Applied Materials Today 27 (2022) 101427

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Applied Materials Today

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Novel ferromagnetism and negative magnetoresistance in BaBiO3

nanoparticles
Kavil Veettil Shilna, Subasa Chandra Sahoo∗, Kalarikad Jonah Thomas∗
Department of Physics, Central University of Kerala, Periya, Kasaragod, Kerala 671320, India

a r t i c l e i n f o a b s t r a c t

Article history: Materials showing semiconducting and magnetic properties have significant commercial value presently,
Received 27 November 2021 particularly in the field of spintronics. We report a novel ferromagnetic behavior and a negative mag-
Revised 31 January 2022
netoresistance in the non-magnetic semiconductor perovskite material BaBiO3 at room temperature. We
Accepted 12 February 2022
also observe an associated exchange spring like magnetic behavior in the sample annealed at a higher
temperature. We discuss these effects based on a model of defect induced magnetic centers and mag-
Keywords: netic domains in the material. The enhanced magnetization and exchange spring like behavior observed
BaBiO3 in the sample annealed at a higher temperature of 800 °C is attributed to higher number of magnetic
Perovskite defects and two dominant sizes of magnetic clusters. Photoluminescence and energy dispersive X-ray
Defects
spectra corroborate the explanation based on charge induced defects in the material. Interplay of Bi3+
Ferromagnetism
and Bi5+ states in BaBiO3 , leads to a semiconducting behavior at room temperature. From the temper-
Magnetoresistance
ature dependence of the resistivity two distinct activation energies of 0.21 eV and 0.14 eV above and
below 256 K, respectively, have been measured.
© 2022 Elsevier Ltd. All rights reserved.

1. Introduction ditions during the growth. We discuss our observations within a

Magnetic semiconductors are a potential candidate for the re-
alization of multifunctional spintronic devices [1–4]. The desired
materials are generally grown by controlled doping and fine tuning
of the synthesis conditions. Transition metals are generically used
as dopants in non-magnetic oxides for tuning their ferromagnetic
property. However, doping could lead to the formation of mag-
netic impurity clusters, as a result, practical applications of these
doped materials are limited in spintronics. However, non-magnetic
semiconductors where ferromagnetism is established without any
magnetic dopants, and whose charge and spin can be internally
manipulated are of great significance. Several non-magnetic oxide
materials showing room temperature ferromagnetism have been
studied [4–12], however, the reasons for the exhibition of ferro-
magnetism are not fully understood. In these previous studies,
cation and/or anion defect induced ferromagnetism have been pro-
posed, see for example, Al2 O3 [4], SnO2 [4], ZnO [4,5], In2 O3 [4,6],
CeO2 [7], ZrO2 [8], NiO [9], HfO2 [10], TiO2 [11] and LaMnO3 [12].
Here we study such a material, BaBiO3 , a perovskite semiconduc-
tor, which shows an interesting ferromagnetic behavior at room
temperature, which can be varied by changing the annealiing con-
∗
Corresponding authors.
E-mail addresses: subasa@cukerala.ac.in (S.C. Sahoo), kj_thomas@cukerala.ac.in
(K.J. Thomas).
model of defect induced magnetic centers and magnetic domains.
Magnetoresistance (MR) studies are a powerful tool in under-
standing the nature of transport in such materials, which could
be used to realize giant magnetoresistance devices. MR arises due
to the magnetic scattering caused by localized spin fluctuations,
which can lead to a positive or a negative MR depending upon the
state of the spin fluctuation. MR has been widely studied and re-
ported for several ferromagnetic perovskite oxide (ABO3 ) and dou-
ble perovskite (A2 BB’O6 ) compound [13–17]. Also, certain binary
and ternary oxide materials have shown negative MR at room tem-
perature [18–20]. In our study we observe a negative MR in BaBiO3
nanoparticles which is found to increase in samples annealed at a
higher temperarture.
BaBiO3 (Ba2 Bi3+ Bi5+ O6 ), one of the ABO3 type layered per-
ovskites, with interconnected BiO6 octahedra, has a unique elec-
tronic structure owing to the charge disproportionation and
breathing distortions of the octahedra. It is a diamagnetic semi-
conductor due to an inherent charge density wave property. This
ternary compound has found several applications in the fields of
photovoltaics [21], photocatalysis [22] and superconductivity [23].
It is the first oxide topological insulator proposed with a high for-
bidden bandgap [24], exhibiting a two-dimensional electron gas at
the surface [25] though this has not yet experimentally been es-
tablished. Various methods, such as solid-state reaction [26–29],
sol-gel [30,31], and hydrothermal techniques [26,32] have been

