Journal of Electronic Materials

[Link]

28TH INTERNATIONAL CONFERENCE ON NUCLEAR TRACKS AND RADIATION

MEASUREMENTS

Investigation of the Structural, Microstructural and Optical Properties

of Cobalt‑Doped Silver Sodium Niobate Ceramics
Meenu Rani1,2 · Y. P. Singh1 · Sheela Devi3 · Shilpi Jindal4

Received: 22 January 2024 / Accepted: 27 August 2024

© The Minerals, Metals & Materials Society 2024

Abstract
As a replacement for lead-based ceramics, pure and cobalt-doped silver sodium niobate (ANN) perovskite ceramics
­Ag0.2CoxNa0.8−xNbO3 (where x = 0, 0.02, 0.04, 0.06, 0.08) were synthesized by solid-state reaction. In the present study, the
effect of cobalt doping at the A-site on the structural, microstructural and optical properties of prepared ANN specimens
is presented. Perovskite orthorhombic specimens were confirmed by x-ray diffraction (XRD) along with a decrease in the
average crystallite size with the increase in Co doping. Scanning electron microscopy (SEM) and energy-dispersive x-ray
spectroscopy (EDX) were conducted to determine the morphology of the fabricated samples. The average grain size of the
samples, as found by using ImageJ software, was in the micrometre range and showed a reduction on increasing Co con-
centration. The optical properties of the samples were studied by photoluminescence (PL) spectroscopy, Fourier transform
infrared (FT-IR) spectroscopy, ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS) and micro-Raman spec-
troscopy at room temperature. PL analysis confirmed the presence of emission peaks in the visible region at wavelengths of
438 nm, 465 nm, 481 nm, 490 nm, 544 nm and 656 nm. Using UV-Vis DRS analysis, the direct band gap of the samples was
calculated by drawing Tauc plots using the Kubelka–Munk equation. The results showed values of 3.21 eV for the pure ANN
sample and 3.10 eV, 3.08 eV, 3.05 eV and 3.03 eV for Co-doped samples where x = 0.02, 0.04, 0.06 and 0.08, respectively.
The FT-IR spectra indicated a strong and sharp absorption peak around 534 ­cm−1 for all the prepared samples, showing the
presence of Nb-O bond stretching and Nb-O-Nb bond bending. Analysis of the recorded Raman spectra showed vibration
bands of the prepared ANN samples.

Keywords Silver sodium niobate · ceramics · perovskite · structural · microstructural · optical

Introduction dielectric materials. The investigation of certain features

such as homogeneity and particle size has led to the manu-
With the ever-increasing demand for new and low-cost facturing of dielectric materials with the desired properties.
devices with better performance quality, there is an imme- Compounds with A ­ BO3 perovskite structure also belong
diate need for controlling the required characteristics of to the family of dielectric materials. They are important
because of their unique properties and their use in various
applications.1 The ­ABO3 structure contains an array of dis-
* Shilpi Jindal torted ­BO6 octahedral corners shared by a variety of inter-
shilpi.85bansal@[Link] stices. Monovalent or divalent cations such as A ­ g+, ­Na+, ­Li+,
+ 2+ 2+
1
Department of Physics Institute of Applied Sciences,
­K , ­Ca and B ­ a generally occupy A-sites, and B-sites are
Mangalayatan University, Beswan, Aligarh, India generally occupied by tetravalent or pentavalent cations such
2
Department of Physics, Hindu College Sonipat, Sonipat,
as ­Nb5+, ­Ti4+ and T­ a5+. There is an opportunity for substitu-
India tion by many types of cations on both A- and B-sites because
3
Department of Physics, MSIT, Janakpuri, New Delhi,
of their open structure. This substitution on either A or B
Delhi 110058, India or on both sites can cause a change in the various physical,
4
Department of Physics, Chandigarh University,
optical and electrical characteristics of the materials.2 ­ABO3
Gharuan, Mohali, India perovskite ceramics are important in fields such as electronic

Vol.:(0123456789)
 M. Rani et al.

