Materials Chemistry and Physics 322 (2024) 129523

Contents lists available at ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Unveiling the magnetic and optical properties of barium bismuthate thin

films with distinct Ba/Bi ratios
G. Acero a, b, M.A. Ponce c, F. Moura d, A.Z. Simões a, b, *
a
School of Engineering and Sciences, Guaratinguetá, Brazil
b
São Paulo State University – UNESP, Guaratinguetá, SP, Brazil
c
Institute for Materials Science and Technology Research (INTEMA) (CONICET-National University of Mar del Plata) Juan B. Justo 4302, 7600, Mar del Plata,
Argentina
d
Advanced Materials Interdisciplinary Laboratory, Federal University of Itajuba, UNIFEI – Campus Itabira, MG, Brazil

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• BaBiO3.films were obtained by PPM.

• Ba/Bi ratios can tune the magnetic
properties.
• Grain morphology and oxygen va­
cancies affects the properties of BaBiO3.

A R T I C L E I N F O A B S T R A C T

Keywords: This research aims to investigate the optical and magnetic properties of BaBiO3 (80:20), BaBiO3 (50:50), and
BaBiO3 BaBiO3 (30:70) thin films obtained by the polymeric precursor method. For better sample designations, the
Chemical synthesis following codes were employed: (80:20) (BBO82), (50:50) (BBO55), and (30:70) (BBO37). The observed prop­
Magnetism
erties for barium bismuthates thin films were elucidated in terms of bismuth and oxygen vacancies as well as
Photoluminescence
grain morphology, which can be controlled by stoichiometric changes (Ba/Bi ratios). According to the x-ray
Thin films
results the films crystallize in a rhombohedral BaBiO3 structure with an R-3R space group without any secondary
phase as confirmed by Rietveld analyses. According to the photoluminescence results, x-ray photoelectron
spectroscopy measurements as well as the law of approach to saturation (LAS), there are a significant presence of
[ ]
oxygen vacancies and vacancy clusters BiO5 .Vo. in the films with high proportion of bismuth. The optical and
magnetic properties developed by these films are originated from the following factors: tilting of BiO6 clusters
which changes the length and angle of Bi–O–Bi bonds, creating a magnetic field responsible for the distinct Mr/
Ms ratios, the formation of bipolarons caused by charge transfer between [BiO6] and [BiO5. V⋅o] due to the oxygen
vacancies formation, plate-like morphology which makes the domains easier to be switched under an applied
external field resulting in a superparamagnetic behavior, charge disproportionation of various valence states
(Bi+3 and Bi+5). Based on these results, new potential devices can emerge as possible tools to be applied in
switches, actuators, spintronics, magnetic field sensors, etc.

* Corresponding author. School of Engineering and Sciences, Guaratinguetá, Brazil.

E-mail address: zirpoli.simoes@unesp.br (A.Z. Simões).

https://doi.org/10.1016/j.matchemphys.2024.129523
Received 17 February 2024; Received in revised form 10 May 2024; Accepted 28 May 2024
Available online 29 May 2024
0254-0584/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