https://doi.org/10.1016/j.apmt.2022.101427
2352-9407/© 2022 Elsevier Ltd. All rights reserved.
K.V. Shilna, S.C. Sahoo and K.J. Thomas Applied Materials Today 27 (2022) 101427

employed to synthesize BaBiO3 powder samples. The method of

preparation has been found to have subtle impacts on the struc-
ture and properties of this compound. Several investigations on
BaBiO3 have reported paramagnetic and/or diamagnetic magnetic
properties [33–36]. In this paper, we report that BaBiO3 nanoparti-
cles prepared by sol-gel technique not only show a ferromagnetic
behavior but also an exchange spring like magnetic behavior and a
negative magnetoresistance.

2. Experimental techniques

BaBiO3 nanoparticles were synthesized by sol-gel technique.

Barium nitrate (Ba(NO3 )2 , (purity ≥ 99%; Himedia Laboratories Pvt.
Ltd., India) and Bismuth nitrate (Bi(NO3 )3 .5H2 O), (purity ≥ 98%;
Himedia Laboratories Pvt. Ltd., India) were dissolved in ethylene
glycol (purity ≥ 99%; Sisco Research Laboratories Pvt. Ltd., India), Fig. 1. XRD patterns of BaBiO3 nanoparticle samples annealed at 700 °C and 800 °C
keeping the metal nitrate molar ratio as 1:1. The sol was stirred compared against the JCPDS data.
continuously for one hour and was heated at 60 °C for 30 min to
obtain a gel like composite. The temperature was raised to 150 °C Table 1
to remove the solvent by evaporation. With further heating at the Lattice parameters and crystallite size (D) of BaBiO3 samples annealed
same temperature, it was self-ignited. The residue was collected at at 700 °C and 800 °C. (Standard lattice constants from the JCPDS file
are a = 6.1736 Å, b = 6.1237 Å, c = 8.6507 Å).
room temperature and ground well using an agate mortar and pes-
tle. The fine powder was annealed at two different temperatures; Sample Lattice Parameters D (nm)
700 °C and 800 °C in air for three hours. a (Å) b (Å) c (Å)
Structural characterization of the powdered samples was per-
700 o C 6.180 6.260 8.568 29
formed using a Rigaku Miniflex X-ray diffractometer with Cu-Kα 800 o C 6.187 6.271 8.642 35
radiation (1.5406 Å). Fourier Transform Infrared (FTIR) spectra of
the samples were recorded using a Perkin Elmer Spectrum 2 in-
frared spectrometer. The morphology of the samples was investi- Table 2
Peak position, full width at half maximum (FWHM) and relative inten-
gated by a Field Emission Scanning Electron Microscopy (FE-SEM, sity of the peaks observed in Raman spectra of BaBiO3 samples an-
 IGMA, ZEISS) and elemental composition was determined by an nealed at 700 °C and 800 °C.
energy-dispersive X-ray (EDX) analysis attached with FE-SEM in-
Peak Position (cm−1 ) FWHM (cm−1 ) Relative Intensity (%)
strument. The powders were dispersed on a conductive double
sided adhesive carbon tape for SEM and EDX analyses. Raman 700 o C 800 o C 700 o C 800 o C 700 o C 800 o C