and microelectronic devices, optoelectronic devices, micro- transition metals. While traditional experimentation remains
wave tuneable devices, piezoelectric transducers, microelec- crucial, researchers have increasingly turned to simulation
tromechanical systems (MEMS), pyroelectric detectors and studies and machine learning techniques to advance material
sensors. Lead-based materials such as lead zirconate and development and ensure sustainability.8–13 This approach has
lead titanate fulfil the requirements as suitable candidates for the potential to save costs associated with extensive experi-
most of these applications. But lead, being toxic in nature, mentation using various materials. Simulation studies have
needs to be replaced, and for this, many efforts have been put shown promise in manipulating the optical properties of
forth worldwide to develop lead-free materials with proper- materials, with implications for applications such as space
ties comparable to or better than lead-based materials suit- propulsion. By integrating these advanced methodologies,
able for practical applications. Considerable research has we aim to comprehensively improve the properties of anti-
been carried out to study various properties of perovskite ferroelectric ceramics, opening new avenues for techno-
ceramics. The ferroelectric, structural, magnetic, photocata- logical advancement. In the present study, we report on the
lytic and dielectric properties of Co- and Fe-doped ­LaCrO3 impact of cobalt substitution at the A-site in A
­ g0.2CoxNa0.8−x
perovskite prepared by microemulsion were studied, and a ­NbO3 (where x = 0, 0.02, 0.04, 0.06, 0.08) on the structural,
significant change in these properties as a function of dopant microstructural and optical properties. By structural prop-
concentration was reported.1 The impact of copper dopant erties, we mean information regarding the arrangement of
on barium titanate ­BaTi1−xMxO3 (M = Cu, x = 0, 0.02, 0.04) atoms in the crystal structure, while microstructural proper-
perovskite ferroelectric ceramics formed using solid-state ties include grain size, grain boundary, shape and distribu-
reaction was investigated. The prepared specimens exhibited tion of particles.
a tetragonal crystal structure, and the crystallite size was
reported to decrease with an increase in copper dopant.2 A Novelty
study of the structural, optical and photoluminescence prop-
erties of ­K0.5Na0.5NbO3 ceramics prepared by the sol–gel Detailed structural, microstructural and optical proper-
method was also performed. The specimens were found to ties are reported in this paper. Enhanced optical properties
have a perovskite orthorhombic crystal structure at room along with interesting structural and vibrational properties
temperature, and an emission band in the UV/visible region are observed. According to a literature survey, no work has
in the PL spectra was observed. Also, with an increase in been reported for cobalt-doped silver sodium niobate ceram-
sintering temperature, a decrease in optical band energy and ics. Enhancement of its various properties with a significant
a change in the frequency of internal modes of vibration change in the average crystallite size, particle size and band
were noted.3 Sodium niobate (­ NaNbO3) fine powders were gap energy are observed. This work is not under considera-
prepared by a hydrothermal method and then characterized. tion for publication elsewhere.
The particle size of sodium niobate was found to be 2–3 µm
and the band gap was estimated to be 3.45 eV.4 Structural,
electrical and Fourier transform infrared (FT-IR) studies Experimental
of lead-free ­NaMeO3 (Me = Nb, Ta) perovskite ceramics
synthesized by solid-state reaction were carried out. The Materials and Method
prepared samples were reported to have a single-phase
orthorhombic structure, and the dielectric studies showed Polycrystalline samples of pure and Co-doped perovskite
a diffuse phase transition at 394°C for N ­ aNbO3 and 430°C silver sodium niobate (ANN) A ­ g0.2CoxNa0.8−xNbO3 (where
for ­NaTaO3.5 In another study, barium calcium titanate ((Ba, x = 0, 0.02, 0.04, 0.06, 0.08) were prepared by conventional
Ca)TiO3) ceramics were synthesized, and the vibration of solid-state reaction. The precursors used for synthesizing
crystal lattices was investigated by FT-IR spectroscopy.6 the samples including silver oxide ­(Ag2O), sodium carbon-
Amongst developments in lead-free perovskite ceramics, ate ­(Na2CO3), niobium pentoxide (­ Nb2O5) and cobalt oxide
­ABO3-type niobate ceramics form a group of oxide crystals (CoO), all of 99.99% purity, were weighed in proper stoi-
which have significant dielectric, ferroelectric, piezoelectric chiometric ratios. They were then ground using a mortar and
and electro-optical properties with great scientific and tech- pestle. These samples were calcined in a muffle furnace at
nological application potential.7 Perovskite niobates have a very high temperature of 1050°C for 2 h, after which the
been found to be significant functional materials for future calcined samples were ground again with the addition of
technology because of recent developments in telecommu- a few drops of polyvinyl alcohol (PVA). PVA acted as a
nication, electro-optics and piezoelectric components. Silver binder in this calcined powder owing to its water solubil-
sodium niobate is a very important member of this group. ity and excellent adhesive strength because of the presence
Our research focuses on enhancing the structural and opti- of many hydroxyl groups. PVA was easily absorbed by the
cal properties of antiferroelectric ceramics by substituting porous calcined powder and it created a very strong bond
Investigation of the Structural, Microstructural and Optical Properties of Cobalt‑Doped…

