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Synthesis, structural and optical properties of nanocrystalline
Ba2NaNb5O15
Swarup Kundua and K. B. R. Varma*b
Published on 04 September 2013. Downloaded by Université Laval on 05/09/2013 12:21:38.
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5 DOI: 10.1039/b000000x
Fine powders comprising nano crystallites of barium
sodium niobate, Ba2NaNb5O15 (BNN) were obtained via
citrate assisted sol-gel route at much lower temperature than
that of conventional solid-state reaction route. The phase
10 evolution of BNN as a function of temperature was
investigated by thermo gravimetric analysis (TGA),
differential thermal analysis (DTA), Fourier transform
infrared spectroscopy (FTIR) and X-ray powder diffraction
(XRD). DTA data followed by XRD studies confirmed the
15 BNN formation temperature to be around 923 K. The as-
synthesized powders heat-treated at 923 K/10h attained
orthorhombic structure akin to that of parent BNN phase.
Transmission electron microscopy revealed that the
nanocrystallites are associated with dislocations. The optical
20 band gap was calculated using Kubelka-Munk function.
These nanocrystallites exhibited strong visible
photoluminescence (PL) at room temperature. The PL
mechanism was explained by invoking the dielectric
confinement effect, defect states and generation of self-
25 trapped excitons.
Introduction
Niobium containing polar materials have been very useful as
30 they possess various interesting physical properties that include
high dielectric constants,1 relatively high non-linear optical
coefficients,2-4 intense photoluminescence5-7 etc. It would be of
both scientific and technological interest to visualize physical
properties of polar materials comprising nanometer scale
35 crystallites as most physical properties are crystallite size
dependent. Size effects on the properties of materials have
become an intriguing area of research.8 In particular the size
dependent optical properties are very much important because of
the miniaturization of the modern devices. Phosphor materials are
40 in great demand for making digital displays, energy efficient light
emitting diodes (LEDs) etc. These optical properties are
significantly dependent on not only the composition but also the
crystal structure of the material. The materials associated with
tungsten bronze structures are of special interest.
45
Barium sodium niobate, Ba2NaNb5O15 (BNN) belongs to the
tungsten bronze family with general formula (A1)4(A2)2B10O30
where A1 is fifteen coordinated, A2 is twelve coordinated and B is
This journal is © The Royal Society of Chemistry [year]
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DOI: 10.1039/C3CE41250D
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CrystEngComm Accepted Manuscript
six coordinated. At room temperature BNN belongs to
50 orthorhombic crystal structure (space group Pba2) with lattice
parameters a = 12.425(2) Å, b = 12.484(9) Å and c = 3.977(2) Å.
BNN is an interesting material from its excellent electro-optic2,
non-linear optical2, 9 properties view point in addition to its very
high power laser damage threshold compared to that of LiNbO3
55 and KDP single crystals. This material has also been found to
have acousto-optic10 and piezoelectric11 properties comparable to
those of LiNbO3. In fact, the aforementioned physical properties
were reported only for BNN single crystals grown by Czochralski
method at 1703 K.12 There are several reports on the synthesis of
60 polycrystalline powders of BNN via solid-state reaction and sol-
gel methods.13 In the sol-gel method a molecular level mixing
could be achieved by complexing the metal ions with carboxyl
group. Therefore it is possible to obtain high purity, uniform
grain size and chemically homogeneous products. But
65 nevertheless, the synthesis of nano material with multiple metal
ions is quite challenging.
The complex precursor prepared in the present work reveals
the unique thermal decomposition behaviour leading to the
70 formation of phase-pure BNN at a temperature as low as 923
K/10h in contrast with that of solid-state reaction route in which
the formation temperature was 1173 K. The structural and optical
properties of these nano crystallites have been investigated
systemically.
75
Experimental methods
The reactants that were used to prepare the nanometer sized
BNN powders were ammonium niobate (V) oxalate pentahydrate
80 (NH4[NbO(C2O4)2].5H2O, H.C. Starck GmbH), anhydrous citric
acid (C6H8O7, Sigma-Aldrich), hydrogen peroxide (H2O2, 30%
w/v, SDFCL), ammonia solution (SDFCL), sodium acetate
(CH3COONa, Fisher Scientific Co.) and barium nitrate
(Ba(NO3)2, Sigma-Aldrich).
85
The key steps involved in the synthesis of the powder are
summarized in a flow chart (Fig. 1). Initially, the peroxo-citro-
niobium precursor solution was prepared as per the procedure
outlined by Narendar et. al.14 To a glass beaker containing 30 ml
90 of H2O2 citric acid was added while stirring the solution. After 30
[journal], [year], [vol], 00–00 | 1
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DOI: 10.1039/C3CE41250D