spectra were recorded at room temperature using Witec Alpha 300
Confocal Raman Microscope with 532 nm excitation source op-
erating at 42 mW. Optical absorption spectra were recorded us-
ing Agilent Cary 50 0 0 UV-Vis NIR spectrophotometer. Photolumi-
nescence (PL) spectra were measured by a Horiba Fluorolog Fluo-
rescence Spectrometer. Electrical transport and magnetic measure-
ments were performed on pelletized samples, prepared by com-
pacting the powder by applying a load of 2 tons. Magnetization
of the pelletized samples was measured at different temperatures
ranging from 50 K to 310 K using vibrating sample magnetome-
ter (VSM) of a physical property measurement system (Versa Lab,
Quantum Design, USA). The zero-field cooling (ZFC) and field cool-
ing (FC) temperature dependent magnetizations (M–T) were also
measured. Electrical transport measurements were carried out in
a low temperature cryostat (Cryogenics, UK) between 180 K and
300 K on pelletized samples of size 4 mm × 4 mm × 1 mm. Elec-
trical contacts were made on the pellets by connecting fine copper
wires using silver paste in a standard van der Pauw configuration.
Extreme care has been taken to eliminate chances of contamina-
tion by any magnetic materials during the sample preparation and
the measurements.
3. Results and discussion
Fig. 1 shows X-ray diffraction (XRD) patterns of the prepared
nanoparticle samples annealed at 700 °C and 800 °C. All the ob-
served peaks are indexed to monoclinic perovskite phase of BaBiO3
(JCPDS card No. 01-070-0651). For the sample annealed at 700 °C,
a small additional peak around 24° (marked with ∗ in Fig. 1)) cor-
responding to BaCO3 was observed. The average crystallite size (D)
corresponding to the most intense peak has been calculated using
.9λ
Scherrer’s equation, D = β0cos θ where λ is the wavelength of the
309 304 71 50 10 15
560 533 136 151 65 77
566 561 59 69 100 100
incident X- ray, β is the full width at half maximum (FWHM) in ra-
dian and θ is the Bragg angle. Calculated crystallite size and lattice
parameters are shown in Table 1. Lattice parameters of the samples
are in agreement with the reported data [35]. With the increase
in annealing temperature, there is a slight shift in the position of
peaks towards the lower 2θ value (Supplementary Fig. S1). This
may be due to the strain induced in the nanoparticles or due to Bi
vacancies in the perovskite unit cell leading to a lattice distortion
[37]. The crystallite size of the 700 °C annealed sample was found
to be 29 nm and it increases to 35 nm in the sample annealed at
800 °C. FTIR spectra of both the samples confirm the formation of
BaBiO3 as shown in Supplementary Fig. S2.
Raman spectra of the samples annealed at 700 °C and 800 °C,
measured at room temperature, are shown in Fig. 2. The two dis-
tinct peaks around 300 and 565 cm−1 are characteristic finger-
prints of BaBiO3 . The strongest peak at 565 cm−1 refers to the
breathing mode of BiO6 octahedra [38] and the peak around 300
cm−1 is due to the asymmetrical breathing mode of BiO6 octahe-
dra [39], or bending mode of Bi–O bond [40]. The Raman spectra
were fitted using multiple peaks as shown in Fig. 2 and the peak
positions are listed in Table 2. As seen in Fig. 2, the broad band
around 565 cm−1 was deconvoluted into two peaks. The Bi-O bond
distance is different for Bi3+ - O (2.29 Å) and Bi5+ - O (2.11 Å) [37];
therefore they have different bond strengths. So, it is inferred that
the observed two peaks in the breathing mode signify the presence
of both Bi3+ and Bi5+ in the compound due to charge disproportion-
ation of Bi4+ . It is also seen in the Table 2 that there is an increase

