Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Synthesis and characterization of nanocrystaline hexagonal boron

nitride powders: XRD and luminescence properties
Branko Matović a,n, Jelena Luković a, Marko Nikolić b, Biljana Babić a, Nadežda Stanković a,
Bojan Jokić c, Branislav Jelenković b
a
Institute for Nuclear Sciences Vinca, Centre of Excellence, Belgrade University, Serbia
b
Institute for Physics, Centre of Excellence, Belgrade University, Serbia
c
Faculty of Technology and Metallurgy, Belgrade University, Serbia

art ic l e i nf o a b s t r a c t

Article history: Nanocrystalline hexagonal boron nitride powders (h-BN) were synthesized from urea and boric acid
Received 2 June 2016 followed by pirolysis and subsequent heat treatment in nitrogen atmosphere. Materials have been
Received in revised form analyzed by means of X-ray diffraction, Photoluminescence and Field emission electron microscopy
13 July 2016
methods. Obtained results show that starting h-BN powder, synthesized at 750 °C, is composed of
11
Accepted 14 July 2016
layer crystallites with average crystallite thickness and crystallite lateral size of 3.94 and 10.4 nm, re-
spectively. A broad emission and intense luminescence intensity were observed due to the large atomic
Keywords: disorder. Higher annealing temperature increases crystallite size and turbostratic h-BN transforms to
Nanomaterials well crystallized h-BN at 1500 °C.
Boron nitride
& 2016 Published by Elsevier Ltd and Techna Group S.r.l.
Photoluminescence

1. Introduction
Nanoscale hexagonal boron nitride (h-BN) possesses many
unique thermal, electrical, optical, chemical and mechanical
properties such as high thermal conductivity, lubricity, hardness,
chemical inertness, the capability of hydrogen uptake, low di-
electric constant and loss [1–7]. In addition, h-BN has attracted
increasing attention recently due to the diverse functionalities
such as strong deep UV luminescence and field emission proper-
ties [8–10] which give a great potential for a wide application in
advanced technologies.
The structure of h-BN is similar to that of graphite. It consists of
layered structure comprising of a network of (BN)3 rings which
hold together by van der Walls forces, with an interlayer spacing of
∼0.33 nm, which enable easy gliding of the layers with respect to
each other [11,12] and development of 2D BN sheets [13,14]. The
thermal stability, specific surface area, oxidation behavior, particle
shape and size of BN materials are significantly influenced by the
degree of crystallinity. Thus, nucleation and growth reactions of
h-BN are of general interest to understand the formation of well-
ordered BN powders. Great variety of methods for h-BN synthesis
had been published in the literature [15–23]. However, searaching
for new method that gives reproducible power properties, high
yield and is energy effective, still occupies the activity of scientists.
n
Corresponding author.
E-mail address: mato@vinca.rs (B. Matović).
The aim of this work is to present a low temperature and cost
effective method for obtaining nano-BN powder and to investigate
ordering-layerlattice of BN and its luminescence properties de-
pending on thermal treatment.
2. Materials and methods
Boron nitride BN was synthesized from cheap starting materi-
als: Boron acid (H3BO3 -Zorka Sabac Co.) and Urea (CO(NH2)2
-Harnstoff). A mixture of H3BO3 and CO(NH2)2 with a molar ratio
of 1:5 was dissolved in distilled water (H2O) and stirred for 2 h at
70 °C using a hot magnetic stirrer. The obtained powder was in-
itially thermal treated at 750 °C in N2 atmosphere for 16 h with
heating rate of 4 °C/min. The obtained powder was calcined at
650 °C in ambient atmosphere for 2 h using heating rate of 10 °C/
min. After cooling down at room temperature, the powder was
centrifuged five times (i.e. three times water and two times in
ethanol) for 5 min at 4500 rpm in order to remove all residual
impurities. In the next step, powder was dried in air at 70 °C and
heat treated at 1000, 1250 and 1500 °C in N2 atmosphere for 1 h
with heating rate of 10 °C/min. About 40 mass % of the starting
mixture of H3BO3 and CO(NH2)2 was converted into approx-
imatelly 1 g of h-BN powder.
The phase purity and crystallinity of obtained and calcined BN
powders were examined using X-ray diffraction (Raguku Ultima
IV, Japan) and Raman spectroscopy The X-ray beam was nickel-
filtered CuKα1 radiation (λ ¼0.1540 nm, operating at 40 kV and

http://dx.doi.org/10.1016/j.ceramint.2016.07.096
0272-8842/& 2016 Published by Elsevier Ltd and Techna Group S.r.l.

