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Materials Chemistry
Cite this: J. Mater. Chem., 2011, 21, 12629
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Intense green and yellow emissions from electrospun BCNO phosphor
nanofibers
Adi Bagus Suryamas,a Muhammad Miftahul Munir,ab Takashi Ogi,a Khairurrijalb and Kikuo Okuyama*a
Received 9th June 2011, Accepted 8th July 2011
DOI: 10.1039/c1jm12654g
Published on 25 July 2011 on http://pubs.rsc.org | doi:10.1039/C1JM12654G
Downloaded by HIROSHIMA DAIGAKU on 01 September 2011
BCNO phosphor nanofibers, composed of polycrystalline-BCN and
B2O3 crystal, were prepared by electrospinning followed by calci-
nation at 700
C. These showed intense green and yellow emissions
under UV-light irradiation that could be seen by the naked eye. The
prepared nanofibers were uniform, non-agglomerate, thermally
resistant, and had a good atomic distribution.
Boron carbon oxynitrides (BCNOs) are a new class of phosphor
materials with great advantages such as raw materials that are inex-
pensive, a free rare-earth element, low-temperature synthesis, and
multi-color photoluminescence properties. BCNO may find potential
applications in lighting, optoelectronics, and even in medical appli-
cations.1–6 Prior studies of BCNO were concerned on the strategy of
liquid-phase processing to synthesize BCNO particles. However, the
application of BCNO particles still remains a problem. The
morphology of as-synthesized particles composed of a huge
agglomeration of nanocrystals forms an irregular shape. On the other
hand, control over the shape of nanocrystals is indispensable for its
applications.7
Recently, Dong et al.8 prepared hybrid BCNO/polymer nanofibers
using poly(vinylpyrrolidone) (PVP). Size-selected BCNO particles
were dispersed in the PVP/ethanol solution followed by electro-
spinning, and then the resulting BCNO particles were encapsulated in
PVP nanofibers. In order to improve the physical properties,
synthesis of precursor-derived BCNO nanofibers is necessary.
Here, a different strategy is presented to prepare BCNO nanofibers
by electrospinning. A precursor containing boron, carbon, and
nitrogen sources was electrospun followed by calcination. The
morphology, crystal structure, photoluminescence, and surface
properties are reported herein. The results of the present study show
great opportunities for application of BCNO phosphor materials.
Preparation of the starting materials is critical to producing high-
quality phosphors; therefore, careful attention is needed. The starting
material was prepared by dispersing a certain amount of boric acid
(H3BO3, Wako Chemicals, Japan) in 3 g of N,N-dimethylformamide
(C3H7NO, DMF, Sigma Aldrich, USA). The solution was then
a
Department of Chemical Engineering, Graduate School of Engineering,
Hiroshima University, 1-4-1 Kagamiyama, Higashi Hiroshima,
Hiroshima, 739-8527, Japan. E-mail: okuyama@hiroshima-u.ac.jp
b
Department of Physics, Bandung Institute of Technology, Jalan Ganesa
10, Bandung, 40132, Indonesia
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slowly dropped into 10 g of polymer/DMF solution composed of
polyacrylonitrile ((C3H3N)n, PAN, Mw ¼ 150,000, Sigma Aldrich,
USA) at 10 wt%, under vigorous stirring. All solutions were stirred at
85
C for at least 1 day to obtain clear and viscous solutions. The
precursor was subsequently electrospun using a similar set-up
described in our previous work.9 The high voltage, syringe distance,
and precursor flow rate were kept constant at 15 kV, 20 cm, and
20 mL min1. As-prepared composite nanofibers were then heated
under an atmospheric environment at 700
C for 30 min, at a heating
rate of 16
C min1.
The morphology of the nanofibers was examined using a trans-
mission electron microscope (TEM; JEM-3000F; JEOL) and a field
emission scanning electron microscope (FE-SEM; Hitachi S-5200).
X-ray diffraction (XRD) patterns were obtained at room tempera-
ture using a Rigaku RINT2000 X-ray diffractometer with nickel-
filtered Cu-Ka (l ¼ 0.154 nm) radiation at 40 kV and 30 mA with
a scanning step size of 0.02
/2q. Photoluminescence (PL) spectra were
recorded using a Shimadzu RF-5300 PC spectrophotometer equip-
ped with a Xe source. The phosphor fibers were pressed into
a cylindrical aluminum holder. The excitation light from the Xe
source was directed to the sample using the reflection mode. The
chemical bonding state was examined by a PerkinElmer Spectrum
One Fourier-transform infra-red (FTIR) spectrometer.
Boric acid was used as a boron source; meanwhile, DMF and
PAN were used, not only as carbon and nitrogen sources, but also as
a solvent and nanofiber template. In a typical process, electrospinning
strongly depends on electrospinnability, as determined from the
surface properties of the precursor.10 In the present study, a site
percolation process was observed when the boric acid solution was
dropped into a polymer solution that constrained its electro-
spinnability. The percolation threshold was found to be x ¼ 17.5
mmol, where x represents the concentration of boric acid. With x >
17.5 mmol, gel formation occurred, and the precursor could not be
electrospun. At lower concentration, x < 5 mmol, as-prepared
nanofibers were completely removed at 700
C. In addition, the
production yield of BCNO phosphor nanofibers increased as boric
acid concentration increased. It can be argued that boiling-point
elevation occurred in the precursor solutions.
Photoluminescence (PL) properties of BCNO nanofibers were
examined under excitation at 365 nm as a function of boric acid
concentration in precursors. Fig. 1 shows that the PL spectra from
the precursors contained 5, 10, 15, and 17.5 mmol of boric acid. The
upper inset shows the relationship between peak wavelength, PL
J. Mater. Chem., 2011, 21, 12629–12631 | 12629
 View Online

