In the high-resolution electron microscope study, Pd
intercalation in graphite was produced by electron-
beam irradiation of amorphous carbon with Pd clusters
in Fig. 4(d) [34,39]. HREM observation and Fourier
transform (Fig. 5(a,b)) showed the increase of the lat-
tice distance ( 0.4 nm) of graphite {002} planes and
appearance of ordered black contrast between the
graphite {002} planes with a periodicity of 0.4 nm,
which indicates that the Pd atoms are intercalated in
the graphite {002}. The structural model (Fig. 5(c,d))
for Pd intercalation was proposed, and image calcula-
tion based on this model agree well with the experimen-
tal results. Structural calculation by ab initio ultrasoft
pseudopotential was carried out, and the optimized
lattice parameters of the Pd intercalated graphite also
agree well with the experimental data [40,41]. The
present result indicates that the combination of atomic
observation with theoretical calculation is an effective
method for atomic structure determination.
212 T. Oku et al. / Materials Science and Engineering B74 (2000) 206–217
Atomic intercalation in the graphite sheets has been
studied for various elements such as Cs, Rb and K [42].
For the ordinary intercalation, the d-value between
graphite {002} planes is in the range of 0.4 –0.6 nm,
which is fairly large compared to the present Pd inter-
calation (0.38–0.44 nm). In addition, the image con-
trast of Pd positions in the experimental image (Fig.
5(a)) is not so dark compared to the simulated image.
This indicates that the Pd intercalation in the graphite
layer in the present work is incomplete, i.e. the occu-
pancy of Pd in the graphite sheets is less than unity.
Pd intercalation in the graphite layers was observed
in the present work. Atomic intercalation of Al in the
carbon onions has been reported [43], which leads to
spherical structures whereas Pd intercalation results in
the disordering of the onion structure as shown in the
present work, which would be due to the larger atomic
number (size) of Pd cf. Al. For both metals, onions
formed in the graphite matrix, although onions gener-
ally form on the surface of carbon matrix. This also
suggests that distortions in the atomic-intercalated
onions are relaxed in the carbon matrix. The formation
of atomic-intercalated onions with low strain is interest-
ing in terms of scientific research and applications, and
can be readily synthesized by electron-beam irradiation.
Nanotubes are very interesting for providing the
one-dimensional nanostructure. Fig. 6(a)Fig. 6(b) are
HREM images of BN nanocage and BN nanotube,
respectively. Carbon nanocages were observed as de-
scribed in the previous paper [12,13], which have spher-
ical structures. Compared with the carbon nanocages,
the BN nanocages and nanotubes have sharp inner
angular and peculiar structure for the tip because of
four-membered rings, as indicated by arrows in both
images of Fig. 6.
Fig. 6. HREM images of (a) BN nanocage and (b) BN nanotube.
5. Carbon nanocapsules
SiC nanoparticles prepared with polyvinyl alcohol
were annealed at 500°C in an Ar gas atmosphere. The
particle size of SiC is in the range of 5–50 nm. All the
SiC particles are surrounded by graphite sheets, and the
number of the graphite sheets are in the range of 1–6.
An enlarged HREM image of a carbon nanocapsule is
shown in Fig. 7(a). Lattice fringes with a distance of
0.25 nm which corresponds to the distance of {111}
planes of b-SiC are observed in the nanoparticle. Two
{002} planes of graphite grow on the b-SiC nanoparti-
cle. The PL spectrum of the carbon nanocapsules en-
casing SiC clusters is shown in Fig. 7(b). A
luminescence peak is observed at 382 nm, which corre-
sponds to  3.2 eV. The bulk SiC has an energy gap of
3.00 eV. The present carbon nanocapsules with SiC
clusters have higher energy compared to the bulk SiC,
which would be due to the quantum size effect of SiC
as shown in Fig. 7(a).