obtained. Then to adjust the pH to ~6.5, aqueous ammonia was

H2O2+C6H8O7 added to it. Subsequently, this solution was slowly added to the
initially prepared peroxo-citro-niobium precursor solution while
Stirring at room temperature 20 stirring. Then the temperature was raised to 403 K at which water
for 30 minutes started evaporating and a viscous gel was found to form. The
A transparent solution temperature was further raised to 573 K. At this temperature the
gel started burning leaving behind a residue (black precursor
powder). This black powder was analyzed by subjecting to
Add NH4H2[NbO(C2O4)3].5H2O 25 various stages of heat-treatment.

Stirring at 343 K for 1 h For comparison, Ba2NaNb5O15 powder at micrometer scale

was also synthesized via conventional solid-state reaction
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a yellowish solution
method. For this, reagent grade BaCO3, Na2CO3 and Nb2O5 were
30 mixed in stoichiometric amounts and the mixed powder was
calcined in the 873K-1173 K temperature range in air.
Add ammonia aqueous solution

CrystEngComm Accepted Manuscript

to adjust pH ~ 6.5
Characterization

35 Thermo analytical studies were carried out on the as-prepared

Stirring at 343 K for 10 minutes
powders in the temperature range of 300 K-1020 K using a
commercial TA-instrument, TG-DTA thermal analyzer at a
Add Ba(NO3)2, CH3COONa, C6H8O7, H2O heating rate of 10 K/min. FT-IR spectra were recorded using
Parkin-Elmer (Model: Spectrum 1000) spectrometer in the range
and adjust the pH ~ 6.5
40 of 400-4000 cm-1. For this, the powder sample was mixed with
KBr and pelletized. To confirm the phase formation X-ray
Stirring at 343 K for 1 h diffraction patterns were recorded using Pan Analytical
diffractometer with Cu-Kα (1.5408 Å) radiation in the 2θ range of
Precursor solution 10-80o. The morphology and the crystallite size distribution in
45 the as-synthesized powder were studied by scanning electron
microscope (FEI Inspect F50). To determine the crystallite size
Raise the temperature to 403 K for 2 h
distribution several SEM micrographs were analysed using
SigmaScan Pro 4.0 software package developed by Jandel
Precursor gel Scientific. The well separated crystallites were marked separately
50 with a pixel calibrated scale bar and then a statistical average was
Raise the temperature to 573 K for 2 h done. Transmission electron microscope (TEM) was used to
determine the structure and analyze the crystallinity. The TEM
images were recorded with the help of JEOL JEM-2001F at an
Precursor black powder accelerating voltage of 200 kV. The diffuse reflectance spectra
55 were recorded for powders using UV-Vis Perkin-Elmer Lambda
750. The Kubelka-Munk function was used to calculate the band
Heat-treat the resulted powder at gap. Photoluminescence (PL) spectra were recorded using WITec
different temperatures. system with a 355 nm Nd:YAG laser as an excitation source. The
optical photographs were recorded after filtering the 355 nm laser
Fig. 1 Flow chart for the synthesis of BNN nano powder via citrate 60 beam.
assisted sol-gel method