1. Introduction state reaction method doped lanthanum manganites La1− xCaxMnO3

with five different concentrations of Ca (x = 0.1, 0.2, 0.3, 0.4 and 0.5).
Due to their high Curie temperatures and thermal stability, BaBiO3 UV–Visible analysis reveals that the band gap decreases with the
(BBO) thin films have generated significant interest in the context of incorporation of Ca. The synthesized samples were investigated for
ABO3-type perovskites, where A represents an alkali/alkaline earth charge density distribution using maximum entropy method, utilizing
metal and B denotes a transition metal [1–6]. BBO can be formed the XRD data sets. From the charge density analysis, it is found that the
through distortions in oxygen octahedra, have found extensive use in bond lengths for La–O and Mn–O bonds decrease with the addition of Ca.
various electronic applications. At room temperature, BBO stands out The ionic nature between La and O atoms and covalent nature between
among high critical temperature (Tc) superconductors and is considered Mn and O atoms are enhanced for 40 % of calcium-doping. For 50 % of
an insulator. Superconductivity arises in the presence of Bi due to a Ca-doped sample, ionic nature between La and O atoms and covalent
relativistic contraction of the Bi 6s2 electron pair, producing valence nature between Mn and O atoms decrease. All the prepared samples
changes on Bi4+ [7,8]. Strong electron-lattice coupling in perovskite exhibit ferromagnetism at 20 K and paramagnetism at 300 K [47].
oxides is induced by the existence of deformed [BO6] octahedral in the In the ongoing debate regarding the insulating behavior of BBO, two
ABO3 (Jahn-Teller effect), where B displays a degenerate electronic state conjectures have emerged as the most significant. The first is the
[9]. Different methods can be used to synthesize BBO having strong disproportion of the Bi3+ and Bi5+ charges, while the second is the bond
impacts on the structure and properties of this compound finding many hybridization of the Bi 6s and O 2p orbitals. Both of these mechanisms
applications in spintronics [5,10–12], photovoltaics [13,14], photo­ result in distortions in the oxygen octahedral, which have been experi­
catalysis [4,15–18], and superconductivity [19–28]. mentally observed. Using hybrid functional models, optical, electronic,
Materials combining both semiconductor and magnetic properties structural, and vibrational properties were found, with a bandgap en­
have a high potential in the development of multifunctional spintronic ergy of approximately 0.4 eV [15]. In a previous work we demonstrate
devices [29–32]. Certainly, adjusting the synthesis parameters is the polar behavior of barium bismuthates thin films with different Ba/Bi
imperative for achieving ferromagnetic characteristics. Transition ratios. The influence of oxygen vacancies, and the structural de­
metals are frequently employed in the doping of non-magnetic mate­ formations were discussed. The importance of oxygen defects at the
rials, a process that may result in the formation of magnetic impurity surface and interface of the perovskite BaBiO3 were elucidated. The
clusters. On the other hand, there exists non-magnetic semiconductors hysteretic strain, dielectric, ferroelectric, and piezoelectric properties of
that exhibit ferromagnetic properties without doping, where charge and BaBiO3 thin films are strongly dependent on the electronic structure.
spin can be internally manipulated [32–40]. This type of material has BBO55 showed a distinguished preferred orientation along the (341)
been the subject of numerous studies, for instance Al2O3 [29], SnO2 plane with a low associated coercive field (66.87 kV/cm), free of imprint
[29], ZnO [29,30], In2O3 [29,31], CeO2 [35], ZrO2 [36], NiO [37], HfO2 and with no polarization gap compared to samples BBO37 and BBO82.
[38], TiO2 [39], and LaMnO3 [40]. However, these type of materials still BBO55 presented the highest piezoelectric (d33-eff≈ 45.7 p.m./V) and
lacks a complete understanding. The magnetic properties of the semi­ ferroelectric (Pr ≈ 19.87 μC/cm2) response. This behavior can be
conductor perovskite BBO can vary when synthesis conditions are ascribed to a highly textured film, which generates less strain
modified, among other factors. BBO consists of interconnected layers throughout the crystal lattice, facilitating the polarization switching
that manifest a distinctive electronic structure attributable to charge mechanism and improving piezo/ferroelectricity [48]. As an extension
disproportionation and the breathing distortion of the octahedra. It can of previous work, in this study, our objectives were twofold: (i) to
be considered a diamagnetic semiconductor due its intrinsic charge advance our understanding of the mechanisms governing photo­
density wave. Additionally, it exhibits ferromagnetic properties at room luminescence emissions in BBO thin films by investigating the impact of
temperature, making it suitable for various applications, as mentioned Ba/Bi ratios, grain size, and oxygen vacancies, and (ii) to comprehend
earlier [41–44]. The electrical and magnetic properties of short-periodic the mechanisms associated with magnetism in perovskite structures,
superlattices (SLs) (SrIrO3)n/(SrRuO3)n (n = 1–5) epitaxially grown on elucidating the reasons behind the enhanced magnetization observed in
the (001)-oriented SrTiO3 substrate show itinerant ferromagnetism with films with a high proportion of Bi. Hence, this study presents a metic­
recovered Curie temperature and magnetic moment in spite of both ulously controlled synthesis of BBO thin films employing the polymeric
individual components being antiferromagnetic insulators in ultrathin precursor method. Additionally, we delve into the analysis of morpho­
films (n ⩽ 3). This material displays higher perpendicular magnetic logical, structural, and magnetic properties. Our findings carry signifi­
anisotropy (1.6× 106 erg/cm3) when n = 1 [45]. P. Kumar et al. have cant implications, fostering the development of novel and
synthesized CoxFe3-xO4 (0.8 ≤ x ≤ 0) magnetic nanoparticles by a wet high-performing materials tailored for diverse electronic applications.
chemical method which were dispersed in a nanomagnetic fluids This includes, the optimization of switches, actuators, magnetic field
(NMFs). The effect of cobalt concentration on magnetic properties has sensors, and the exploration of innovative electronic memory devices.
been probed in detail. The anisotropy and magnetic properties are
significantly dependent on the concentration of the cobalt which has 2. Experimental procedure
been investigated by room temperature dc magnetic measurement (M −
H). The M − H plot indicates that the optimized concentration of the 2.1. BaBiO3 film preparation
cobalt in the system leads to an increase in the saturation magnetization
of the NMFs from 43.87 emu/g to 61.78 emu/g at an optimized con­ The following reagents were employed for the synthesis of polyester
centration (x = 0.2). This can be correlated to the distribution of cations resin: (BaCO3 -Aldrich) with a purity grade of 99.98 %, (Bi2O3- Vetec)
on tetrahedral and octahedral sites. A 24 % Cobalt (Co2+) substitution with a purity grade of 98 %, deionized water (H2O), Nitric Acid (HNO3-
from tetrahedral sites in place of Fe3+ ions increases the exchange Synth) with a purity grade of 65 %, anhydrous citric acid (C6H8O7-
interaction among tetrahedral and octahedral sites resulting in Qhemis) with a purity grade of 99.5–100 %, ethylene glycol (C2H6O2-
improvement in the magnetic performance of the NMFs. The structural Synth) with a purity grade of 99.5 %, Ethylenediamine (C2H8N2- Nu­
distribution correlated with the magnetic properties indicates that the clear) with a purity grade of 98–100 %.
variation in the composition of the mixed ferrites systems significantly According to the Pechini patent [49], precursor BBO solutions were
affects the magnetic behavior. The optimized concentration of doping produced using metal, citric acid, and ethylene glycol in the 1:4:16 ra­
helps in improving the performance of NMFs which is a key bottleneck tios. According to the method, the polybasic acid chelates with multiple
in the development of NMF applications such as biomedical, thermo­ cations can be formed by organic acids with α-hydroxycarboxylic
electric, EMI shielding, and spintronics [46]. groups. When a polyhydroxylic alcohol is added and heated, the chelate
N. Thenmozhi et al. have synthesized by high-temperature solid- changes into a polymer containing cations that are evenly distributed. At