A HREM image of the surface of a carbon nanocap-
sule with SiC nanoparticle is shown in Fig. 7(c). Car-
bon {002} planes grow epitaxially on the SiC {111},
but disordered carbon structure is observed on the SiC
{200}. Epitaxial growth of carbon {002} on the b-SiC
{111} planes was often observed at the nanocapsule/
nanoparticle interface in the present work. A similar
epitaxial relationship was observed at the carbon/b-SiC
in previous studies [44–46]. The information on atomic
arrangement at the carbon/SiC interface was obtained
from the HREM images in the present work, and two
structural models of the carbon/SiC interface were con-
structed, as shown in Fig. 7(d). In Fig. 7(d), carbon
atoms which belong to the SiC structure connect with
carbon atoms of the graphite. From the present high-
 T. Oku et al. / Materials Science and Engineering B74 (2000) 206–217
Fig. 7. (a) HREM image of carbon nanocapsules with SiC cluster. (b) Photoluminescence spectrum of (a). (c) HREM image of surface of carbon
nanocapsule with SiC together with calculated image based on the proposed interfacial model (d).
resolution observation, the carbon {002} is parallel to
the SiC {111}, and carbon [11( 0] is nearly parallel to SiC
[011( ]. (If the incidence is parallel to carbon [010],
two-dimensional lattice fringes should be observed.)
The distance between the SiC crystal and graphite layer
was assumed to be 0.335 nm, which is the same as that
of graphite {002} planes. Based on these models,
HREM images are calculated as shown in Fig. 7(c) as
an inset. In the observed images of Fig. 4(b–d), the
distance between the dark contrast of the first carbon
layer and the top of the SiC crystal is almost the same
as that of carbon {002}, which indicates that carbon
atoms of the graphite-type structure directly connect
with carbon atoms which belong to the SiC structure.
Graphitizaton of amorphous carbon on SiC {111}
planes would be easier compared to the SiC {200}. It is
believed that the carbon surface of SiC would have a
low activation energy for graphite growth, which results
in the heterogeneous nucleation growth of graphite.
Synthesis of carbon nanocapsules with various ele-
ments such as Au, Ge, and GeO2, Fe, and Co, was also
tried. Formation of partial carbon nanocapsules with
Au was observed after annealing at 400°C. The 13
graphite layers partially encapsulate the Au nanoparti-
cle. Amorphous carbon is also observed around the
nanoparticle.
213
The formation model of carbon nanocapsules by
pyrolysis of polyvinyl alcohol was proposed. In the
as-prepared samples, the nanoparticle is encapsulated in
amorphous polyvinyl alcohol. The polyvinyl alcohol
has a basic formula of [CH2CH(OH)]m –
[CH2CH(OCOCH3)]n, which decomposes into H2O and
CO2 at 120–170°C in air. During annealing, the
polyvinyl alcohol decomposes into H2O and CO2. After
annealing at 400–500°C in Ar gas atmosphere, only
carbon atoms remain, and graphite layers grow on the
surface of nanoparticles. In the present work, only SiC
nanoparticles formed perfect carbon nanocapsules, and
others produced carbon layers with amorphous struc-
ture except Co nanoparticles. This suggests that the
carbide-based materials would be effective for graphite
growth.
The graphitization of amorphous carbon was ob-
served by changing included elements. Various types of
transition metals accelerate the graphitization of carbon
[47,48] by the solution–precipitation mechanism, which
results in disconnection of carbon–carbon bonds by the
catalytic particles. The carbon atoms dissolve in the
metal particles, and diffuse and precipitate as graphite
at the particle surfaces. Encapsulation of small Pd
particles in the graphite structure was reported, and the
214 T. Oku et al. / Materials Science and Engineering B74 (2000) 206–217
Pd-catalyzed graphitization of amorphous carbon oc-
curred after annealing at temperatures above 600°C
[48]. In the present work, the annealing temperatures
were below 600°C, which is lower compared to the
ordinary graphitization mechanism. For the Au and Ge
nanoparticles, the graphitization of amorphous carbon
was due to the catalytic effect. However, for the SiC
nanoparticles, the graphitization was attributed to the
existence of carbon atoms at the nanoparticle surface,
which results in graphite growth from amorphous car-
bon produced by polyvinyl alcohol. The driving force
Fig. 8. (a) HREM image; (b) EDX spectra and (c) PL spectrum of
BN nanocapsule with Ag nanoparticle.
of this graphitization was the free energy difference
between the initial and final forms of carbon [42].