and hardened as it dried. Next, pellets 10 mm in diameter Results and Discussion

and 1 mm thick were formed using a hydraulic press by
applying 1 ton pressure. Then the pellets were again placed EDX Analysis
in a muffle furnace, and sintering was performed at a tem-
perature of 1150°C for 1 h to obtain densified samples. In order to obtain information regarding the desired elemen-
tal composition of prepared samples, EDX was performed.
Characterization The EDX profiles of all prepared samples are shown in
Fig. 1. The EDX profile of ­Ag0.2Na0.8NbO3 shows promi-
X‑ray Diffraction (XRD) Pattern nent elemental peaks corresponding to Ag, Na, Nb and oxy-
gen atoms, and the EDX profile of the Co-doped samples
To find the structural information, XRD patterns of samples demonstrates the presence of an additional elemental peak
were acquired on a Philips x-ray diffractometer using Cu-Kα corresponding to cobalt atoms. The presence of the Co ele-
radiation with a wavelength of 1.54056 Å in the 2θ range of mental peak along with A ­ g0.2Na0.8NbO3 peaks proves that
20°–80°. substitution of the desired element has successfully taken
place. A reduction in the Na elemental peak was observed,
thus confirming the substitution of Na with Co atoms in the
Scanning Electron Micrographs
host lattice.
The atomic and weight percentages of various elements
Microstructural analysis was carried out by scanning elec-
present in all specimens as measured from EDX analysis are
tron microscopy (SEM) (TESCAN VEGA3 LM) coupled
presented in Table I.
with energy-dispersive x-ray spectroscopy (EDX).
Structural Analysis
Photoluminescence (PL) Spectroscopy
The XRD patterns of the prepared samples recorded for the
Photoluminescence excitation spectra of all samples were purpose of structural analysis are shown in Fig. 2a.
obtained with a Fluorolog-3 (Horiba Jobin Yvon) using a Diffraction peaks are observed at Bragg angle
xenon arc lamp as the source of light at an excitation wave- 2θ = 22.63°, 22.83°, 28.92°, 32.07°, 32.38°, 41.55°, 46.24°,
length of 400 nm over an emission wavelength range of 46.68°, 51.82°, 52.34°, 52.49°, 57.39°, 57.83° and 67.83°,
415–750 nm. and these peaks correspond to the (101), (020), (021), (200),
(121), (131), (202), (040), (301), (103), (141), (321), (123)
Fourier Transform Infrared (FT‑IR) Spectroscopy and (004) planes, respectively. Peak indexing was done using
Joint Committee on Powder Diffraction Standards (JCPDS)
Infrared spectra of specimens were recorded on a Perki- data card No. 01-082-0606 ­(NaNbO3).14 The most intense
nElmer FT-IR spectrometer in the wavelength range of peak is observed at 32.38°, thus indicating the preferred
400–4000 ­cm−1 using the KBr method. growth of the prepared samples in the (121) plane direction.
The diffraction peaks recorded at 22.83°, 32.07° and 67.83°
were used to find the interplanar spacing, which was further
Ultraviolet–Visible Diffuse Reflectance Spectroscopy
used to calculate unit cell parameters a, b and c. The results
(UV‑Vis DRS)
obtained establish that all pure and Co-doped samples of
ANN have a pure perovskite orthorhombic structure. Similar
For all powdered samples, a double-beam UV/Vis/near-
results have been reported previously.3,5 In the case of per-
infrared (NIR) spectrophotometer (Lambda 750, Perki-
ovskite ­ABO3, the phase stability and degree of distortion is
nElmer, USA) was used to record steady-state diffuse reflec-
found by calculating the tolerance factor (t) of the structure
tance spectra.
because it provides us an estimation of the distance up to
which atoms can move from their ideal packing position in
Raman Spectroscopy the crystal lattice.15,16 The tolerance factor (t) was calculated
using the formula given in Eq. 1.
Raman spectra of the powdered samples were acquired in [ ]
the wavelength range of 150–800 ­cm−1 using a micro-Raman 0.2 × rAg + x × rCo + (0.8 − x) × rNa + rO
t= (1)
spectrometer with a 514-nm argon ion laser at a power level
√ ( )
2 rNb + rO
of ≤ 10 mW with resolution better than 1 ­cm−1.
 M. Rani et al.

­ 2−(1.40 Å) anions, respectively. ­Co2+ ions occupy the

O
A-site of perovskite structure ­ABO3 with coordination num-
­ o2+ with coordination number 6 can exist in both low
ber 6. C
and high spin states. The ionic radius of ­Co2+ is different in
these states. As the ionic radius of ­Co2+ is used in the calcu-
lation of the tolerance factor, the tolerance factor for all the
compositions was calculated for both low and high spin of
­Co2+ and is presented in Table II.
The value of t for a stable orthorhombic perovskite
structure should lie between 0.71 and 0.9. Table II shows
that the calculated values of t lie within this range for all
compositions, thereby confirming that stable orthorhom-
bic perovskite specimens have been prepared. The XRD
patterns reveal that as we continue to increase the cobalt
concentration, there is a slight shifting of the most intense
peak to the increasing angle side as displayed in Fig. 2b,
thus indicating a slight decrease in the values of unit cell
parameters a, b and c. This reduction in the values of a, b
and c can be explained in terms of replacing the larger Na
cation with a large ionic radius with the smaller Co cation
with a small ionic radius at the A-site positions of the host
lattice. The average crystallite size D of all the composi-
tions was calculated with the help of Scherrer’s formula,
given by Eq. 2.17
K𝜆
D= (2)
𝛽Cos𝜃

where K represents the Bragg constant and its value is 0.94,

λ is the wavelength of Cu-Kα radiation used for x-ray diffrac-
tion and it is 1.54056 Å, β is the full width at half maximum
(FWHM) and θ is the Bragg angle. Both β and θ are taken
corresponding to the most intense diffraction peak observed
in the x-ray diffraction patterns. The average crystallite size
of the specimens is found to decrease with the increase in the
concentration of Co. This is in agreement with the observed
decrease in unit cell parameters.
Rietveld refinement of all compositions was also per-
formed using FullProf software, and the observed, cal-
culated and difference in the XRD patterns are shown in
Fig. 3.
Lattice microstrain ε is determined using Eq. 3.
𝛽
𝜀= (3)
4tan𝜃
Here, both β and θ correspond to the most intense dif-
fraction peak obtained in XRD patterns. The lattice micro-
Fig. 1  EDX spectra of A ­ g0.2CoxNa0.8−xNbO3 with composition (a) strain increases when the concentration of Co increases,
x = 0, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e) x = 0.08. thus supporting the decrease in average crystallite size
and unit cell parameters. The microstrain values obtained
­ g+(1.15
where rAg, rCo, rNa, rNb and rO are the ionic radii of A from Eq. 3 are listed in Table III. The lattice microstrain
2+
Å), ­Co (0.65 Å for low spin and 0.745 Å for high spin), was also measured from the Williamson–Hall (W–H) plot
­Na +(1.02 Å), ­N b 5+(0.64 Å) cations (all CN = 6) and according to Eq. 4.
Investigation of the Structural, Microstructural and Optical Properties of Cobalt‑Doped…