2
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

temperatures as low as 300 ◦ C, the organic component is then removed, binding energy of the elements was the O 1s peak at 530 eV.
resulting in the formation of reactive oxides with well-controlled stoi­
chiometry. In this study, we employed the same procedure as previous 2.3. Magnetic response
described in the literature [50–54]. In order to guarantee the stoichi­
ometry of BBO without any impurities we have determine the exactly A VSM (Versa Lab VSM, Quantum Design) was employed to quantify
metal concentration for each individual polyester resin by gravimetry. In the magnetic hysteresis of BBO films with various Ba/Bi ratios. The
this analytical technique, a well-known mass of metal citrate is placed in measurements were performed at room with applied magnetic fields
a pre-tared alumina crucible. In order to calculate the metal concen­ ranging from − 1.5 ≤ H (T) ≤ 1.5.
tration per gram of solution, the residue was calcined at an adequate
temperature. The amount of Ba and Bi changed according to the Ba/Bi 3. Results and discussion
ratios. The quantity of these ions into the solution were previously
padronized by gravimetry. A Brookfield viscometer was utilized to Barium Bismuthate (BBO) thin films were deposited on the (111)Pt/
monitor water content and adjust the viscosity. Designations such as Ti/SiO2/Si substrates and were evaluated by means at long interatomic
(80:20) (BBO82), (50:50) (BBO55), and (30:70) (BBO37) were distances, Fig. 1a-c. Platinum was chosen as substrate due to its recog­
employed to denote more suitable samples. Employing spin coating, the nized thermal and chemical stability and because does not exhibit
final solution was deposited onto Pt/Ti/SiO2/Si substrates at a rotational magnetic properties. The prominent peak observed at ~40.0◦ is asso­
speed of 5000 rpm for 30 s. Hot plates were employed to pre-fire the ciated with the Pt layer, indicating its preferential orientation along the
films for at 1 min at 100 ◦ C, 4 min at 250 ◦ C, and 4 min at 350 ◦ C. This (111) direction. X-ray diffraction patterns revealed distinct peaks at 2θ
procedure was repeated until reach the six layers. Subsequently, the ≈ 22.7◦ (011), 32.3◦ (10–1), 46.5◦ (311), and 57.3◦ (003) for all sam­
films were crystallized for 30 min (10 ◦ C/minute) at 600 ◦ C in a standard ples. These peaks were correlated with the rhombohedral structure of
furnace with static air. BBO (ICSD #151895; space group R–3R). The rhombohedral structure of
BBO manifests both tilt distortions and breathing-in mode distortions. It
2.2. Structural, morphological and optical characterization is noteworthy that BBO37 and BBO82 films exhibit their most prominent
peak attributed to the (311) plane (~46.5◦ ), while sample BBO55 dis­
X-ray diffraction (XRD) analysis [55] was conducted based on pat­ plays the most intense peak at ~69.5◦ , correlated with the (341) plane.
terns acquired at room temperature using a Rigaku-DMax 2000 PC with This phenomenon suggests that films exhibiting these planes have a
Cu-Kα radiation in the 2θ range from 20 to 70◦ . The XRD measurements higher electronic density [57,58]. These findings demonstrate that the
were performed at a scanning speed of 0.2◦ /min, with a step size of 0.02◦ prepared films exhibit a high degree of texture, and the Ba/Bi ratios
and a receiving aperture of 0.3 mm. Subsequently, the XRD data were significantly influences this characteristic.
analyzed using Topas V5 [56]. TEM patterns of cross-sectional samples, Apart from how the Ba/Bi ratios affects the long-range structure of
fabricated on 300-mesh Cu grids, were employed to gain a deeper un­ the films, the lack of impurities in the XRD patterns indicates there is no
derstanding of the morphology of barium bismuthates. Cross-sectional bismuth excess evaporation during annealing, and the films exhibit a
specimens were prepared by cutting the thin film-covered substrate homogenous morphology without any interaction with the substrate.
wafers into slices. Two of these slices were glued together face-to-face Additionally, it is crucial to highlight that sample BBO37 exhibited
joining the film-covered surfaces. This sandwich structure was then significantly higher intensity diffraction peaks at (311) plane (see
cast in epoxy resin in such a way that the center of the samples contained Fig. 1a). This observation may be linked to the deformation of the BiO6
the joint wafer surfaces in edge-on orientation. After mechanical octahedral breathing mode, a phenomenon that can be ascribed to
grinding and dimpling, these specimens were ion-milled to perforation variations in the Bi–O bond lengths, increasing the atomic density at
in a stage cooled by liquid nitrogen. Micrographs were acquired utilizing those specific diffraction planes, which contribute to the diffraction
a Philips model CM 200 apparatus with an accelerating voltage of 200 signal [59,60]. According to Shilna et al. [5], intensity of the diffraction
kV. The ultraviolet–visible (UV–Vis) spectra of the samples were peaks may vary due to the disproportionation of Bi4+ in Bi3+ and Bi5+
collected using a Lambda 1050 spectrometer from PerkinElmer oper­ ions, which leads to the changes to the Bi–O length (2.29 Å and 2.11 Å,
ating in diffuse reflectance mode. Employing the Kubelka-Munk func­ respectively), as well as to the Bi–O–Bi angles, resulting in the tilting of
tion, the UV–Vis data underwent transformation into Tauc plots for [BiO6] octahedra. Thus, it can be concluded that the [BiO6] octahedral
bandgap energy estimation, accounting for indirect type allowed tran­ distortion determines the preferred orientation of the films. The dis­
sitions for the samples (n = 2). The x-axis of the plot represents the placements of bismuth atoms, identified as network formers, is indica­
photon energy, while the y-axis corresponds to the transformed tive of distortions or strain in the lattice. These deviations are attributed
Kubelka-Munk function ([F (R∞)hv]2). The point of intersection be­ to defects sustained by [BiO6] and [BaO12] clusters.
tween the x-axis and the extrapolation of the linear fit of the curves Rietveld analysis allows to determine the crystallographic informa­
corresponds to the bandgap energy. The Fluorolog-3 FL3–122 instru­ tion of the films, (Fig. 2). All Rietveld parameters (χ 2, Rwp, Rp) are pre­
ment manufactured by Horiba Jobin Yvon was employed to assess the sented in Table 1, demonstrating a consistent fit of the X-ray diffraction
photoluminescent response (PL) at room temperature within the data. The Rwp factor, reflecting the convergence of refinement to the
370–650 nm range. The acquired PL data were subjected to deconvo­ observed data, emerges as a crucial indicator for evaluating the quality
lution using a Gaussian function. X-ray photoelectron spectroscopy of the structural refinement. Our results reveal that the refinement ex­
(XPS) measurements were conducted at approximately 10− 7 Pa using a hibits high reliability, with Rwp values below 11.0 for all samples. Thus, a
commercial spectrometer (UNI-SPECS UHV) to perform an elemental homogeneous and dense structure is established resulting in films
composition analysis of the film surfaces. An analyzer pass energy of 10 through the nucleation and growth process; this aspect proves to be
eV was applied, and Mg–K radiation (hυ = 1253.6 eV) was employed. essential for the magnetic and optical properties of BBO-based thin
Shirley’s approach was utilized to remove the inelastic background from films. Distortions or deformations induced by [BiO6] and [BaO12] clus­
the Bi 4f electron core-level spectra. Scofield’s sensitivity factors for the ters influence the parameters of the crystal lattice. Disparities in thermal
relevant elements were employed, and the ratio of relative peak areas expansion coefficients between platinum and barium bismuthate may
was utilized to ascertain the composition of the region adjacent to the give rise to minor fluctuations in lattice parameters and unit cell vol­
surface with an accuracy of ±10 %. The spectra were fitted employing umes. From the XRD pattern using the quantitative phase analysis
multiple Voigt profiles, without imposing any constraints. With a peak (Rietveld method) the obtained lattice parameters were 4.1832 (1) for
position accuracy of ±0.1 eV, the full width at half maximum (FWHM) BBO37, 4.1622 (2) for BBO82 and 4.1231 (2) for BBO55, respectively.
ranged from 1.2 to 2.1 eV. The calibration reference point for the Assuming that the lattice constant of Pt (111) is 4.0 A we have

3
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

Figure 1. X-ray diffractograms for BBO37, BBO55 and BBO82 films deposited on Pt (111)/Ti/SiO2/Si substrate and heat treated at 600 ◦ C in static air for 30 min.