Formation of the graphite layer around nanoparticles
is useful for cluster protection against grain growth of
nanoparticles. For various nanostructured materials,
nanograins are needed to obtain the various mechani-
cal, electronic, and magnetic properties. Similar forma-
tion of graphite layers had been reported in the SiC
ceramics prepared by polysilastyrene at 1800°C in an
Ar gas atmosphere [49] and by liquid phase sintering of
SiC at 1700°C in vacuum [50]. Formation of carbon
nanotubes had also been reported by decomposition of
SiC at 1700°C in vacuum [51]. In addition, graphite
structure was produced by pyrolysis of a polyvinylidene
chloride polymer at temperatures in the range of 2100–
2600°C in an inert atmosphere [52]. In the present
work, we have succeeded in producing the carbon
nanocapsules at ‘low’ temperatures of  500°C in an
Ar gas atmosphere. Although the carbon nanocapsules
had been produced with the aid of the catalytic effect
by metal elements such as Fe, Co, and Ni [6,9], these
catalytic elements are not needed in the present work. It
is difficult to control the formation of nanocapsules by
the ordinary arc discharge method. In the present work,
the number of graphite sheets is in the range of 1–13,
which could be controlled by the solution concentration
of the polyvinyl alcohol.
6. BN nanocapsules
An HREM image of Ag nanoparticles encapsulated
in BN nanocapsules prepared at 700°C is shown in Fig.
8(a). The particle size of Ag is in the range of 10–20
nm, and all Ag nanoparticles are encapsulated in BN
{002} sheets. An XRD pattern of the BN nanocapsules
showed Ag reflections of 111, 200, 220 and 311. A weak
peak of BN 002 is also observed, which indicates the
formation of turbostratic BN. EDX spectra of the BN
nanocapsules with Ag nanoparticles are shown in Fig.
8(c). A nitrogen peak is as high as the boron peak,
which indicates the formation of boron nitride. Ag
peaks are from Ag nanoparticles, and a Cu peak is due
to the HREM grid. Although oxygen atoms remain in
the sample, no carbon is detected.
PL spectra of the present BN nanocapsules and
commercial BN powder (Denka, 9 mm) are shown in
Fig. 8(c). The luminescence was observed at 336 and
360 nm, which corresponds to 3.7 and 3.4 eV, respec-
tively. The mechanism of the photoluminescence is
considered to originate in interband transition of BN
by impurities of carbon and hydrogen [53]. The blue
shift of the PL spectra of the BN nanocapsules is
believed to be the spherical structure of hexagonal BN
bonding formed by BN nanocapsules.
 T. Oku et al. / Materials Science and Engineering B74 (2000) 206–217 215

Fig. 9. (a) HREM image of BN nanocapsule encaging Fe3O4 nanoparticle. (b) Nano-sized BN nanocapsules with Fe3O4. (c) Temperature
dependence of magnetization of the BN nanocapsules. (d) EELS spectrum of BN nanocapsules.

The formation mechanism of BN nanocapsules syn-
thesized in the present work is believed to be described
overall as follows: 2H3BO3 +CO(NH2)2 +AgNO3 +
H2 “Ag+ 2BN+6H2O  + CO  +NOx . AgNO3 is
soluble for water, and Ag+ and 2NO− 3 would be
formed in the present ion exchanged water. After an-
nealing at 300°C, silver clusters and amorphous BN
with low nitrogen content were formed, and oxygen
would be included in the BN matrix. After annealing at
700°C, t-BN layers were formed around the silver
nanoparticles by the reduction and crystallization of
BN matrix with H2.