Table I  Atomic and weight Elements Composition

percentages of various elements
in ­Ag0.2CoxNa0.8−xNbO3 (where x=0 x = 0.02 x = 0.04 x = 0.06 x = 0.08
x = 0, 0.02, 0.04, 0.06, 0.08)
Mass% Atom% Mass% Atom% Mass% Atom% Mass% Atom% Mass% Atom%

Ag 13.34 5.13 7.26 3.55 8.98 3.44 16.19 7.29 29.32 22.90
Na 8.64 15.58 6.05 13.90 9.09 16.33 3.55 7.51 0.47 1.71
Nb 57.27 25.55 72.10 40.96 60.38 26.84 62.91 32.91 63.55 57.61
O 20.74 53.74 11.87 39.17 20.37 52.57 17.17 52.14 2.16 11.35
Co Nd Nd 2.71 2.42 1.19 0.83 0.19 0.16 4.51 6.44

Table II  Tolerance factors of ­

Ag0.2Cox ­Na0.8−xNbO3 (where x = 0,
0.02, 0.04, 0.06, 0.08)
Composition (x) Tolerance factor (t)
­ o2+
With low-spin C With high-
spin ­Co2+

0 0.848 0.848
0.02 0.845 0.870
0.04 0.843 0.844
0.06 0.847 0.842
0.08 0.838 0.840

The lattice microstrain values as measured from the W–H

plots are 1.60 × ­10−3, 1.80 × ­10−3, 2.14 × ­10−3, 5.34 × ­10−3 and
5.69 × ­10−3 for ceramics with composition x = 0, 0.02, 0.04,
0.06 and 0.08, respectively.
The volume of the unit cell, V, is calculated using Eq. 5.18
V=a × b × c (5)
The variation in unit cell parameters, unit cell volume, aver-
age crystallite size and lattice microstrain with the composition
is listed in Table III.
The x-ray density is found using Eq. 6.19
𝜌X−ray = zMW
NA V (6)

Here, z determines the number of atoms in one unit cell, Mw

is the molecular mass, NA is Avogadro’s number and V is the
Fig. 2  For ­Ag0.2CoxNa0.8−xNbO3 (where x = 0, 0.02, 0.04, 0.06, 0.08):
volume of the unit cell. In order to calculate the bulk density,
(a) XRD patterns over the 2θ range from 20° to 80° and (b) magnified Eq. 7 20 was used.
image of XRD patterns.
m
𝜌Bulk =
v (7)

Here, m and v are the mass and volume, respectively, of the

K𝜆 pellet formed. After calculating ρx-ray and ρbulk, %porosity was
𝛽 cos 𝜃 = + 4 sin 𝜃 (4)
D calculated using Eq. 8.21
In the W–H plot, when β cos θ is plotted along the
( ( ))
𝜌Bulk
Y-axis and 4sin θ is plotted along the X-axis, then the slope %Porosity = 1 − × 100 (8)
𝜌X−ray
of this curve provides the lattice microstrain. The W–H
plots of all ceramics are depicted in Fig. 4.
 M. Rani et al.

Fig. 3  Rietveld plots of ­Ag0.2CoxNa0.8−xNbO3 with composition (a) x = 0, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e) x = 0.08.

The values of ρx-ray, ρbulk and %porosity for all the com- to some extent. A higher porosity value indicates lower
positions are given in Table IV. strength. In the present work, the calculated values of
%porosity is an important parameter to determine the %porosity are small, suggesting that the prepared specimens
strength and stability of synthesized ceramic specimens have high strength and are well densified. High densification
Investigation of the Structural, Microstructural and Optical Properties of Cobalt‑Doped…

Table III  Crystallographic parameters of A

­ g0.2CoxNa0.8−xNbO3 (where x = 0, 0.02, 0.04, 0.06, 0.08)
Composition (x) Unit cell parameters Unit cell vol- Average crystallite Lattice microstrain ε RWp Chi-square
ume V (Å3) size D (nm)
a (Å) b (Å) c (Å)

0 5.5182 7.8410 5.5178 238.75 63.03 2.06 × ­10−3 0.141 1.18

0.02 5.5161 7.8201 5.5175 238.01 58.66 2.21 × ­10−3 0.141 1.2
0.04 5.5146 7.8124 5.5170 237.96 50.63 2.56 × ­10−3 0.139 1.3
0.06 5.5127 7.8053 5.5164 237.36 48.18 2.69 × ­10−3 0.136 1.20
0.08 5.5050 7.8011 5.5158 236.88 46.89 2.76 × ­10−3 0.125 1.8

Fig. 4  W–H plots of A

­ g0.2CoxNa0.8−xNbO3 with composition (a) x = 0, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e) x = 0.08.
 M. Rani et al.

Table IV  The calculated values of ρx-ray and ρbulk and %porosity of and low porosity were observed due to the presence of
­ g0.2CoxNa0.8−xNbO3 (where x = 0, 0.02, 0.04, 0.06, 0.08)
A smaller grains in the space between larger grains.
Composition (x) ρx-ray (g/cm3) ρbulk (g/cm3) %porosity
Microstructural Analysis
0 6.289 5.095 18.99
0.02 6.334 5.095 19.56
SEM micrographs of all samples are shown in Fig. 5.
0.04 6.360 5.095 19.89
The average grain size was determined using ImageJ soft-
0.06 6.402 5.095 20.42
ware. Histogram plots of SEM micrographs of specimens
0.08 6.440 5.095 20.89
showing the distribution of grain size were also drawn and
are shown in Fig. 6.
It was found that the average grain size for samples
decreases from 1.65 µm to 1.29 µm with the increase in Co