2
K.V. Shilna, S.C. Sahoo and K.J. Thomas
Fig. 2. Raman spectra of BaBiO3 powder samples annealed at 700 °C and 800 °C.
Gaussian fitted peaks are also shown along with the recorded peak.
Fig. 3. EDX spectra of BaBiO3 powder samples annealed at (a) 700 °C and (b)
800 °C.
in the relative intensity for the 800 °C annealed sample which may
be due to the increased crystallite size [41].
Morphological features imaged using SEM at different mag-
nifications are shown in Supplementary Fig. S3, which depicts
nanometer sized particles in the samples. It is also seen that the
smaller nanoparticles are agglomerated to form bigger particles in
these samples. Chemical composition from EDX, shown in Fig. 3,
confirms the formation of BaBiO3 . The Bi: Ba ratio in perovskite
BaBiO3 is equal to 1. However, the data from the EDX show that
the ratio is 0.86 for 700 °C and 0.81 for 800 °C annealed samples.
These results indicate that the atomic percentage of Bi is lower in
3
Applied Materials Today 27 (2022) 101427
both the samples and the Bi concentration decreases (Bi vacancy
increases) with the increase in annealing temperature. This defi-
ciency of Bi induces cation defects in the BaBiO3 perovskite.
Optical absorption data were used to calculate the optical band
gap (Eg ) energy of the samples using the Tauc’s model.
(α hν )n = A(hν −Eg )
Here, α is the absorption coefficient, h is the Planck’s constant, ν
is the photon frequency, n is a constant that determines the type
of optical transition, A is a constant and Eg is the optical energy
band gap. UV absorption spectra and Tauc plot ((α hν )2 vs. hν plot)
of the samples are shown in Fig. 4. Optical band gap energies of
2.07 eV and 1.81 eV were obtained from Tauc plot for the samples
annealed at 700 °C and 800 °C respectively, which are consistent
with the previously reported values ranging between 2.25 eV and
1.80 eV [21,26,28,29,39]]. Our study shows that with the increase
in crystallite size the optical band gap decreases [42]. The optical
band gap in nanoparticles is possibly affected by charge dispropor-
tionation of Bi4+ into Bi3+ and Bi5+ states [43].
Photoluminescence (PL) spectra of the 700 °C and 800 °C an-
nealed samples at excitation wavelength of 370 nm is shown in
Fig. 5. The wide visible emission spectra obtained between 500 and
680 nm is comparable to previously reported data [26,28]. Broad
PL emission results from different kinds of defects within the same
sample [5,44]. The sample annealed at a higher temperature of
800 °C shows a lower PL intensity than the 700 °C annealed sam-
ple, this is consistent with that reported by other research groups
[28].
Fig. 6 illustrates the deconvoluted PL spectra for both the sam-
ples under excitation wavelength 370 nm. The deconvoluted peaks
correspond to different emissions. Several defects at the inter-
stices and vacancies can coexist in the sample. These defects show
emissions near the blue green (≈ 480–550 nm), yellow (≈ 550–
610 nm) and orange-red (≈ 610–750 nm) regions [5,45]. Generally,
the singly charged oxygen vacancies (F+ centers) are responsible
for emission in blue-green region, while the doubly charged oxy-
gen vacancies (F++ centers) show yellow emission and the excess
oxygen results in orange-red emission [5,45]. From Table 3, it is
observed that the relative intensity and the FWHM of the peaks
in yellow region decreases with the increase in annealing temper-
ature. Moreover, the intensity ratio of the peaks observed in blue-
green region (P1) to the peaks observed in yellow region (P3 and
P4) increases with the increase in annealing temperature. It shows
the increase of singly charged oxygen vacancies (F+ centers) in the
800 °C annealed sample.
Fig. 7 shows magnetization versus applied field (M-H) curves
for both the samples. The magnetic hysteresis loops measured for
the two samples are qualitatively and quantitatively different. The
sample annealed at 700 °C showed both ferromagnetic and dia-
magnetic contributions (See Fig. S5). The diamagnetic contribution
has been subtracted from the raw data (Fig. S5) and the ferromag-
netic part is shown in Fig. 7(a). However, the data for the sample
annealed at 800 °C is presented in Fig. 7(b) as measured, which
shows a strong ferromagnetic behavior. The sample annealed at
700 °C has a lower saturation magnetization (Ms ), remanent mag-
netization (Mr ) and coercivity (Hc ), while the sample annealed at
800 °C show higher values. Moreover, a wasp-waisted hysteresis
loop was observed in the sample annealed at 800 °C. The Ms ,
Mr , Hc and the squareness ratio (Mr / Ms ) obtained from the M-
H curves of these samples are listed in Table 4. As observed in
Table 4, the sample annealed at 800 °C shows an enhanced Ms ,
and Mr values, up to two orders of magnitude higher than the
sample annealed at 700 °C. Also, there is an increase of one or-
der of magnitude in Hc for the sample annealed at 800 °C. The
Mr /Ms ratio increases with the increase in the annealing tempera-
K.V. Shilna, S.C. Sahoo and K.J. Thomas Applied Materials Today 27 (2022) 101427

Fig. 4. Tauc plot and absorption spectra of BaBiO3 nanoparticle samples annealed at (a) 700 °C and (b) 800 °C.