Please cite this article as: B. Matović, et al., Synthesis and characterization of nanocrystaline hexagonal boron nitride powders: XRD and
luminescence properties, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.07.096i
2 B. Matović et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎
40 mA). XRD data were collected from 4 to 80° (2θ) at a scanning
rate of 2°/min. A refinement of the structure of powders was un-
dertaken in order to elucidate the crystal structure and micro-
structure of BN phase. Phase analysis accompanied with Rietveld
refinement was done by using the PDXL2 software (version
2.0.3.0) [24], with reference to the patterns of the International
Centre for Diffraction Database (ICDD) [25], version 2012. Crys-
tallite sizes were determined from the XRD line broadening using
the Scherrer equation and the integral peak breadth (PDXL2
software).
The interlayer distances (d) were calculated from the 002 re-
flections by applying Bragg's law, while the crystallite thicknesses
(Lc) and lateral sizes (La) were estimated from the 002 and 100
reflections, respectively, using Scherrer's equation [26]. Since the
shape factor k from Scherrer relation varies depending on the
reflection plane and the shape of the crystallite, k ¼0.9 and k¼ 1.84
where used for Lc and La determination, respectively [27]. The
morphology and grain size images were taken by FESEM TESCAN
Mira XMU, at 20 kV. The luminescence measurements were per-
formed at room temperature on the Spex Fluorolog spectro-
fluorometer system with C31034 cooled photomultiplier, utilizing
500 W Xenon lamp as excitation source. Photoluminescence
emission spectra were measured within the spectral region from
350 to 600 nm and excitation from 250 to 400 nm.
3. Results and discussion
Fig. 1. presents the XRD patterns of BN samples collected dur-
ing different annealing temperatures, including the as-prepared
BN material, denoted hereafter as BN750 and the thermal treated
samples in the range 1000–1500 °C, denoted hereafter as BN1000,
BN1250 and BN1500, respectively. XRD analysis of starting h-BN
obtained at 750 °C exhibits very diffuse diffraction lines, in such
way that some atomic planes are impossible to indicate, only the
diffraction lines h00 (100), 00l (002) were visible. The principle
reflection is located around 2θ
26.6° and can be assigned to the
(002) reflection of the graphite-like h-BN structure [28]. Addi-
tional yet much weaker peaks are observed around
42.3°, cor-
responding to the (100)/(101) reflections, in close agreement with
the Joint Committee on Powder Diffraction Standards (JCPDS) card
no. 34–0421. Diffraction lines 10 l formed broadened 10 bands,
002
Intensity (a.u.)
100
004
101
(d)
(c)
(b)
(a) 10-band
10 20 30 40 50 60
2θ degree
Fig. 1. XRD patterns of the (a) as-prepared BN-raw powder, calcined at (b) 1000 °C,
(c) 1250 °C and (d) 1500 °C.
Please cite this article as: B. Matović, et al., Synthesis and characterization of nanocrystaline hexagonal boron nitride powders: XRD and
luminescence properties, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.07.096i
which is according to Warren theory characteristic for the stacking
faults located on the (001) planes [29]. However, random-layer
lattice structure h-BN defect led to the formation of 10 bands in
the XRD pattern and is known as a turbostratic structure [30].
Turbostratic BN crystallites exhibit a similar hexagonal-layered
structure to that of h-BN, however lacking a high orientation
among their layers; i.e. the planar arrangement could be con-
sidered a random one [31]. In spite of higher calcining tempera-
ture, a similar XRD patterns were obtained for samples obtained at
1000 and 1250 °C. There is a slightly narrowing of the diffraction
lines, however, diffraction peaks around
42.3°, 10 band, which
correspond to the (100)/(101) atomic planes are overlap and can-
not be separated. On the other side in sample annealed at 1500 °C
the reflections (100) and (101) can be well distinguished, as well as
(004 and 110), indicating that stacking faults started to disappear.
The interlayer spacing of the (002) atomic plane of the samples
thermally treated at different temperatures presented with the
slight shift of the peak to the higher 2θ angles. The shift of the
peak is due to the increasing degree of ordering, and approach the
value of 0.334 nm, which is closer to the ideal value of 0.333 nm
for hexagonal BN. Ideal value was useful indicator for assigning the
lattice deflects and turbostratic structure, and a decrease of this
value by heat treatments is widely accepted indication of an or-
dering in the crystal structure. The structural properties of the
thermal treated samples were summarized in Table 1. Starting
h-BN powder is composed of
11 layer crystallites with average
crystallite thickness and crystallite lateral size of 3.94 and 10.4 nm,
respectively. Increasing annealing temperature increases crystal-
lite size and the number of layers, i.e., triggers the transformation
of turbostratic h-BN to the ordered-layerlattice BN, leading to
“complete” three-dimensional ordering.
Fig. 2, displays the typical SEM image of h-BN material calcined
at different temperatures. It reveals that morphologies of starting
powder is agglomerated and consists of somewhat irregular and
platelike crystals. Further increase in annealing temperature
changes the morphology of the powders, especially for sample
calcined at 1500 °C. The building blocks tend to agglomerate to
form a wide range of particle sizes. The change in morphology can
be ascribed to high annealing temperature which provides fast
diffusion necessary for crystallite growth in the form of nanopla-
telets. It can be roughly estimated that the particle size of sample
annealed at 1250 °C possess lateral size of ∼40 nm and thickness
∼20 nm, whilst the platelike size of sample annealed at 1500 °C
lies in the range of 100–150 nm, and thickness of sheet is about
20–30 nm. The average crystallite size calculated from Sherrer's
formula is 24 nm what is in good agreement with the platelet
thickness.
The photoluminescent emission spectrums of BN samples after
excitation by the laser at 315 nm, are shown in Fig. 3. Broad
emission and intense narrow lines in the emission spectrum are
the result of the defect transition in BN [32,33]. The two different
emission spectrums tips can be seen in the case of samples with
different annealing temperature. The first upper spectrum of BN
annealed at 750 °C have broad emission as a result of the high
structure disorder. Increasing of annealing temperature leads to
the growth of structure order and to reduction of the defects
110
number. This further leads to decrease in luminescence intensity
and the appearance of narrow emission lines as a result of the
existence of just a few defect levels. This is in good correlation
with XRD and FESEM data, which confirm that, the transformation
of turbostratic h-BN to the ordered BN with higher annealing
temperature lead to decrease of defect levels.
70 80
The similar overall reduction of luminescence intensity is seen
in the excitation spectrum. In Fig. 4 are shown excitation spec-
trums of h-BN samples annealed at different temperatures mon-
itored at 432 nm. Increasing the annealing temperature leads to a
 B. Matović et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 3