Fig. 5  SEM micrographs of ­Ag0.2CoxNa0.8−xNbO3 with composition (a) x = 0, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e) x = 0.08.
Investigation of the Structural, Microstructural and Optical Properties of Cobalt‑Doped…

Fig. 6  Histogram plots of A

­ g0.2CoxNa0.8−xNbO3 with composition (a) x = 0, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e) x = 0.08.

doping from x = 0 to 0.08 as depicted in Table V. A similar positive charge as compared to the substituted A ion or B
reduction in average grain size was reported previously with ion,22–24 the excess positive charge of the dopant is compen-
increasing dopant concentration.1 sated by the creation of cation vacancies that undergo inter-
The decrease in average grain size with increasing Co action with the oxygen vacancies, resulting in a decrease in
content is in line with the decrease in average crystallite size their mobility. These oxygen vacancies play an important
calculated from the XRD data. In the case of ceramics with role in the structure mobility; hence, a decrease in both the
a perovskite structure, heterovalent dopants can be either a average crystallite size and average grain size is observed.
donor or acceptor. In the case of donor dopants with more
 M. Rani et al.

PL Analysis visible region. These peaks are related to defects present in

the sample. The green emission band is due to the presence
The photoluminescence spectra of the powdered samples of oxygen vacancies in the samples. These oxygen vacancies
recorded at an excitation wavelength of 400 nm are shown and crystal defects create intermediate energy levels, leading
in Fig. 7. to the observed emission bands of defect states, which in
The recorded PL spectra of the specimens are similar and turn results in blue/green/red emission bands.3 The presence
show emission peaks at wavelengths of 438 nm, 465 nm, of visible emissions in the PL spectra indicates the utility of
481 nm, 490 nm, 544 nm and 656 nm. The values of the the prepared ANN samples in the generation of visible laser.
energy band gap corresponding to these wavelengths can be Further, these samples are suitable for use in optoelectronic
calculated using Eq. 9. devices such as LEDs, telecommunication devices and opti-
cal storage technologies.
1240
Eg (eV) = (9)
𝜆(nm) FT‑IR Analysis
Here, Eg is the band gap energy (eV) and λ is the wave-
length of the emission peak (nm). The band gap values cal- FT-IR spectra recorded in the wavenumber range of
culated for these wavelengths are 2.83 eV, 2.67 eV, 2.58 eV, 4000–400 ­cm−1 are shown in Fig. 8.
2.53 eV, 2.28 eV and 1.89 eV, respectively. Similar PL emis- FT-IR measurement was performed to study the crys-
sion in the visible region was previously reported in sodium tal lattice vibrations. A strong and sharp absorption peak
potassium niobate ceramics.3 The peaks at 438 nm, 465 nm, was observed around 534 ­cm−1 for all pure and Co-doped
481 nm and 490 nm are related to a blue emission band, ANN samples which is attributed to vibration of the Na-
the peak at 544 nm is related to a green emission band and Niobate framework involving Nb-O stretching, Nb-O-Nb
the peak at 656 nm is related to a red emission band in the bending and the lattice vibrations.4 The spectra also reveal
multiple peaks (A-O absorption bands) in the frequency
Table V  Variation in average
grain size with different values
Composition (x) Average region between 1400 c­ m−1 and 1700 ­cm−1 at 1421 ­cm−1,
grain size 1462 ­cm−1, 1569 ­cm−1 and 1695 ­cm−1. These are assigned
of x of A
­ g0.2CoxNa0.8−xNbO3 (µm)
to the presence of Na-O vibrations.5 It is noted that the
0 1.65 FT-IR spectra of the pure and Co-doped samples are simi-
0.02 1.59 lar, with the difference that the wavenumber correspond-
0.04 1.48 ing to the most intense absorption peak is 531 ­cm−1 in
0.06 1.38 ­Ag0.2Na0.8NbO3, which is slightly smaller than the wave-
0.08 1.29 number of the corresponding absorption peak of the doped
samples. In the case of the Co-doped samples, the wavenum-
bers of the main absorption peaks are 533 ­cm−1, 534 ­cm−1,

Fig. 7  PL spectra of A

­ g0.2CoxNa0.8−xNbO3 (where x = 0, 0.02, 0.04, Fig. 8  FT-IR spectra of ­
Ag0.2CoxNa0.8−xNbO3 (where x = 0, 0.02,
0.06, 0.08). 0.04, 0.06, 0.08).
Investigation of the Structural, Microstructural and Optical Properties of Cobalt‑Doped…