Figure 2. Rietveld analysis of samples (a) BBO37, (b) BBO55 and (c) BBO82 deposited on Pt (111)/Ti/SiO2/Si substrate and heat treated at 600 ◦ C in static air for
30 min.

4
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

Table 1
Index refinements for BBO37, BBO55 and BBO82 films, deposited on Pt (111)/Ti/SiO2/Si substrate and heat treated at 600 ◦ C in static air for 30 min.
Sample BBO Pt Rietveld parameters –
3 3 2
phase (%) V ±30 (Å ) RBragg phase (%) V ±28 (Å ) RBragg Rwp Rp χ Average grain size (nm)

BBO37 45.0 155 18.5 55.0 59.7 4.2 8.3 4.9 2.6 38.7
BBO55 40.0 150 25.8 60.0 59.9 5.9 11.0 7.3 3.4 31.6
BBO82 21.0 155 21.8 79.0 59.7 3.7 9.5 5.5 2.3 33.6

Atomic Positions Socc

A1 A2 B1 B2 O1 O2 O3 O4 O5 Bi(A1) O Stoichiometry Refinement

0; 0; 0.067 0; 0; 0.21 0; 0; ½ 0; 0; 0.37 ¼; ¼; 0 ¼; ¼; ¼ 0; 0; 0.44 0; 0; 0.32 ¼; ¼; 0.12 0.75 0.92 Ba0⋅3Bi0⋅7O3 Ba0⋅25Bi0⋅65O2.64
0; 0; 0.067 0; 0; 0.21 0; 0; ½ 0; 0; 0.37 ¼; ¼; 0 ¼; ¼; ¼ 0; 0; 0.44 0; 0; 0.33 ¼; ¼; 0.11 1 0.92 BaBiO3 BaBiO2.85
0; 0; 0.067 0; 0; 0.21 0; 0; ½ 0; 0; 0.37 ¼; ¼; 0 ¼; ¼; ¼ 0; 0; 0.44 0; 0; 0.32 ¼; ¼; 0.12 0.86 0.91 Ba0⋅8Bi0⋅2O3 Ba0⋅75Bi0⋅18O2.6

determined the lattice mismatch of 4.38 %, 3.89 % and 2.98 % for displacements on Bi atoms (network formers) are indicative of distor­
BBO37, BBO82 and BBO55, respectively. The low mismatch between tions/strain in the lattice caused by or arising from defects promoted by
suggest that the coatings are strain-free and there are no significant off- [BiO6] and [BaO12] clusters. Additionally, sample BBO55 presented
stoichiometries [61]. smaller crystallites (d = 14.5 nm) compared to BBO37 and BBO82
The main differences in crystal lattice parameters and the thermal samples (19.2 and 17.4, respectively). Consequently, the reduction in
expansion behavior between the film and the underlying substrate can crystallite size may be correlated with increased structural strain in the
lead to small changes in lattice parameters and unit cell volumes. The BBO55 films, as evidenced by a slight peak shift or broadening. This

Figure 3. TEM, FEG-SEM (inset), and size distribution plots for the (a) BBO37, (b) BBO55 and (c) BBO82 films, deposited on Pt (111)/Ti/SiO2/Si substrate and heat
treated at 600 ◦ C in static air for 30 min.

5
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

Figure 4. Tauc plot of Kubelka-Munk function for BBO37, BBO55 and BBO82 thin films deposited on Pt (111)/Ti/SiO2/Si substrate and heat treated at 600 ◦ C in
static air for 30 min.