Table 3
Analysis of PL spectra of 700 °C and 800 °C annealed samples under the excitation wavelegth of 370 nm.

Peak Position (cm−1 ) FWHM (cm−1 ) Relative Intensity (I) Intensity Ratio
Peak o o o o o o
700 C 800 C 700 C 800 C 700 C 800 C 700 o C 800 o C

P1 543 544 15 15 43 44
P2 558 560 24 23 100 100
P3 575 577 33 29 88 82 0.49 (IP1 /IP3 ) 0.54 (IP1 /IP3 )
P4 605 606 48 24 40 23 1.07 (IP1 /IP4 ) 1.91 (IP1 /IP4 )
P5 645 624 9 18 3 6

Table 4
Magnetic properties obtained from the M-H loops for the samples annealed at 700 °C
and 800 °C.

Sample T (K) Ms (10−4 emu g−1 ) Mr (10−4 emu g−1 ) Hc (Oe) Mr /Ms
o
700 C 300 3.83 0.95 265 0.248
1.15
60 4.30 459 0.267
800 o C 300 623 235
1016 0.377
279
60 723 1205 0.386

modes continuously decreases with increasing temperature. The ir-

Fig. 5. PL spectra of BaBiO3 nanoparticle samples annealed at 700 °C and 800 °C
recorded for excitation wavelength 370 nm.
ture. At 60 K, all the above magnetic parameters were found to be
enhanced from those at 300 K.
Fig. 8 shows the temperature dependence of magnetization (M-
T) curves both in ZFC and FC modes for the sample annealed
at 800 °C under an applied magnetic field of 100Oe. The ferro-
magnetic signal at 100Oe for the sample annealed at 700 °C was
rather weak (not shown). The magnetization in both ZFC and FC
reversibility temperature (Tirr ), where ZFC and FC meet, was noted
around 250 K, indicating that all the spins are unblocked above
this temperature. M-T measurement also confirms the ferromag-
netic behavior of BaBiO3 nanoparticles.
It has been reported in the literature that BaBiO3 can exist in
different valence states, i.e. both Bi3+ and Bi5+ are present along
with Bi4+ in the compound due to charge disproportionation of
Bi4+ [21,29,46,32,39,46,47]. Raman study also supports this as we
have observed two peaks in the BiO6 octahedral breathing mode
due to different Bi-O bond lengths (Fig. 2). Moreover, if Bi ions
were present only in 4+ state (5d10 6s1 ), a half-filled 6s conduc-
tion band is expected to give rise to a metallic behavior of the
compound [23,30]. However, optical measurements (Figs. 4 and 5)
show semiconducting behavior with a band gap. Bi4+ (5d10 6s1 )
with one unpaired electron can contribute to a paramagnetic be-
havior [33,35]. Bi3+ (5d10 6s2 ) and Bi5+ (5d10 6s0 ) have completely
filled orbitals which give rise to a diamagnetic behavior. In the
present study we observe a significanlty large ferromagnetic be-
havior (Fig. 7). If Bi3+ ion is in an excited state with electronic
configuration 5d10 6s1 6p1 , then the unpaired electrons may have
their associated magnetic moments ferromagnetically aligned to
give a net magnetic moment. Presence of anion vacanies i.e. singly
charged oxygen vacancies (F+ centers) in the compound, as ob-
served in the PL spectra, has also one unpaired electron in each va-
cancy site, which caries a magnetic moment. However, the doubly
charged oxygen vacancies (F++ centers) with paired electrons do
not contribute to ferromagnetism. Moreover, as we have observed