536 ­cm−1 and 537 ­cm−1 for x = 0.02, 0.04, 0.06, 0.08, respec- Table VI  Variation in Nb-O bond length with different values of x of
tively. A similar increase in wavenumber was reported by ­Ag0.2CoxNa0.8−xNbO3
Jin et al.6 This increase in wavenumber is explained by the Composition (x) Wavenumber Force constant Bond length (Å)
fact that when doping of Co is performed, most of the C ­ o2+ ­(cm−1) (M dyne/cm)
+ 2+
ions replace ­Na ions. The smaller ionic radius of ­Co ions
0 531 0.22677338 2.47280
relative to ­Na+ ions results in a decrease in unit cell volume
0.02 533 0.22848487 2.46957
on doping. This was also confirmed from XRD patterns of
0.04 534 0.22934301 2.46796
prepared specimens, according to which an increase in the
0.06 536 0.23106417 2.46475
diffraction angle and decrease in interplanar spacing on dop-
0.08 537 0.23192715 2.46316
ing was observed. As a result, the force constant undergoes
an increase due to the decrease in the length of the Nb-O
bond. Hence, an increase in wavenumber is observed on
Co doping as compared to pure ANN.6 The length of the Eq. 13 was provided by Tauc in order to calculate the band
Nb-O bond for all samples corresponding to the most intense gap.
absorption peak around 534 ­cm−1 was also calculated using 1
Badger’s rule. The formula for finding bond length R is (13)
( )
(𝛼h𝜈) n = A h𝜈 − Eg
given in Eq. 10.25,26
Here, α is the absorption coefficient, Eg is the band gap, h
is Planck’s constant, ν is the frequency of incident photons
√
cij
R=
3
+ dij (10)
K and n denotes the index that tells which type of transition
is occurring in the sample. The value of n is 1/2 for direct
Here, K is the force constant expressed in units of M allowed transitions in the sample. Now, the obtained diffuse
dyne/cm, and 1 N ­ m−1 = 0.001 M dyne/cm. cij and dij are reflectance spectra are changed to the Kubelka–Munk func-
fitting constants, and their values depend on the period tion. For this, the Y-axis is changed to the Kubelka–Munk
number of the bonded atoms in the periodic table. In the function F(R), which is proportional to the absorption coef-
present study, these bonded atoms are Nb and O, and cij ficient α and is given as
and dij values for the Nb-O bond are 0.490 Å and 1.18 Å,
respectively.26 To calculate force constant K, Hooke’s law is F(R) =
1 − R2
(14)
employed and Eq. 11 is used.27 2R

1
√
K where R is the reflectance of the material. Hence, α in Tauc's
v= (11) Eq. 13 is replaced with F(R). On replacing α with F(R) and
2𝜋c 𝜇
inserting values of n, Eq. 13 is converted to the form given
The value of K determines the bond strength: the greater by Eq. 15.
the bond length, the less strong the bond will be, and vice
(F(R)h𝜈)2 = A h𝜈 − Eg (15)
( )
versa. In Eq. 11, µ is the reduced mass of the bonded atoms
in kilograms and can be calculated using Eq. 12.25
Then a curve is drawn taking (F(R)h𝜈)2 along the Y-axis
m1 m2 and photon energy h𝜈 along the X-axis, known as a Tauc
𝜇=
m1 + m2 (12) plot. These plots for all the samples are shown in Fig. 10.
The direct band gap Eg is determined by extrapolating the
In this equation, ­m1 and ­m2 represent the atomic masses linear region of the(F(R)h𝜈)2 vs hν curve towards the X-axis.
of atoms involved in bond formation. Table VI presents the The value of hν corresponding to the point of intersection
Nb-O bond length for all the compositions. on the X-axis provides the direct band gap Eg. The value
of Eg is found to be 3.21 eV for the pure ANN sample and
3.10 eV, 3.08 eV, 3.05 eV and 3.03 eV for the Co-doped
DRS Analysis samples for x = 0, 0.02, 0.04, 0.06 and 0.08, respectively.
A slight reduction in band gap is observed on increasing
Diffuse reflectance spectroscopy (DRS) measurement was
Co doping. This is because oxygen vacancies and crystal
performed on specimens in powdered form to determine
defects are produced in the specimen due to cobalt doping,
their direct band gap, Eg. Figure 9 shows the recorded reflec-
which creates intermediate energy levels, thus explaining the
tance spectra of the specimens.
reduction in band gap on doping. Similar behaviour has been
To determine the direct band gap of the samples,
reported in Co-doped lead titanate materials.30 The calcu-
Kubelka–Munk theory was used.28,29 The relation given by
lated band gap values support the results obtained from PL
 M. Rani et al.

Fig. 9  Reflectance spectra of ­Ag0.2CoxNa0.8−xNbO3 with composition (a) x = 0, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e) x = 0.08.

analysis regarding the use of the prepared samples in various powdered specimens. Figure 11 presents the recorded spec-
optoelectronic applications. tra for all samples, and Fig. 12 presents the fitting of the
Raman spectra for the pure ANN sample, A ­ g0.2 ­Na0.8 ­NbO3,
Raman Spectroscopy Analysis to the Lorentzian function.
In all the specimens, peaks are observed around 177 ­cm−1,
Micro-Raman spectroscopy was performed in order to 213 ­cm−1, 270 ­cm−1, 547 ­cm−1 and 593 ­cm−1. Similar results
study the vibrations of molecular bonds of all the prepared were reported in a La-modified ­AgNbO3 ceramic system.31
Investigation of the Structural, Microstructural and Optical Properties of Cobalt‑Doped…

Fig. 10  Plot of (F(R)hν)2 vs photon energy for A

­ g0.2CoxNa0.8−xNbO3 with composition (a) x = 0, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e)
x = 0.08.

The peaks at 213 ­cm−1 and 593 ­cm−1 are attributed to the peak at 547 ­cm−1 indicates Nb-O-Nb stretching.34 A slight
triply degenerate symmetric O-Nb-O bending vibration and displacement of the peak around 593 ­cm−1 towards a higher
doubly degenerate symmetric O-Nb-O stretching vibration, wavenumber is also observed as the concentration of the Co
respectively, due to the internal modes of vibration of the dopant increases from x = 0 to x = 0.08. This shifting of the
­NbO6 octahedron.32,33 The peak at 270 ­cm−1 is due to the peak towards the higher wavenumber indicates the shorter
presence of O-Nb-O stretching vibration. The presence of a bond length. This is in agreement with the results obtained
 M. Rani et al.

to 1.29 µm with the increase in Co concentration from

x = 0.02 to x = 0.08. PL analysis revealed the presence of
visible emission bands indicating the utility of the fabricated
samples in laser generation in the visible region and in opto-
electronic devices such as LEDs, telecommunication devices
and optical storage technologies. FT-IR analysis indicated
a strong and sharp absorption peak around 534 ­cm−1 for
all samples, which was assigned to the presence of Nb-O
bond stretching and Nb-O-Nb bond bending. Micro-Raman
analysis revealed internal modes of vibration of molecular
bonds, and shifting of the peak around 593 ­cm−1 slightly
towards higher a wavenumber with an increase in Co content
was also observed.