Fig. 2 (a) FTIR spectra and (b) XRD pattern of BCNO phosphor
nanofibers prepared at a boric acid concentration of 15 mmol.
Published on 25 July 2011 on http://pubs.rsc.org | doi:10.1039/C1JM12654G

composed of a polycrystalline-BCN and B2O3 system. The presence

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of polycrystalline-BCN was confirmed by B–C, B–N, and C^N

Fig. 1 Photoluminescence spectra of prepared BCNO phosphor nano- vibration peaks, which were observed at 1194, 1414, and 2226
fibers as a function of boric acid concentration. Upper inset shows the cm1.2,15 The vibration at 885 cm1 corresponded to stretching
relationship of boric acid concentration to peak wavelength and relative vibrations of tetrahedral BO4 units in B2O3 crystal.16 Based on these
PL intensity. Lower inset shows a photograph image of BCNO phosphor observations, we hypothesized that BCNO nanofibers are composed
nanofibers. of polycrystalline-BCN and B2O3.
The morphology of the prepared nanofibers was examined via FE-
SEM and TEM observation. Prior to observation, prepared samples
intensity, and boric acid concentration. All prepared nanofibers
were dispersed in ethanol via ultra-sonication for 10 min. Fig. 3(a)
showed intense green and yellow emissions under UV-light irradia-
confirmed the existence of nanofiber morphology, with a diameter of
tion that could be seen by the naked eye, as shown in the lower inset
approximately 200 nm. Neither calcination nor ultra-sonication
of Fig. 1. Our group previously reported a single-peak emission in
caused a morphological change in the BCNO phosphor nanofibers,
yellow-emitting BCNO particles.2 In the present study, however,
which is usually observed in BCNO particles. This fact shows that
a double-peak emission was observed in BCNO phosphor nano-
BCNO nanofiber is resist to thermal and ultra-sonic vibration energy.
fibers. Small shoulders of peaks appeared at 470 nm, whereas the
Furthermore, prepared nanofibers were non-agglomerated, as shown
other high intensity peaks were in the range of 528–552 nm, which is
in Fig. 3(b). Fig. 3(c) and (d) show the high-resolution TEM images
ideal for green to yellow emissions. Based on this observation, the
with the corresponding FFT image that represents the polycrystalline
origin luminescence in BCNO nanofibers could be ascribed to
properties of BCNO nanofibers.
a defect in the BCN system11 (at 470 nm), and the boron-oxygen
To determine the atomic distribution and chemical composition of
luminescence center12 (at 528–552 nm). The photoluminescence
the prepared samples, elemental mapping and energy-dispersive
mechanism in BCNO, however, still must be explored in detail.
X-ray spectroscopy were obtained. Elemental mapping is rarely
Further theoretical study is necessary to investigate the origin of
reported in BCNO-related research. Fig. 4(a) shows the elemental
luminescence. The highest intensity of photoluminescence is found at
mapping of B, C, N, and O inside nanofibers. B, C, N, and O were
boric acid concentration of 15 mmol, emitted yellow light, while at
well distributed inside the nanofibers. The atomic distribution in
a boric acid concentration of 17.5 mmol, the PL intensity was slightly
BCNO phosphor nanofibers was much better than the distribution in