4
K.V. Shilna, S.C. Sahoo and K.J. Thomas
Fig. 6. Deconvoluted PL spectra of the (a) 700 °C and (b) 800 °C annealed samples.
Fig. 7. M-H loops of BaBiO3 nanoparticle samples annealed at (a) 700 °C and (b) 800 °C measured at 300 K and 60 K, for the applied field range -10–10 kOe. Full range M-H
loops from -30 to 30 kOe are shown as insets in the respective figures. Note: The diamagnetic contribution was subtracted from the raw data in (a) and presented, where
(b) is presented as measured.
Fig. 8. ZFC and FC magnetization curves of the 800 °C annealed sample under an
applied field of 100 Oe. Tirr is approximately 250 K.
in EDX data, there is Bi deficiency (cationic vacancy) in the com-
pound. When there is a vacancy, either of Bi3+ or Bi5+ in the BiO6
octahedral site, the sorrounding six oxygen will contribute their
electron to cationic vacancy site for charge neutrality. So, either
5
Applied Materials Today 27 (2022) 101427
three or five electrons in the cationic vacancy site contribute to-
wards the net magnetic moment.
The double exchange interaction between the excited Bi3+ ion
having unpaired electron (6s1 6p1 ) and Bi5+ (6s0 ) having no un-
paired electron will lead to ferromagnetism in the compound.
Moreover, the direct exchange interactions between the local mag-
netic moments at F+ centers (F+ – F+ ) or indirect interaction by
mediation of conduction electrons (F+ – conduction electron –
F+ ), lead to ferromagnetism [5,45,48,49]. In addition, the inter-
sublattice interaction between the magnetic centres at cationic or
anionic vacancy sites in the unit cell could also lead to long-range
ferromagnetic ordering in BaBiO3 .
The enhanced magnetization in the 800 °C annealed sample is
due to the formation of more number of magnetic centers due to
the increased cationic vacancy (observed in EDX) and anionic va-
cancy (F+ centres observed in PL spectra) in the sample [49]. An
increase in crystallite size also leads to an increase in Ms values in
ferro/ferri-magnetic materials [50,51].
As we have observed cationic and anionic vacancies in the com-
pound, it is inferred that the anisotropy in the sample is mainly
induced by the defects. Therefore larger Hc and Mr values are ex-
pected in the sample where there is a larger number of defects.
The dM/dH vs H plot (Supplementary Fig. S6) of 800 °C an-
nealed sample shows two stepped magnetic behavior correspond-
K.V. Shilna, S.C. Sahoo and K.J. Thomas
Fig. 9. Schematic illustration of the possible distribution of magnetic moments in (a) 700 °C (b) 800 °C annealed BaBiO3 samples.
Fig. 10. (a): Temperature dependence of electrical resistivity of BaBiO3 (800 °C annealed sample) (b) Arrhenius plot showing two distinct activation energies below and
above 256 K.
ing to two different anisotropy and coercive fields. On the other
hand, 700 °C annealed sample shows only single-step behavior.
Fig. 9 illustrates a cartoon of possible magnetic domain distribu-
tion within the material. Coherent rotation of magnetic moments
in the magnetic clusters and isolated moments produce a single
step magnetic behavior in the 700 °C annealed sample. However, in
the 800 °C annealed sample, magnetic domains of nearly two dif-
ferent sizes having different anisotropies rotate at different fields
when the applied field reverses the direction showing two step
magnetic behavior. Ferro or ferrimagnetic materials having grains
of two different sizes having different anisotropies also show such
type of exchange spring magnetic behavior [50].
Resistivity of the 800 °C annealed sample measured in the tem-
perature range of 180 K to 300 K is shown in Fig. 10(a). Resistance
of the 700 °C sample was beyond the measurable limit of the in-
strument. As seen in Fig. 10(a), BaBiO3 nanoparticles show a semi-
conducting nature. From the Arrhenius plot shown in Fig. 10(b),
two distinct activation energies of 0.21 eV and 0.14 eV are observed
for temperatures T > 256 K and T < 256 K, respectively. These val-
ues are consistent with previously reported results [36,52].
6
Applied Materials Today 27 (2022) 101427
The electrical properties of BaBiO3 are related to the oxida-
tion state of Bi. As discussed above, the disproportionation of
Bi4+ into Bi3+ and Bi5+ is the reason for the semiconducting nature
in BaBiO3 [32,46,47,52]. This configuration constructs an ordered
structure leading to an alternating expansion and contraction of
BiO6 octahedra in the perovskite lattice sites [29,34]. The resul-
tant static charge density wave or breathing mode distortion cre-