Acknowledgments The authors are grateful to the Central Research

Facility (CRF), IIT, Delhi, for providing laboratory facilities for micro-
Raman spectroscopy.
Fig. 11  Raman spectra of ­Ag0.2Cox ­Na0.8−x ­NbO3 (where x = 0, 0.02,
0.04, 0.06, 0.08). Conflict of interest The authors declare that they have no conflict of
interest.

References
1. M. Aamir, I. Bibi, S. Ata, K. Jilani, F. Majid, S. Kamal, N. Alwa-
dai, M.A.S. Raza, M. Bashir, S. Iqbal, M. Aadil, and M. Iqbal,
Ferroelectric, dielectric, magnetic, structural and photocatalytic
properties of Co and Fe doped ­LaCrO3 perovskite synthesized via
micro-emulsion route. Ceram. Int. 47(12), 16696 (2021).
2. H. Sharma, S. Jindal, and N. Aggarwal, Impact of copper doping
on perovskite structure ferroelectric ceramic. Mater. Today Proc.
33, 1632 (2019).
3. S. Kumar, M. Shandilya, S. Thakur, and N. Thakur, Structural,
optical and photoluminescence properties of ­K0.5Na0.5NbO3
ceramics synthesized by sol–gel reaction method. J. Sol-
Gel Sci. Technol. 88(3), 646 (2018). [Link]
s10971-​018-​4791-y.
4. P. Vlazan, P. Sfirloaga, and F.S. Rus, Synthesis and characteri-
zation of lead-free sodium niobate powder. Studia Universitatis
Babes-Bolyai, Chemia. 61(1) (2016)
5. S.K. Roy, S.N. Singh, K. Kumar, and K. Prasad, Structural, FTIR
Fig. 12  Fitting of Raman spectra of A
­ g0.2 ­Na0.8 ­NbO3 to the Lorentz- and ac conductivity studies of N­ aMeO3 (Me ≡ Nb, Ta) ceramics.
ian function. Adv. Mater. Res. 2(3), 173 (2013).
6. X. Jin, D. Sun, M. Zhang, Y. Zhu, and J. Qian, Investigation
on FTIR spectra of barium calcium titanate ceramics. J. Elec-
from XRD analysis, as the XRD analysis shows a decrease troceram. 22(1–3), 285 (2009).
7. S.C. Bhatt, K. Singh, M. Uniyal, O. Prakash, K.P. Singh, R. Sax-
in the average crystallite size with the increase in the con-
ena, and B.S. Semwal, Temperature dependence of dielectric
centration of Co, thus confirming the decreased bond length. properties of sodium potassium niobate ceramics. Indian J. Pure
Appl. Phys. 45, 609 (2007).
8. L. Malik, G.S. Saini, and A. Tevatia, A self-sustained machine
learning model to predict the in-flight mechanical properties of a
Conclusion rocket nozzle by inputting material properties and environmental
conditions, Handbook of Sustainable Materials: Modelling Char-
Pure and Co-doped ANN samples were prepared by solid- acterization and Optimization. ed. A. Tevatia (Boca Raton: CRC
state reaction. XRD analysis confirmed that all specimens Press, 2023), p. 431.
9. L. Malik, G.S. Saini, M. Malik, and A. Tevatia, Sustainability
had an orthorhombic perovskite structure, with a decrease in
of wind turbine blade: instantaneous real-time prediction of its
the average crystallite size on increasing Co content. SEM failure using machine learning and solution based on materi-
analysis indicated that the average grain size of the pure als and design, Handbook of Sustainable Materials: Modelling,
sample for x = 0 was 1.65 µm, and it decreased from 1.59 µm
Investigation of the Structural, Microstructural and Optical Properties of Cobalt‑Doped…