Table 1
XRD structural properties of the h-BN phase obtained annealing at different temperatures.

Temperature [°C] ao [nm] co [nm] d [nm] FWHM [°] Lc [nm] La [nm] n [no.]

750 0.24769 0.67612 0.33806 2.076 3.94 10.4 11.6

1000 0.24829 0.67185 0.33592 1.553 5.27 9.16 15.68
1250 0.24919 0.66793 0.33396 0.749 11.0 15.6 32.9
1500 0.24977 0.66805 0.334025 0.343 24 24 71.8

ao, co: lattice parameter, d: interlayer distance calculated by Bragg's law, FWHM: full-width at half maximum, Lc: crystallite thickness derived by Scherrer's equation, La:
crystallite lateral size derived by Scherrer's equation, n: number of layers estimated by the ratio Lc/d.

Fig. 2. FESEM images of h-BN powder calcined at different temperatures (a) as-prepared BN at 750 °C; calcined at (b) 1000 °C, (c) 1250 °C and (d) 1500 °C.

decrease in luminescence intensity and the visibility of sharp ex-
citation peaks.
4. Conclusion
We have demonstrated that the Semi-crystalline, turbostratic
boron nitride (h-BN) can be successfully synthesized from cheap
starting materials, Boron acid (H3BO3) and Urea (CO(NH2)2 fol-
lowed by heat treatment in N2 and air atmospheres, respectively.
XRD analysis confirmed that calcining temperature takes an
important role in the transformation turbostratic to the ordered
BN leading to a reduction of defects in the nano size h-BN. Due to
the high structure disorder starting material has broad emission
and intense luminescence intensity which decrease with higher
annealing temperature. This simple and effective method can be
used to prepare boron nitride in large scale.
Acknowledgment
This project was financially supported by the Ministry of