minutes of vigorous stirring a stoichiometric amount (13 mol of
5 H2O2 : 1 mol of oxalic group) of niobium ammonium oxalate was
added to it. The mixture was again stirred at 343 K for 1 h to
decompose the oxalate salt completely. A clear yellowish
solution was formed. After that an appreciable amount of
ammonia solution was added to adjust the pH to ~6.5. The
10 stirring was continued for about another 1 h at 343 K, to ensure
the decomposition of unreacted H2O2 in the solution. In this step
peroxo-niobium complex reacts with citrate ions and forms
ternary peroxo-citrate-niobium complex,
(NH4)4[NbO(O2)C6H5O7)]2. Appropriate amounts of C6H8O7,
15 Ba(NO3)2 and CH3COONa were dissolved one after the other in
25 ml of deionized water and finally a clear solution was
Results and discussion
The thermal behaviour of the precursor powder was
65 investigated by subjecting the as-synthesized powders to TG-
DTA analysis (Fig. 2). In the TGA the weight loss (~4%) in the
300 - 410 K temperature range was observed owing to the
dehydration of the powder. A weak endothermic dip that is
observed in the same temperature range in the DTA confirms the
70 dehydration process. In the 410 - 1015 K temperature range a
weight loss of 38.6% was noticed which is ascribed to the
decomposition (decarboxylation and dehydration) of oxalate
ligands present in the complex precursor.14 An exothermic peak
that is observed around 923 K in DTA confirms the