Characterization, and Optimization. (Boca Raton: CRC Press, characteristics of barium titanate powder. Ind. Eng. Manag. 4(3),
2023), p. 399. 1000166 (2015).
10. L. Malik, Novel concept of tailorable magnetic field and electron 25. M. Kaupp, D. Danovih, and S. Shaik, Chemistry is about energy
pressure distribution in a magnetic nozzle for effective space pro- and its changes: a critique of bond-length/bond-strength correla-
pulsion. Propuls. Power Res. 12(1), 59 (2023). tions. Coor. Chem. Rev. 344, 355 (2017).
11. L. Malik, S. Rawat, M. Kumar, and A. Tevatia, Simulation studies 26. R.M. Badger, The relation between the internuclear distances and
on aerodynamic features of Eurofighter Typhoon and Dassault force constants of molecules and its application to polyatomic
Rafale combat aircraft. Mater. Today Proc. 38, 191 (2021). molecules. J. Chem. Phys. 3, 710 (1935).
12. L. Malik, In-flight plume control and thrust tuning in magnetic 27. S. Kaya, E. Chamorro, D. Petrov, and C. Kaya, New insights from
nozzle using tapered-coils system under the effect of density gra- the relation between lattice energy and bond stretching force con-
dient. IEEE Trans. Plasma Sci. 51, 1325 (2023). stant in simple ionic compounds. Polyhedron 123, 411 (2017).
13. L. Malik and A. Tevatia, Comparative analysis of aerodynamic 28. C. Aydin, O.A. Al-Hartomy, A.A. Al-Ghamdi, F. Al-Hazmi, I.S.
characteristics of F16 and F22 combat aircraft using computa- Yahia, F. El-Tantawy, and F. Yakuphanoglu, Controlling of crystal
tional fluid dynamics. Defence Sci. J. 71(2) (2021) size and optical band gap of CdO nanopowder semiconductors by
14. JCPDS Data Card Number 01-082-0606 low and high Fe contents. J. Electroceram. 29, 155 (2012).
15. Y. Du, Z.X. Cheng, X.L. Wang, and S.X. Dou, Structure, mag- 29. T.V. Vineeshkumar, D.R. Raj, S. Prasanth, N.V. Unnikrishnan,
netic, and thermal properties of ­Nd1-xLaxCrO3 (0≤x≤10). J. Appl. V.P.M. Pillai, and C. Sudarasanakumar, Fe induced optical limit-
Phys. 108, 093914 (2010). ing properties of ­Zn1-xFexS nanospheres. Opt. Laser Technol. 99,
16. T. Bora, and S. Ravi, Sign reversal of magnetization and tun- 220 (2018).
able exchange bias field in ­NdCr1-xFexO3 (x=0.05–0.2). J. Magn. 30. Z. Chchiyai, F.E. Bachraoui, Y. Tamraoui, L. Bih, E.M. Haily, A.
Magn. Mater. 386, 85 (2015). Lahmar, M.E. Marssi, J. Alami, and B. Manoun, Effect of cobalt
17. M. Aadil, S. Zulfiqar, M.F. Warsi, P.O. Agboola, and I. Sha- doping on the crystal structure, magnetic, dielectric, electrical
kir, Free-standing urchin-like nanoarchitectures of C ­ o3O4 for and optical properties of P ­ bTi1−xCoxO3-δ perovskite materials. J.
advanced energy storage applications. J. Mater. Res. Technol. 9, Alloys Compd. 927, 1669799 (2022).
12697 (2020). 31. K.F.S. Jesus, A.C. Silva, Y. Mendez-González, and J.D.S. Guerra,
18. M.H. Carvalho, E.C. Pereira, and A.J.A. de Oliveira, Orthorhom- Structural study of the La-modified A ­ gNbO3 lead-free ceramic
bic ­SnO2 phase observed composite (­ Sn1-xCex)O2 synthesized by system. J. Phys. Conf. Ser. 2298(1), 012012 (2022).
sol–gel route. RSC Adv. 8, 3958 (2018). 32. M. Lal, M. Shandilya, A.S. Kumar, R. Rai, S.S. Nair, and R.
19. S. Selman, F. Hussain, and N. Bakr, Structural study of Palai, Study of structural and magnetoelectric properties of 1–x
­Ba1-xCaxTiO3 ceramic perovskite material using x-ray diffraction ­(Ba0.96Ca0.04TiO3)-x ­(ZnFe2O4) ceramic composites. J. Mater. Sci.
analysis. J. Nanotechnol. Adv. Mater. Int. J. 4, 1 (2016). Mater. Electron. 29, 80 (2018).
20. M. Aadil, S. Zulfiqar, H. Sabeeh, M.F. Warsi, M. Shahid, I.A. 33. Y. Dai, X. Zhang, and G. Zhou, Phase transitional behavior in
Alsafari, and I. Shakir, Enhanced electrochemical energy storage ­K0.5Na0.5NbO3-Li ­TaO3 ceramics. Appl. Phys. Lett. 90(26), 2903
properties of carbon coated ­Co3O4 nanoparticles-reduced gra- (2007).
phene oxide ternary nano-hybrids. Ceram. Int. 46, 17836 (2020). 34. K. Sarkar, V. Kumar, S.B. Das, M. Kumar, and R. Srivastava,
21. A. Ur Rehman, M. Aadil, S. Zulfiqar, P.O. Agboola, I. Shakir, Investigation of opto-electronic properties and morphological
M.F.A. Aboud, S. Haider, and M.F. Warsi, Fabrication of binary characterization of magnesium niobate ceramics synthesized by
metal doped CuO nanocatalyst and their application for the indus- two-stage process. Mater. Today Proc. 49, 446 (2021).
trial effluents treatment. Ceram. Int. 47, 5929 (2021).
22. F.D. Morrison, D.C. Sinclair, and A.R. West, Electrical and struc- Publisher's Note Springer Nature remains neutral with regard to
tural characteristics of lanthanum-doped barium titanate ceramics. jurisdictional claims in published maps and institutional affiliations.
J. Appl. Phys. 11, 6355 (1999).
23. M.S. Zhang, Z. Yin, Q. Chen, W. Zhang, and W. Chen, Study Springer Nature or its licensor (e.g. a society or other partner) holds
of structural and photoluminescent properties in barium titanate exclusive rights to this article under a publishing agreement with the
nano crystals synthesized by hydrothermal process. Solid State author(s) or other rightsholder(s); author self-archiving of the accepted
Commun. 12, 659 (2001). manuscript version of this article is solely governed by the terms of
24. M.K. Trivedi, G. Nayak, S. Patil, R.M. Tallapragada, O. Latiyal, such publishing agreement and applicable law.
and S. Jana, Impact of biofield treatment on atomic and structural