Please cite this article as: B. Matović, et al., Synthesis and characterization of nanocrystaline hexagonal boron nitride powders: XRD and
luminescence properties, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.07.096i
4 B. Matović et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎
Fig. 3. Emission spectrums of h-BN samples annealed at different temperatures
with 315 nm excitation wavelength.
Fig. 4. Excitation spectrums of h-BN samples annealed at different temperatures
monitored at 432 nm.
Education and Science and Technological Development of Serbia.
References
[1] X.-F. Jiang, Q. Weng, X.-B. Wang, X. Li, J. Zhang, D. Golberg, Y. Bando, Recent
Progress on Fabrications and Applications of Boron Nitride Nanomaterials: A
Review, J. Mater. Sci. Technol. 31 (2015) 589–598.
[2] N. Kostoglou, K. Polychronopoulou, C. Rebholz, Thermal and chemical stability
of hexagonal boron nitride (h-BN) nanoplatelets, Vacuum 112 (2015) 42–45.
[3] L.H. Li, Y. Chen, Atomically Thin Boron Nitride: Unique Properties and Appli-
cations, Adv. Funct. Mater. 26 (2016) 2594–2608.
[4] G. Lian, X. Zhang, S. Zhang, D. Liu, D. Cui, Q. Wang, Controlled fabrication of
Please cite this article as: B. Matović, et al., Synthesis and characterization of nanocrystaline hexagonal boron nitride powders: XRD and
luminescence properties, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.07.096i
ultrathin-shell BN hollow spheres with excellent performance in hydrogen
storage and wastewater treatment, Energy Environ. Sci. 5 (2012) 7072–7080.
[5] M.J. Meziani, W.-L. Song, P. Wang, F. Lu, Z. Hou, A. Anderson, H. Maimaiti, Y.-
P. Sun, Boron Nitride Nanomaterials for Thermal Management Applications,
Chemphyschem 16 (2015) 1339–1346.
[6] A. Pakdel, Y. Bando, D. Golberg, Nano boron nitride flatland, Chem. Soc. Rev. 43
(2014) 934–959.
[7] A. Pakdel, C. Zhi, Y. Bando, D. Golberg, Low-dimensional boron nitride nano-
materials, Mater. Today 15 (2012) 256–265.
[8] D. Golberg, Y. Bando, Y. Huang, T. Terao, M. Mitome, C. Tang, C. Zhi, Boron
Nitride Nanotubes and Nanosheets, ACS Nano 4 (2010) 2979–2993.
[9] Y. Kubota, K. Watanabe, O. Tsuda, T. Taniguchi, Deep Ultraviolet Light-Emitting
Hexagonal Boron Nitride Synthesized at Atmospheric Pressure, Science 317
(2007) 932–934.
[10] K. Watanabe, T. Taniguchi, T. Niiyama, K. Miya, M. Taniguchi, Far-ultraviolet
plane-emission handheld device based on hexagonal boron nitride, Nat.
Photon. 3 (2009) 591–594.
[11] J. Eichler, C. Lesniak, Boron nitride (BN) and BN composites for high-tem-
perature applications, J. Eur. Ceram. Soc. 28 (2008) 1105–1109.
[12] R. Pease, An X-ray study of boron nitride, Acta Crystallogr. 5 (1952) 356–361.
[13] L. Hua, Li, Y. Chen, B.-M. Cheng, M.-Y. Lin, S.-L. Chou, Y.-C. Peng, Photo-
luminescence of boron nitride nanosheets exfoliated by ball milling, Appl.
Phys. Lett. 100 (2012) 261108.
[14] H. Zeng, C. Zhi, Z. Zhang, X. Wei, X. Wang, W. Guo, Y. Bando, D. Golberg, “White