6
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

effect potentially implies the formation of a perovskite structure, reported in the literature [9,12,25,64–66]. The discrepancies in the
wherein the reduction in crystallite size ensues due to distortions and band gap values are dependent on the Ba/Bi ratios. Such factors are
strain in the lattice induced by [BiO6] and [BaO12] clusters. This phe­ linked to structural defects or additional localized states within the
nomenon becomes more pronounced with diminishing grain size. The material, stemming from two factors: variations in grain size and the
Socc is the occupation factor of two atoms and the form used to calculate presence of distinct types of oxygen vacancies. A certain structural dis­
refined stoichiometry. Socc values are affected by the Ba/Bi ratios which order degree is an indicative that localized states within the bandgap is
indicates that the charge density of bismuth is different from that of being creating with the increase of vacancies presenting. The findings
barium, having a greater electronic density on the part of the ion. The suggest a correlation between grain size [67], number of vacancies [68],
refinement of oxygen vacancies indicates that the atoms in the O2 and the crystallite size [69] and the optical band gap. Additionally, the
O4 positions only contribute to the formation of vacancies. Oxygen charge disproportionation contributes to variations in the optical band
atoms in O1 and O5 positions can’t be refined, as they are linked to the gap [66]. Alterations in the size of oxygen octahedra, through contrac­
barium forming a dodecahedral geometry. Oxygen atom in the O3 po­ tion or expansion, induce changes in the Bi–O bond lengths, thereby
sition was difficult to refine since this oxygen is linked to the Bi1 atom, influencing the formation of the energy gap [8,9]. Considering that the
which has no vacancy, since the bismuth is linked to it. However, both morphology of grains as well as the band gap energy are affected by the
atoms in the O2 and O4 positions contribute to the origin of the va­ charge disproportionation of Bi+4 we can explain the formation of ox­
cancies, since the Bi2, or the vacancy is free in the structure to migrate ygen vacancies as follows: oxygen vacancies are the entities that dis­
through alternating layers of Bi2, O2 and O4. The amount of vacancies tributes the electrons, once the neutral (Vxo) one has two unpaired
for low bismuth content occurs in the ratio 30.9 % of O2 to 69.1 % of O4, electrons while the doubly-ionized oxygen vacancy (V..o) doesn’t have
since 2 atoms of Bi are removed, 4 atoms of O2 and 9 atoms of O4. any. On the other hand, the singly-ionized oxygen vacancy (V.o) has one
Fig. 3(a–c) display the transmission electron microscopy (TEM) mi­ excited electron which is responsible for the charge transfer, accepting
crographs of the films while the inset reveals the field emission gun and donating electrons. Therefore, we have active quantum clusters
scanning electron microscopy (FEG-SEM) of the respective samples. The with singly-ionized oxygen vacancies and inactive ones with neutral and
BBO37, BBO55, and BBO82 samples exhibited an average grain size of doubly-ionized vacancies. The balance of these entities rises or reduces
38.7, 31.6, and 33.6 nm, respectively. Modulating the Ba/Bi ratios in­ the distinct surfaces’ activities, while the structural defects are those
duces discernible alterations in texture, attributable to the nucleation who excites the electrons on the forbidden band gap, with a consequent
effect of Ba/Bi atoms on the substrate, thereby introducing disorder in stretching/contraction of the crystalline lattice at short, mid, and
the atomic positions, particularly evident in the film with higher Bi long-range orders. Therefore, the control of morphology is mandatory to
content. The grains display regularly defined shapes, and the insets in obtain shape-oriented nanocrystals with tailored structural and mag­
Fig. 3(a–c) illustrate the associated grain size distribution. The presence netic and optical properties, which can be associated with singular
of clearly discernible grains suggests that the films exhibit well- chemical environments observed along the exposed planes.
crystallized characteristics [62]. As the amount of bismuth is Photoluminescence (PL) technique is based on the emission of light
enhanced, the shape of the grains tends to assume a plate-like due to the excitation energy derived from absorbed radiation. It is useful
morphology. Alterations in the film morphology can be ascribed to an for analyzing the electronic transition between the ground state of en­
elevated surface energy associated with higher Bi content. This height­ ergy. When light is incident on a material, electrons absorb energy,
ened surface energy promotes the adsorption of reactant species onto the transitioning to an excited state, upon returning to their ground state,
substrate during the release of organic matter and nucleation process. the electrons release energy. This technique is also capable of analyzing
An increased Ba content tends to result in a substrate surface with lower impurities, imperfections, and defects in samples. The PL spectrum is
energy, attributed to its capacity to dissipate or absorb thermal energy, analyzed by fitting it with multiple Gaussian curves, through deconvo­
thereby contributing to a rounded grain morphology. The BBO55 film lution. As shown in Fig. 5, five peaks (P1, P2, P3, P4, and P5) were found
exhibits suppressed grain growth, aligning with the observations from with different relative intensities, bandwidths, and energy positions.
XRD patterns. In XRD, a lower FWHM suggests an enhancement in the Such peaks can be attributed to energy traps or defects [5], in the band
long-range order of the structure [63]. gap which may be related to interstitials, imperfections, vacancies, im­
The Tauc model was employed for the calculation of the indirect purities, anti-sites, and different types of oxygen vacancies [5]. The
optical band gap (Eg) using experimental optical absorption data ob­ visible region can be divided into four categories: Indigo (~400–480
tained for (various Ba/Bi ratios.
) The Tauc plot of Kubelka-Munk function, nm), Blue-Green (~480–550 nm), Yellow (~550–610 nm), and
depicting (F(R)hν)2 vs hν for the three samples, is illustrated in Fig. 4. Orange-Red (~610–750 nm) [5,33,69]. In the indigo emission, one
The following values were obtained: 2.86, 2.72 and 3.08 eV, corre­ centered peak (P1) related to the intrinsic electron transition of Bi+3
sponding to the optical band gap of the BBO82, BBO55, and BBO37 thin [66] is observed. In this transition, oxygen vacancies with charge +1 and
[ ]
films, respectively. These values are higher with similar findings clusters BiO5 .Vo. were formed according to Bi5+ →Bi3+ + 2Vo. .

Figure 5. Deconvoluted PL spectra of the (a) BBO37, (b) BBO55 and (c) BBO82 thin films deposited on Pt (111)/Ti/SiO2/Si substrate and heat treated at 600 ◦ C in
static air for 30 min.

7
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

Table 2
Peak position, FWHM, Relative Intensity and Intensity ratio obtained from the PL measurements for BBO37, BBO55 and BBO82 thin films deposited on Pt (111)/Ti/
SiO2/Si substrate and heat treated at 600 ◦ C in static air for 30 min.
Peak Peak Position FWHM Relative Intensity Intensity Ratio

(cm− 1) (cm− 1) (I) x (10− 6)

BBO37 BBO55 BBO82 BBO37 BBO55 BBO82 BBO37 BBO55 BBO82 BBO37 BBO55 BBO82

P1 438.6 438.6 438.6 75.03 41.41 46.57 3.34 0.77 1.01

P2 486.5 486.5 485.8 72.44 74.78 76.32 4.04 2.53 3.25 0.83 (IP1/IP2) 0.30 (IP1/IP2) 0.31 (IP1/IP2)
P3 548.6 547.9 548.6 80.85 80.21 77.62 3.29 6.66 4.16
P4 608.1 608.7 608.1 91.20 90.56 85.39 3.09 6.0 4.28
P5 659.8 660.5 660.5 137.8 152.7 131.9 3.26 5.99 4.34