ates a bandgap at the Fermi level which gives rise to semiconduct-
ing properties [29,32,35]. BaBiO3 may contain site occupancy shift
of Bi to the Ba site which may contribute to an increased electri-
cal resistivity [29]. A kink in the temperature dependent resistivity
is observed around 256 K as reported previously and has been at-
tributed to the changes in BiO6 octahedra tilting angle and short
Bi-O bond length [52].
MR of the samples were measured at room temperature and are
shown in Fig. 11. MR is defined as,
R (H ) − R (O )
MR% = × 100
R (O )
K.V. Shilna, S.C. Sahoo and K.J. Thomas
Fig. 11. Magnetoresistance of 700 °C and 800 °C annealed BaBiO3 nanoparticle sam-
ples. The arrows indicate the direction of the sweep of H.
where R(H) and R(0) are the resistances with and without an ap-
plied magnetic field respectively. As seen in Fig. 11, a maximum
negative MR of 5% and 15% were observed for the samples an-
nealed at 700 °C and 800 °C, respectively, at H = 30 kOe. An
increase in annealing temperature resulted in a larger MR value
which clearly shows the effect of increased number of ferromag-
netic spin ordering. The number of ferromagnetic clusters induced
in the nanomaterials is more in the 800 °C annealed sample than
in the 700 °C annealed sample. A larger number of magnetic mo-
ments associated with the defect sites in the ferromagnetic clusters
formed in the nanocrystallites results in a stronger ferromagnetic
coupling and a long-range ordering [53], in agreement with our
magnetic measurements. The plot also shows a hysteresis where
the resistance does not revert back to its original value after the
magnetic field is swept to zero; this indicates the presence of mag-
netic domains in the nanomaterial. The effect is more pronounced
in 800 °C annealed sample with larger crystallites.
The negative MR of BaBiO3 samples may also arise due to hop-
ping of the spin polarized electrons between Bi3+ and Bi5+ sites.
Hysteresis nature of MR is indicative of ferromagnetic domains
leading to a memory effect. Conduction mechanism by hopping
has been suggested for the observation of room temperature nega-
tive MR and a memory effect in the bulk polycrystalline Ca2 Fe2 O5
[20]. Recently, room temperature negative MR has also been re-
ported in NiO nanoparticles owing to the spin polarized electron
hopping between Ni2+ and Ni3+ sites [18].
4. Conclusions
BaBiO3 nanoparticles were synthesized by sol-gel technique and
subsequently annealed at 70 0 °C and 80 0 °C in air. Structural stud-
ies show monoclinic BaBiO3 phase in the samples. Optical band
gaps of 2.07 and 1.81 eV were observed in the 70 0 °C and 80 0 °C
annealed samples respectively. Magnetic and resistivity measure-
ments show presence of ferromagnetic domains in the semicon-
ducting BaBiO3 nanoparticles. Exchange spring like magnetic be-
havior with enhanced magnetization was observed in the 800 °C
annealed sample. Existence of mixed oxidation states of Bi, cationic
and anionic vacancies with the associated magnetic moments are
possible sources of ferromagnetism and the negative magnetore-
sistance in these nanoparticles. Tunability of ferromagnetism and
negative magnetoresistance in BaBiO3 with controlled annealing
temperature may find potential applications in the field of spin-
tronics.
7
Applied Materials Today 27 (2022) 101427
Declaration of Competing Interest
Authors have no conflicts of interest.
CRediT authorship contribution statement
Kavil Veettil Shilna: Conceptualization, Data curation, For-
mal analysis, Investigation, Validation, Writing – original draft.
Subasa Chandra Sahoo: Validation, Formal analysis, Writing – re-
view & editing. Kalarikad Jonah Thomas: Conceptualization, Su-
pervision, Writing – review & editing.
Acknowledgments
UGC-DAE Consortium for Scientific Research, Kalpakkam Node,
Kokilamedu is acknowledged for providing laboratory facilities
for conducting part of this work. The authors thank Dr. S.
Chakravarty, Scientist F, UGC-DAE Consortium for Scientific Re-
search, Kalpakkam, Tamilnadu, India for the electrical transport
measurements. Authors thank Dr. Baidyanath Sahu, IIT Bombay,
Mumbai for the scientific discussion on Rietveld ananlysis. K. V.
Shilna acknowledges Kerala State Council for Science, Technology
and Environment (KSCSTE), Kerala, India for Research Fellowship
(Sanction order no. 614/2018/KSCSTE dated 26.10.2018).
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.apmt.2022.101427.
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