decreased due to the rich content of carbon atoms,5 indicated by
a dark appearance as shown in the lower inset of Fig. 1. The emission
color of BCNO particles is reportedly very rich. The color can be
tuned from blue to red by varying the concentration of boric acid,
urea, and polyethylene glycol (PEG). In the present study, blue and
red emissions from BCNO nanofibers were not observed due to the
restriction on the amount of boric acid that potentially affected the
electrospinnability.
Fig. 2 shows the XRD and FTIR spectra of the BCNO nanofibers
prepared at a boric acid concentration of 15 mmol. The XRD pattern
shows distinct peaks at 14.5
and 27.7
corresponding to the crystal
faces, at (111) and (310), respectively, of cubic B2O3 (JCPDS Card
No. 06-0297). A broad bump centered at around 22
was also
observed corresponding to the polycrystalline-BCN.12–14 The distinct
peak of h-BN or t-BN did not appear in the XRD spectra as it does in
BCNO particles due to the absence of urea in the precursor. The Fig. 3 (a) FE-SEM image, (b) TEM image, (c) high resolution TEM
exothermic reaction of urea plays a crucial role in the crystal growth image, and (d) corresponding FFT image of BCNO phosphor nanofibers
of BN. The FTIR spectra confirmed BCNO phosphor nanofibers prepared at a boric acid concentration of 15 mmol.

12630 | J. Mater. Chem., 2011, 21, 12629–12631 This journal is ª The Royal Society of Chemistry 2011

Published on 25 July 2011 on http://pubs.rsc.org | doi:10.1039/C1JM12654G
Downloaded by HIROSHIMA DAIGAKU on 01 September 2011
Fig. 4 (a) Elemental mapping and (b) EDX spectra of BCNO phosphor
nanofibers prepared at a boric acid concentration of 15 mmol.
BCNO particles6 due to the homogeneous distribution of percolation
clusters. Fig. 4(b) shows the EDX spectrum of BCNO nanofibers.
The elements detected by EDX are largely comprised of B, C, N, and
O with mass fractions of 0.13, 0.75, 0.07, and 0.04 respectively. This
result was consistent with the composition of the precursor used in
the experiment. A small fraction (0.01) of other elements was also
detected due to impurities from the TEM grid.
In conclusion, BCNO nanofibers were successfully synthesized by
electrospinning. Intense green and yellow emissions were observed
from BCNO phosphor nanofibers depending on boric acid concen-
tration. XRD and FTIR spectra showed that the BCNO nanofibers
were composed of polycrystalline-BCN and B2O3. FE-SEM and
This journal is ª The Royal Society of Chemistry 2011
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TEM images showed that the BCNO nanofibers were non-agglom-
erated and mechanically strong. This work presents a reliable method
to produce 1-dimensional nanostructures of BCNO, which will be
very useful for applications and functions.
Acknowledgements
We thank Dr Yutaka Kaihatsu for fruitful discussions and Dr Eishi
Tanabe for helping with TEM measurements. This work was sup-
ported by Grant-in-Aid for Scientific Research (A) No. 22246099
from the Japan Society for the Promotion of Science (JSPS). A.B.S.
thanks the Ministry of Education, Culture, Sports, Science, and
Technology of Japan (MEXT) for a doctoral scholarship.
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