long-range order. The main peaks related to the single charged vacancies
(F+ centers) and vacancy clusters follows the order: (BBB37 > BBO82 >
BBO55). In these analyses, P1 and P2 peaks were employed since for the
other peaks (P3, P4 and P5) no linear trend was observed. According to
the PL results, the P1 peak corresponds to the indigo region while the P2
peak corresponds to the blue-green region (P2). Such peaks possess an
increase in the intensity ratio. Therefore, according to the analysis, there
is an increase in single charged vacancies (F+ centers) in the following
order (BBB37 > BBO82 > BBO55). According to Orrego et al. emission
in the indigo region is attributed to deep defects in the bandgap. On the
other hand, emissions in the indigo and blue regions are associated with
surface defects in the bandgap [73]. In this case, the deep defect cor­
[ ]
responds to vacancy clusters BiO5 .Vo. , whereas surface defects corre­
spond to Vo. and vacancy clusters. It is worth noting that vacancies
generally alter the energy levels in the bandgap region, indicating a
disruption in charge transfer [73]. The indigo region is attributed to the
[ ]
disorder state of the BiO5 .Vox clusters, while the blue region corre­
sponds to the ordered state [BiO6 ]x [73]. Charge transfer between these
clusters, as observed in the Kroger-Vink equations in the supplementary
Figure 6. Hysteresis loops (M–H) for the BBO82, BBO55, and BBO37 thin films material (XPS), could be the origin of vacancies in the samples during
deposited on Pt (111)/Ti/SiO2/Si substrate and heat treated at 600 ◦ C in static
synthesis and subsequent thermal treatments. According to the litera­
air for 30 min.
ture, the [BiO6 ]x cluster could be related to monoionized oxygen va­
cancies (Vo. ) [73]. Therefore, monoionized Vo. is present in surface
According to the photoluminescence results, the samples have a con­
defects. Compared to other perovskite materials, the photoluminescence
centration of clusters in the following order: BBO37 > BBO82 > BBO55.
of the BaTiO3 thin film exhibits band edge emission (BNE) at 361 nm
In the Blue-Green emission, one centered peak (P2) is observed due to
(3.43 eV), a value close to the bandgap. Beyond the BNE peak, the
the presence of oxygen vacancies with a +1 charge (F+ center). In the
following defect level emission (DLE) peaks were detected around 424
Yellow emission, two centered peaks (P3) and (P4) are observed, which
nm, 459 nm, 485 nm, and 495 nm, respectively. The broadening of the
can be attributed to double-charged vacancies with a +2 charge (F++
DLE peak (459 nm) with the enhance of thermal treatment temperature
center). The Orange-Red emission is caused by an excess oxygen in the
may be attributed to the increase in interstitial defects or imperfections,
films [5,33,70–72].
or to oxygen vacancies [74]. In contrast, for spinel structures based on
Table 02 illustrates the Peak position, FWHM, Relative Intensity and
NiFe2-xAlxO4 thin films (0.0 ≤ x ≤ 1.0) deposited by spray pyrolysis
Intensity ratio related to the deconvolution of the peaks associated to the
bands near-edge emission between 680 nm and 780 nm are present.
PL results. Setting the composition of the films, one can observe that
These results could be attributed to the presence of closely spaced
BBO37 induces a broader peak compared to BBO55 as indicated by
overlapped peaks, and could also be caused by surface and deep trap­
larger full width at half maximum (FWHM) values, suggesting higher
ping states altering the band gap upon substitution of Al3+ [75].
The M-H curves of distinct barium bismuthate thin films were
recorded at Fig. 6. During the measurement of the magnetic properties
Table 3
of thin films, the influence of the substrate will persist, even when
– Magnetic and thickness data obtained for BBO37, BBO55 and BBO82 thin films
considering that pure platinum, does not exhibit magnetic properties
deposited on Pt (111)/Ti/SiO2/Si substrate and heat treated at 600 ◦ C in static
air for 30 min. [76,77]. In this way, the recorded signal predominantly stems from the
contribution of magnetic domains present in barium bismuthate. The
Samples K1 Ms Hc Mr M r/ Thickness
samples with a higher proportion of Bi, as shown in Table 3, exhibit
κ
Ms
(erg/ (emu/ (G) (emu/ (nm) higher values of Ms (saturation magnetization) and slightly higher
cm3) cm3) cm3)
values of Mr (remanence magnetization) with high Hc (coercive field).
BBO37 8.36 1.99 110.12 15.34 9.40 0.085 288 Additionally, the results of the Mr/Ms ratio are close to zero, indicating a
× 105 × rapid loss of residual magnetism. When Bi content is 70 %, the loss of
10− 5
BBO55 1.19 2.40 51.18 11.12 2.10 0.041 344
residual magnetism is slightly lower compared to the other samples.
× 105 × According to the literature, BBO is characterized by having different
10− 5 valence states such as Bi3+ and Bi5+, which are generated due to the
BBO82 1.72 2.42 78.61 12.46 5.04 0.064 359 charge disproportionation of Bi4+. It also exhibits two types of distor­
× 105
tions in the octahedral structure caused by the different Bi–O bond
×
10− 5

8
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

KB is the Boltzmann constant, μ is the magnetic moment of the particle,

and M0 is the saturation magnetization. The saturation magnitude was
determined by fitting the Langevin function to the experimental data.
Therefore, saturation near to Ms can be described by the following
[ ] ( )
b 8 K21
equation: M = Ms 1 − H2
+ κH, where b = 105 M2s
; H is the applied