In the present work, we have succeeded in developing
a new synthetic process for a large amount (\ 1 g) of
BN nanocapsules with Ag nanoparticles, which is suffi-
cient quantity for various property measurements. We
have also succeeded in producing the BN nanocapsules
at ‘low’ temperature of 700°C. Previous BN nanocap-
sule had been produced by arc-discharge or arc-melting
methods (2000–3000°C), and it is difficult to control
the formation of BN nanocapsules. In the present
work, the control of BN nanocapsule formation is very
easy and reliable because of the ordinary annealing
technique.
BN nanocapsules are expected to have various prop-
erties. It is expected that silver nanoparticles encapsu-
lated in BN nanocapsules enable control of a single
electron through the insulator sheets, and they can be
applied to single electron transistors [15,16]. Formation
of the BN layer around nanoparticles is also useful for
cluster protection. In the present work, AgO nanoparti-
cles with a decomposition temperature of 100°C
were also encapsulated in BN nanocapsules, which
indicates the cluster protection of AgO at elevated
temperature of 700°C. In the present work, formation
processes of nanoscale insulator sheets and cluster-pro-
tection sheets around metal nanoparticles were
developed.
Another type of BN nanocapsule was also synthe-
sized in the present work [54]. An HREM image of a
BN nanocapsule with iron oxide nanoparticle is shown
in Fig. 9(a). The particle size is in the range of 5–20
nm. Lattice fringes with distances of 0.47, 0.23 and 0.20
nm, which correspond to the distances of {111}, {222}
and {400} planes of Fe3O4, are observed in the clusters.
The number of BN sheets is in the range of 15–20
layers, and many defects are observed. Another small
BN nanocapsule with a size of  6 nm is shown in Fig.
9(b). Fig. 9(c) is of magnetization of BN nanocapsules
with Fe3O4 as a function of temperature. The magne-
tization shows the weak superparamagnetism, and in-
creases below 30 K, which would indicate the
216 T. Oku et al. / Materials Science and Engineering B74 (2000) 206–217
appearance of ferromagnetism. This result indicates
that the size of the BN nanocapsules is less than 10 nm.
Fig. 9(d) is an EELS spectrum of BN nanocapsules
with iron oxide. Two distinct absorption features are
observed at 188 and 401 eV, which correspond to boron
K-edge and nitrogen K-edge onsets, respectively. The
fine structure of boron in the EELS spectrum shows the
hexagonal bonding between boron and nitrogen, which
is indicated by presence of a sharp p* peak and the
shape of the s* peak. The EELS spectrum also shows
the weak s* peaks of B and N, which indicate the
spherical structure of BN nanocapsules.
When the iron oxide nanoparticles are divided by BN
sheets with thickness less than 3 nm, superparamag-
netism is expected, and they can be applied to magnetic
refrigeration [18]. In the present work, formation pro-
cesses of non-magnetic sheets around metal nanoparti-
cles were developed, and the method is expected to be
applied to nanostructure devices in the future.
7. Summary
Various C –B–N fullerene materials were synthesized
by polymer pyrolysis, chemical reaction, arc-melting
and electron-beam irradiation. Atomic structure and
formation mechanism were investigated by HREM,
EDS, and EELS. Fullerene clusters and atomic clouds
(atom hopping) were formed on the surface of the C
and BN fullerene materials, which provided angular
and spherical nanocage structures which consist of
four-, five-, six-, and seven-membered ring bonding.
Included clusters showed some crystallographic rela-
tionship with {001} layers of C and BN fullerene
materials, and a structural model was proposed. Mea-
surements of photoluminescence and magnetic proper-
ties of C and BN nanocapsules showed a higher energy
shift of luminescence and superparamagnetism. The
present work indicates that the new C and BN fullerene
materials with various atomic structures and properties
can be produced by various synthesis methods, and are
expected to be the future nanoscale devices.
Acknowledgements
The authors would like to thank Professors G.
Schmid, K. Hiraga, E. Aoyagi, H. Kubota, Y. Kawa-
zoe and H. Tanaka for their useful discussion, experi-
mental help and collaborative work. This work was
partly supported by The Shinsedai Foundation, and
was also supported by Grant-in-Aid for Scientific Re-
search, Ministry of Education, Science, Sports and
Culture, Japan.
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