Graphenes”: Boron Nitride Nanoribbons via Boron Nitride Nanotube Un-
wrapping, Nano Lett. 10 (2010) 5049–5055.
[15] S.P.S. Arya, A. D’Amico, Preparation, properties and applications of boron ni-
tride thin films, Thin Solid Films 157 (1988) 267–282.
[16] J. Economy, R. Anderson, A New Route to Boron Nitride, Inorg. Chem. 5 (1966)
989–992.
[17] L. Shi, Y. Gu, L. Chen, Z. Yang, J. Ma, Y. Qian, Formation of nanocrystalline BN
with a simple chemical route, Mater. Lett. 58 (2004) 3301–3303.
[18] G.-J. Zhang, J.-F. Yang, M. Ando, T. Ohji, Nonoxide–boron nitride composites:
In situ synthesis, microstructure and properties, J. Eur. Ceram. Soc. 22 (2002)
2551–2554.
[19] M. Zheng, Y. Gu, Z. Xu, Y. Liu, Synthesis and characterization of boron nitride
nanoropes, Mater. Lett. 61 (2007) 1943–1945.
[20] J.-Q. Bi, W.-L. Wang, Y.-X. Qi, Y.-J. Bai, L.-L. Pang, H.-L. Zhu, Y. Zhao, Y. Wang,
Large-scale synthesis of BN nanotubes using carbon nanotubes as template,
Mater. Lett. 63 (2009) 1299–1302.
[21] J. Duan, R. Xue, Y. Xu, C. Sun, Low temperature synthesis of h-BN nanoflakes,
Mater. Lett. 62 (2008) 3355–3357.
[22] L. Lin, T. Liu, Y. Zhang, R. Sun, W. Zeng, Z. Wang, Synthesis of boron nitride
nanosheets with a few atomic layers and their gas-sensing performance,
Ceram. Int. 42 (2016) 971–975.
[23] B. Matovic, B. Babic, A. Devecerski, M. Radovic, A. Minovic, M. Miljkovic,
S. Boskovic, New synthetic route for nanocrystalline boron nitride powder,
Mater. Lett. 65 (2011) 307–309.
[24] PDXL Version 2.0.3.0 Integrated X-ray Powder Diffraction Software, Rigaku
Corporation, Tokyo, Japan, 2011, pp. 196–8666.
[25] Powder Diffraction File, PDF-2 Database, International Centre for Diffraction
Data (ICDD), 2012.
[26] P. Scherrer, Bestimmung der Größe und der inneren Struktur von Kolloid-
teilchen mittels Röntgenstrahlen., Nachrichten von der Gesellschaft der Wis-
senschaften zu Göttingen, Math.-Phys. Kl. (1918) 98–100.
[27] J. Thomas, N.E. Weston, T.E. O’Connor, Turbostratic Boron Nitride, Thermal
Transformation to Ordered-layer-lattice Boron Nitride, J. Am. Chem. Soc. 84
(1962) 4619–4622.
[28] R.T. Paine, C.K. Narula, Synthetic routes to boron nitride, Chem. Rev. 90 (1990)
73–91.
[29] W. B, X-Ray diffraction, Addision-Wesley Publishing Company Inc, 1969.
[30] K. A.V, Stacking faults in graphitic boron nitride, Sov. Phys. Crystallogr. 20
(1975) 596–598.
[31] S. Alkoy, C. Toy, T. Gönül, A. Tekin, Crystallization behavior and characteriza-
tion of turbostratic boron nitride, J. Eur. Ceram. Soc. 17 (1997) 1415–1422.
[32] V. Korsaks, B. Berzina, L. Trinklere, Low-temperature 450 nm luminescence of
hexagonal boron nitride, Latv. J. Phys. Tech. Sci. (2011) 55.
[33] M.G. Silly, P. Jaffrennou, J. Barjon, J.S. Lauret, F. Ducastelle, A. Loiseau,
E. Obraztsova, B. Attal-Tretout, E. Rosencher, Luminescence properties of
hexagonal boron nitride: Cathodoluminescence and photoluminescence
spectroscopy measurements, Phys. Rev. B 75 (2007) 085205.