magnetic field, M represents the magnetization, Ms is the saturation

magnetization, K1 is the cubic anisotropy constant, μ0 is the magnetic
permeability of free space, and the term κH is known as forced magne­
tization [75,82–85]. A linear increase in spontaneous magnetization
causes forced magnetization, especially when applying higher intensity
magnetic fields. The anisotropy constant was calculated using the for­
√̅̅̅̅̅̅̅̅
mula K1 = Ms 105b 8 obtained from the LAS equation. The plate-like
morphology specially observed in the BBO37 film influences the mag­
netic anisotropy [86,87] because the domains are easier to be switched
under external field. These results indicate a superparamagnetic
behavior [76,88–90].
Fig. 8a represents the (dM/dH vs H) magnetization curves as a
Figure 7. Fitting to the Law of Approach to Saturation (LAS) for BBO82, function of the applied magnetic field, where dM/dH = χ is called dy­
BBO55, and BBO37 thin films deposited on Pt (111)/Ti/SiO2/Si substrate and namic susceptibility, measured by the amount of magnetization pro­
heat treated at 600 ◦ C in static air for 30 min. duced per unit of the applied magnetic field. The curves exhibit a single
magnetic behavior, indicating magnetic moment rotation of the mag­
lengths [5,9–13,25]. Experimental results revealed that the BBO can netic clusters and isolated moments are present. This indicates the
exhibits paramagnetic behavior when it possesses the Bi4+ valence state presence of a single type of stable magnetic domain [91].
(5 d10 6s1) due the single unpaired spin [5,41,43]. On the other hand, it According to the Rietveld analysis and TEM results, the average grain
exhibits diamagnetic behavior when it adopts the Bi3+ (5 d10 6s2) and sizes and crystallite size depends on the Ba/Bi ratios. The increase in
Bi5+ (5 d10 6s0) valence states due to the presence of paired spins [5,41, grain size with the increment of Bi can be attributed to the rise in surface
43]. It is known that for small grains the formation of magnetic domains energy, wherein the enlarged grains contribute to the enhancement of
is inhibited enabling a ferromagnetic behavior [5,78]. This occurs the coercive field (Hc) [77]. Based on the aforementioned results, the
because the Bi3+ can adopts the electronic configuration (5 d10 6s1 6p1) mechanism governing the development of a plate-like morphology in
which possesses incomplete spins [5]. Changes in the coercivity field for the BBO37 film can be elucidated as follows: during the initial stages of
different Ba/Bi ratios indicates that the changes in grain morphology as particle growth, the elevated degree of supersaturation was attributed to
well as pinning of domain walls are governed by long-range and the larger solubility of small particles. As the soaking time enhances, the
short-range stresses, respectively. Different reasons can be responsible number of small particles vanishes, and the degree of supersaturation
for changes in the coercive field: 1) volume pinning by stress sources; 2) decreased. The nucleation which starts to grown from the edges required
intrinsic fluctuations of material properties; 3) surface irregularities; 4) a high degree of supersaturation, thereby maintaining the thickness of
relaxation phenomena. All these sources can explain the rise in magnetic particles, and becoming the predominant process. Moreover, the
coercivity, just as vacancies influence the fixation of magnetic domains. atomic-level presence of a smooth surface structure played a pivotal role
P.P. Mohapatra et al. have obtained lithium ferrite thin films with in diminishing the growth rate of surfaces characterized by well-defined
different film thickness on Pt (111)/Ti/SiO2/Si substrates. The authors facets. The Ostwald ripening rate was influenced by factors such as the
have observed that the band gap energy varies from (2.58–2.30) eV, diffusion coefficient, solubility, and atomic arrangement of particle
decreasing with increasing thickness. Also, the band gap of these films is surfaces [92]. Consequently, the emergence of edge nucleation was
influenced by strain, crystallinity, and compactness. The saturation contingent upon heightened solubility. Diverse Ba/Bi ratios were iden­
magnetization of this thin film, both in-plane and out-of-plane, exhibits tified as potential enhancers of solubility and diffusion coefficient,
a monotonic decline with increasing thickness, a trend attributed to the thereby fostering an elevated growth rate and the attainment of
diminishing compressive stress [79]. Yao et al. have obtained larger-sized grains, consistent with the findings from TEM images.
NiFe2-xGdxO4 thin films by the sol-gel method. The authors demonstrate Additionally, TEM observations unveiled a rise in the plate-like
that the band gap energy varies from (2.58–2.75 eV) with magnetic morphology with the addition of Bi, influencing the anisotropic con­
saturation of (70.54–145.29 emu/cc) and coercive field (87.57–154.05 stant of the films [86,87]. The increased percentage of Bi induced
Oe) being influenced by Gd doping, exchange interaction, and redistri­ greater deformation in the crystalline structure, resulting in an elonga­
bution of cations [80]. The same trend was observed by K. Bala et al. tion of Bi–O bond lengths.
which synthesized heterostructures based on MnFe2O4/(Pb1-xSrx)TiO3, According to the photoluminescence results, there is a significant
[
evidencing magnetic saturation of (109–119 emu/cc) with remanent presence of oxygen vacancies (F+ centers) and vacancy clusters BiO5 .
]
magnetization of (101–102 Oe), coercive fields (101–102 Oe) and Vo. in the thin films with a higher proportion of Bi and the type of
magnetoelectric coefficient (2.82–4.29 V/Oe cm). The authors have morphology of the grains. As analyzed in the supplementary XPS results
shown that the multiferroic properties are strongly influenced by Sr of the samples, the percentage of oxygen vacancies not only depends on
doping [81]. the concentration of bismuth but also on the morphology of the grains.
To evaluate the saturation of the films we employ the law of These vacancies, due to their incomplete spins, contribute to the net
approach to saturation (LAS). This law describes the dependence of magnetic moment [93]. The reason behind the improvement in the
magnetization when applying a magnetic field (H ≫ Hc), Fig. 7. In our magnetization when the proportion of Bi is increased is attributed to the
study, all films show a coercive field of approximately (22–30 G) with increase in oxygen vacancies and vacancy clusters. Similarly, the in­
SPM behavior at room temperature due to thermal fluctuation. The SPM crease in Ms (saturation magnetization) is a result of the plate-like
behavior can be explained using the Langevin function [63,64], M = morphology of grains which domains can easily be switched under
[ ]
M0 L(βμH) = M0 coth(βμH) − βμ1H , where β = K1B T; T is the temperature, external field [91,94]. Fig. 8b shows the variation of saturation

9
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

Fig 8. (a) The dM/dH vs. H for the magnetization curves according to applied magnetic field and (b) Variation of saturation magnetization (MS), the magneto­
crystalline anisotropy constant (K1) for the BBO82, BBO55, and BBO37 thin films deposited on Pt (111)/Ti/SiO2/Si substrate and heat treated at 600 ◦ C in static air
for 30 min.

magnetization (Ms) and the magnetocrystalline anisotropy constant (K1) slow O2− motion. Additionally, the optical and magnetic of BaBiO3 thin
as a function of Ba/Bi ratios. As can be seen in the graph, the Ms and K1 films are strongly dependent on the electronic structure. BBO37 showed
values increase in a non-linear trend as the Bi content is enhanced. As a plate-like morphology which retained space charges influencing on the
stated above the reasons behind the changes in the Ms and K1 values are magnetic properties since the irregular shape of grains have more
due the presence of oxygen vacancies (F+ centers) and vacancy clusters difficult for switching. This film also exhibited a significant presence of
[ ] [ ]
BiO5 .Vo. in the thin films as well as the grain size and morphology. oxygen vacancies (F+ centers) and vacancy clusters BiO5 .Vo. which
according to the law of approach to saturation (LAS) reveals a higher
4. Conclusion magnetocrystalline anisotropy constant as well as high band gap energy.
According to the photoluminescence results, the films have a concen­
Barium bismuthates thin films were spread over platinum coated tration of clusters in the following order: BBO37 > BBO82 > BBO55.
silicon substrates using spin-coating technique and the polymeric pre­ These results reveal the action of oxygen defects at the interface and
cursor method. (Micro)structural, optical and magnetic properties were surface of the barium bismuthates. X-ray photoelectron spectroscopy
evaluated. Periodicity at long range reveal a rhombohedral BBO struc­ (XPS) analyses reveals that the Ba/Bi ratios affects the oxidation state of
ture, independently of Ba/Bi ratios. TEM images indicated that the Ba/Bi the bismuth element because completely changes the defect states and
ratios influences grain growth, being the suppression more evident in concentration of bismuth species. Such facts are associated with the
the BBO55 film. The decrease in the grain size suggests that oxygen morphologies and the defect clusters. The optical and magnetic behavior
vacancies are suppressed, resulting in a lower grain growth rate and a of barium bismuthates can be caused by the following factors: Tilting of