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 Page 3 of 7 CrystEngComm
crystallization of the final Ba2NaNb5O15 (BNN) phase as
confirmed by X-ray diffraction studies that are described in the
next section.
5 The formation of BNN phase is further confirmed by FTIR
analysis. Fig. 3 shows the FTIR spectra of the dried gel and the
one heat-treated at different temperatures. There is a significant
change in the FTIR spectra with the heat-treatment temperature.
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10 Fig. 2 TGA-DTA profiles for the Ba2NaNb5O15 precursor powder
Fig. 3 Fourier transformed infrared spectra (FT-IR) of the precursor
powder and the powder heat-treated at different temperatures
A strong broad absorption band witnessed in Fig. 3(a) in the 3500
15 – 2500 cm-1 range specifies the presence of hydrogen bonds
associated with O-H (3450 cm-1 due to O-H stretching) and N-H
groups [3160 cm-1 due to ν3(N-H) and 3028 cm-1 due to ν1(N-
H)].14 The intensity of which decreases with increasing heat-
treatment temperature. The as-synthesized powder also exhibits
20 an absorption band in the 1750-1250 cm-1 range which centred
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DOI: 10.1039/C3CE41250D
around 1618 cm-1 and its intensity decreases on increasing the
temperature of heat-treatment. Nevertheless this less intense band
is present even after heating the sample around 773 K/5h which is
due to the presence of a unidentate carboxylate ligand.15 The
25 observed broad band in between 450-830 cm-1 and centered at
620 cm-1 is due to the metal-oxygen (Nb-O) vibrations. The broad
absorption band observed (Fig. 3a) in 1750-1620 cm-1 region is
due to the overlapped absorption from C=O bond and a
prominent absorption around 1630 cm-1 corresponds to the
30 bending mode of H2O.16 The bands observed at 900, 655 and 570
cm-1 are assigned to Nb=O in highly distorted NbO6 octahedra,
symmetric stretching of the niobia polyhedra and ν(Nb-O)
present in slightly distorted NbO6 octahedra respectively.17 The
sharp band observed around 2340 cm-1 is due to the asymmetric
35 stretching mode of carbon dioxide present/trapped in the sample.
CrystEngComm Accepted Manuscript
The IR spectra of the phase pure BNN sample (Fig. 3d-f) did not
exhibit any bands around 2340, 1630 and 3500 cm-1 which
confirm the complete decomposition of the precursor powder and
the absence of entrapped carbon dioxide. There exists absorption
40 bands only in the region of 400-1000 cm-1 which originate from
the mixed vibrations of Nb-O bonds.
Fig. 4 (a-f) represents the X-ray diffraction patterns obtained
for Ba2NaNb5O15 precursor powder, the heat-treated powder at
45 different temperatures along with that of BNN ceramic powder
prepared via solid-state reaction route. The pattern (Fig. 4a)
recorded for the precursor powder does not have any reflections
that could be assigned to BNN phase. But when the temperature
of calcination is raised to 853 K the Bragg diffraction peaks
50 corresponding to BNN phase are observed (Fig. 4b), in addition
Fig.4 X-ray diffraction patterns recorded for the precursor powder (a) as-
prepared, heat-treated at (b) 853 K/5h, (c) 923 K/10h and (d) 1023 K/5h,
(e) 1223 K/5h, (f) via solid-state reaction route
55 to a less intense diffraction peak (marked as ‘*’) suggesting that
the decomposition of the precursor at this temperature has not
reached completion. The XRD pattern (Fig. 4c) obtained for 923
K/10h heat-treated sample showed the Bragg reflections that
could be indexed to an orthorhombic phase of BNN associated
60 with a space group Pba2 (ICSD PDF no. 01-086-0739). The
Journal Name, [year], [vol], 00–00 | 3
 CrystEngComm
average size of the crystallite calculated from (001), (410) and
(131) diffraction peaks using the Scherrer formula was found to
be ~45 nm for the sample heat treated at 923 K/10h. The X-ray
diffraction patterns for the samples heat-treated at 1023 K/5h and
5 1223 K/5h could be indexed with BNN phase (Fig. 4d-e). The
Bragg peaks in the X-ray diffraction pattern (Fig. 4f) recorded for
the powdered sample prepared via solid-state reaction route are
sharp as compared to that of the sample prepared using citrate
assisted sol-gel method indicating larger crystallite sizes
10 associated with the powder. This observation is corroborated by
SEM studies.
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Fig 5. (a-f) shows the FESEM images and crystallite size
distribution (secondary electron used) in citrate assisted sol-gel
15 method derived BNN nanocrystalline powder and the micrometer
sized BNN powder obtained by conventional solid-state reaction
route. The precursor powder heat-treated at 923 K/10h (Fig. 5a-c)
revealed the presence of well crystallized BNN nano crystalline
powder (with an average crystallite length of 110 nm and width
20 of 48 nm) associated mostly with elongated morphology. The
average size of the crystallite determined by this method is higher
than that of the calculated
Fig.5 Representative FE-SEM micrograph of the BNN powder obtained
25 from citrate assisted sol-gel route heat-treated at various temperatures
(a)-(b) low magnification view of 923 K/10h (c) high magnification view
of 923 K/10h (d) 1023 K/5h, (e) 1223 K/5h, (f) solid state reaction route,
inset of (b) is EDS recorded for the sample heat-treated at 923 K/10h.
one based on the X-ray peak broadening. This size difference is
30 attributed to the agglomeration effect. The agglomeration effect
may be due to the Van der Walls forces acting between the
crystallites.18 Smaller crystallites especially at nanometer level
have a tendency to agglomerate in the process of surface free
4 | Journal Name, [year], [vol], 00–00
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DOI: 10.1039/C3CE41250D
energy minimization. The agglomeration could also take place
35 due to the melting of adjacent nanocrystallites.19 The energy
dispersive X-ray spectroscopy (EDS) carried out (inset of Fig. 5b)
on the sample confirmed the chemical compositions to be close to
stoichiometric ratio (within the limits of experimental errors
involved) of BNN. EDS patterns were recorded randomly at five
40 different locations and compositional analyses were done and
found to be very close to each other which corroborate the
homogeneity of the BNN nano crystallites prepared via citrate
assisted sol-gel method. Figures 5d and 5e represent the SEM
micrographs of the sample heat-treated at 1023 K/5h and
1223K/5h respectively. The average crystallite sizes were found
45
to be length 117 nm, width 54 nm for the sample heat-treated at
1023 K/5h and length 149 nm, width 99 nm for the sample heat-
treated at 1223 K/5h (histogram shown in Fig. S1). The SEM
CrystEngComm Accepted Manuscript
micrograph recorded for the powder prepared via solid-state
50 reaction route is shown in Fig. 5f and the crystallite size is larger
than that of powders obtained via citrate assisted sol-gel method.
Further the crystallites are more agglomerated than that prepared
by citrate assisted sol-gel method and due to this reason it was
very difficult to measure crystallite size distribution. All these
55 observations strongly suggest that citrate assisted sol-gel route of
the synthesis of BNN at nanoscale is much superior that could be
exploited for commercial applications.
Fig. 6a depicts the TEM micrograph of the sample heat-treated
60 at 923 K/10h. The average crystallite length and width were
found to be 99 nm and 59 nm respectively (in the supplementary
Fig.6 Transmission electron microscopy images of the BNN nano powder
heat-treated at 923 K/10h (a) bright field image, (b) SAED pattern and (c)
65 HRTEM image, the arrow marks show the position of dislocations (d)
HRTEM image indicates the imperfect crystallite surface (e) Magnified
view of the HRTEM. (f) Schematic illustration of the BNN crystal structure
viewed from [100] direction Nb5+ ions locate at an octahedral sites
coordinated by oxygens and a periodic stacking of Ba2+, Nb5+, Na+ and O2-
70 ions
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 Page 5 of 7 CrystEngComm
information the histograms of length and width were shown in
Fig. S2). Figure 6b represents the SAED pattern of the BNN nano
crystallites which confirms the good crystallinity. The high
resolution TEM image shown in Fig. 6c-d confirm good
5 crystallinity of the prepared nano powder and reveals more
structural details of the BNN nano crystallites. In fig 6c the lattice
fringes with the spacing of ~8 Å correspond to twice that of the
lattice parameter ‘c’ for BNN unit cell. This doubling of unit cell
is common for tungsten bronze structured materials.20 In Fig. 6c,
10 the marked arrows (1 and 2) indicate the presence of dislocations.
Similarly the HRTEM image shown in Fig. 6d confirms the
presence of imperfect nature of the crystallite surface. A
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schematic of the BNN unit cell is drawn with Diamond software
package (Fig. 6f) to visualize and compare with the lattice image
15 shown in Fig. 6e. Figure 6e is a zoomed portion of Fig 6c as
marked on it. The comparison clearly demonstrates the periodic
stacking of Ba2+, Nb5+, Na+ and O2- ions. The spacing between
the two Ba+ ions layer was found to be 8 Å, which is in close
agreement with that of BNN unit cell parameters.
20
Diffuse reflectance spectra were recorded for the
nanocrystalline powder in the 250-2000 nm wavelength range.
The dependence of diffuse reflection on wavelength for BNN
nano powder is shown in the inset of Fig. 7. A sharp cut off was
25 observed around 400 nm. The relation among the diffuse
reflectance (R∞) emanating from infinitely thick sample,
absorption coefficient (K) and the scattering coefficient (S) is
given by the Kubelka-Munk function21 F(R∞)
(1 − R∞ ) 2 K
F ( R∞ ) = = (1)
R∞ S
30
Fig.7 Plot of Kubelka-Munk function and the inset depicts diffuse
reflectance spectra of the samples heat-treated at different
temperatures
In Tauc relation22 for indirect band gap material, the
35 absorption coefficient (α) and the optical band gap (Eg) is related
by α hν = const.(hν − Eg ) 2 . Now considering scattering
coefficient (S) to be constant with the wavelength of light, the
equation (1) and Tauc relation could be combined and
represented by:
This journal is © The Royal Society of Chemistry [year]
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DOI: 10.1039/C3CE41250D
40 [ F ( R∞ )hν ]1/ 2 = cont.(hν − Eg ) (2)
Fig. 7 represents the plot of [F(R∞)hν]1/2 vs hν, from which the
band gap was calculated by straight line fit to the linear portion of
the curve. The band gap obtained is 3.18 eV for the sample heat-
treated at 923 K/10h and 3.11 eV for the sample heat-treated at
45 1223 K/5h. This latter finding is close to that of the band gap of
BNN single crystal (Eg=3.1eV)23. Thus the obtained band gap for
the sample heat-treated at 923 K/10h is higher than that of the
bulk single crystal and is attributed to the well known nano size
effects.24
50
The variation of photoluminescence (PL) spectra for the
sample heat-treated at different temperatures is depicted in Fig.
8a. The PL spectra obtained for the sample heat-treated at 923
CrystEngComm Accepted Manuscript
K/10h showed a strong and broad violet-blue emission. A gradual
55 decrease in PL intensity was observed for the samples heat-
treated in the 923 K to 1223 K temperature range. A schematic of
the possible PL mechanism is shown in Fig. 8b.
Fig.8 (a) PL spectra recorded for the sample heat-treated at different
60 temperatures with excitation wavelength of 355 nm. (Inset: optical
snapshot of the sample surface under excitation), (b) schematic of the PL
mechanism
The energy of the photons used to excite the sample is ~ 3.5
eV (corresponds to the wavelength of 355 nm), but the peak
65 energy of PL emission was found to be ~2.9 eV which is less
than that of the band gap of BNN nano crystals measured from
the diffuse reflection spectra. Therefore, it is believed that the
observed broad PL spectra have its origin in defect states.25 The
high resolution TEM image depicted the presence of defects
Journal Name, [year], [vol], 00–00 | 5
 CrystEngComm
(mostly dislocations) in the nanocrystallites. The difference
between the energy of excitation and the emission is about 0.6 eV
which indicates that there is a strong nonradiative relaxation of
the exciton. The blue emission may be ascribed to the self-
5 trapped exciton (STE) recombination occurring in the NbO6 60
octahedra.26 The binding energy and the radiative lifetime of the
STE are strongly dependent on the grain size as reported in the
literature.27, 28
10 For nanoscale crystallites the binding energy is higher and the
65
radiative lifetime is substantially longer than that of the bulk
material which enhances the PL emission to a great extent. The
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atoms on the surface of nanocrystalline materials are in the
“naked state” associated with a huge number of unsaturated,
15 dangling bonds on the surface. These dangling bonds serve as
70
defect states which could also be responsible for the observed
PL29, 30. These defect states create localized levels within the
forbidden gaps of the materials. The dielectric confinement effect
also plays a significant role in the enhancement of PL because of
20 the increase in binding energy and this effect is more prominent
in nanoscale materials.31 PL intensity observed for the sample 75
heat-treated at 1223 K/5h is almost negligible which is ascribed
to the presence of less defect states as a result of relatively large
crystallite size associated with this sample. The sample that was
25 prepared via solid-state reaction route did not show any
significant photoluminescence. 80
Conclusions
BNN nano powders were synthesized via citrate assisted sol-gel
method at much lower temperatures than that of the conventional
30 solid-state synthesis route as established by DTA combined with 85
XRD and FTIR studies. SEM and TEM studies corroborate the
results obtained by utilizing the above characterization tools.
HRTEM micrograph reveals the presence of dislocations
(defects) in the nanocrystalline BNN sample. Intense visible PL
35 was observed at room temperature in the nanocrystalline BNN. 90
The observed optical properties suggest that this nano crystalline
BNN is a highly promising candidate for PL applications.
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DOI: 10.1039/C3CE41250D

Nanocrystalline barium sodium niobate synthesized via citrate assisted sol-gel route exhibited room
temperature photoluminescence properties.
Published on 04 September 2013. Downloaded by Université Laval on 05/09/2013 12:21:38.

CrystEngComm Accepted Manuscript