10
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

the oxygen octahedral caused by changes in the length and angle of the [8] A.W. Sleight, Bismuthates: BaBiO3 and related superconducting phases, Phys. C
(Amsterdam, Neth.): Supercond. Appl. 514 (2015) 152–165, https://doi.org/
Bi–O–Bi bonds, morphology of the grains, band gap energy, type of
10.1016/j.physc.2015.02.012.
oxygen vacancies, and the strain imposed by the platinum-coated silicon [9] N. Kumar, S.L. Golledge, D.P. Cann, Synthesis and electrical properties of BaBiO3
substrates. All events affect the saturation magnetization (Ms), the and high resistivity BaTiO3–BaBiO3 ceramics, J. Adv. Dielectr. 6 (2016)
coercitive field, the magnetocrystalline anisotropy constant (K1) and the 1650032–1650040, https://doi.org/10.1142/S2010135X16500326.
[10] D.E. Cox, A.W. Sleight, Crystal structure of Ba2 Bi3+ Bi5+ O6, Solid State Commun.
photoluminescence characteristics of barium bismuthates. Therefore, 19 (1976) 969–973, https://doi.org/10.1016/0038-1098(76)90632-3.
controlling Ba/Bi ratios can tune the magnetic properties of barium [11] D.E. Cox, A.W. Sleight, Mixed-valent Ba2 Bi3+ Bi5+ O6: structure and properties,
bismuthates thin films with may find potential applications in the field Acta Crystallogr. B 35 (1979) 1–10, https://doi.org/10.1107/
S0567740879002417.
of spintronics and new types of electronic memory devices. [12] D.S. Shtarev, A.V. Shtareva, R. Kevorkyants, et al., Revisiting the BaBiO3
semiconductor photocatalyst: synthesis, characterization, electronic structure, and
photocatalytic activity, Photochem. Photobiol. Sci. 20 (2021) 1147–1160, https://
CRediT authorship contribution statement doi.org/10.1007/s43630-021-00086-y.
[13] C. Chaillout, J.P. Remeika, A. Santoro, M. Marezio, The determination of the Bi
G. Acero: Formal analysis, Data curation. M.A. Ponce: Methodol­ valence state in BaBiO3 by neutron powder diffraction data, Solid State Commun.
56 (1985) 829–831, https://doi.org/10.1016/0038-1098(85)90414-4.
ogy, Formal analysis. F. Moura: Writing – review & editing, Writing – [14] S. Sarkar, R. Raghunathan, S. Chowdhury, The mystery behind dynamic charge
original draft. A.Z. Simões: Funding acquisition, Conceptualization. disproportionation in BaBiO3, Nano Lett. 21 (19) (2021) 8433–8438, https://doi.
org/10.1021/acs.nanolett.1c03103.
[15] C. Franchini, A. Sanna, M. Marsman, et al., Structural, vibrational, and
quasiparticle properties of the Peierls semiconductor BaBiO3: a hybrid functional
Declaration of competing interest and self-consistent GW+ vertex-corrections study, Phys. Rev. B Condens. Matter 81
(2010) 85213–85220, https://doi.org/10.1103/PhysRevB.81.085213.
[16] N. Feng, et al., Anti-Jahn-Teller effect induced ultrafast insulator to metal
The authors declare the following financial interests/personal re­
transition in perovskite BaBiO3, npj Comput. Mater. 8 (2022) 226–233, https://doi.
lationships which may be considered as potential competing interests. org/10.1038/s41524-022-00901-9.
Alexandre Zirpoli Simoes reports financial support was provided by [17] G. Li, B. Yan, R. Thomale, W. Hanke, Topological nature and the multiple Dirac
UNESP. Alexandre Zirpoli Simoes reports a relationship with São Paulo cones hidden in Bismuth high-Tc superconductors, Sci. Rep. 5 (2015)
10435–10443, https://doi.org/10.1038/srep10435.
State University that includes: employment. If there are other authors, [18] Y. Ma, X. Li, L. Kou, et al., Two-dimensional inversion-asymmetric topological
they declare that they have no known competing financial interests or insulators in functionalized III-Bi bilayers, Phys. Rev. B Condens. Matter 91 (2015)
personal relationships that could have appeared to influence the work 235306–235315, https://doi.org/10.1103/PhysRevB.91.235306.
[19] X. Li, F. Liu, Topological field-effect transistor with quantized ON/OFF
reported in this paper. conductance of helical/chiral dislocation states, Phys. Rev. B Condens. Matter 107
(2023) 224101–224107, https://doi.org/10.1103/PhysRevB.107.224101.
Data availability [20] M. Muta, S. Nishikawa, A. Ichinose, et al., Growth and photo-response of (110)
oriented BaBiO3 films on SrTiO3 (001) substrates, Thin Solid Films 749 (2022)
139167–139173, https://doi.org/10.1016/j.tsf.2022.139167.
Data will be made available on request. [21] R.L. Bouwmeester, A. Brinkman, K. Sotthewes, Thickness-dependent band gap
modification in BaBiO3, Nanomaterials 11 (2021) 882–892, https://doi.org/
10.3390/nano11040882.
Acknowledgements [22] J. Tang, Z. Zou, J. Ye, Efficient photocatalysis on BaBiO3 driven by visible light,
J. Phys. Chem. C 111 34 (2007) 12779–12785, https://doi.org/10.1021/
jp073344l.
The authors are grateful for the Brazilian research support (FAPESP;
[23] S. Biswas, P. Banerjee, M. De Raychaudhury, Correlation-driven metal-insulator
Grant No. 13/07296-2), and Higher Education Personnel Improvement transition in unconventional magnetic metal superoxides, Mater. Res. Bull. 167
Coordination. We would like to thanks U. Wiedwald for the PL (2023) 112389–1123100, https://doi.org/10.1016/j.materresbull.2023.112389.
measurements. [24] B. Men, J. Zhang, C. Diao, et al., Photoluminescence, surface photovoltage and
photocatalytic properties of BaBiO3 powders, J. Mater. Sci. Mater. Electron. 29
(2018) 12729–12734, https://doi.org/10.1007/s10854-018-9390-8.
Appendix A. Supplementary data [25] A.S. Chouhan, E. Athresh, R. Ranjan, et al., BaBiO3: a potential absorber for all-
oxide photovoltaics, Mater. Lett. 210 (2018) 218–222, https://doi.org/10.1016/j.
matlet.2017.09.038.
Supplementary data to this article can be found online at https://doi. [26] B. Yan, M. Jansen, C. Felser, A large-energy-gap oxide topological insulator based
org/10.1016/j.matchemphys.2024.129523. on the superconductor BaBiO3, Nat. Phys. 9 (2013) 709–812, https://doi.org/
10.1038/NPHYS2762.
[27] S. Griffitt, M. Spaić, J. Joe, et al., Local inversion-symmetry breaking in a
References bismuthate high-Tc superconductor, Nat. Commun. 14 (2023) 845–854, https://
doi.org/10.1038/s41467-023-36348-9.
[28] S. Sarkar, R.J. Choudhary, R. Raghunathan, Competing s-p and p-p fluctuations in
[1] J.-J. Qu, S. Li, F. Liu, et al., Effect of phase structures and substrate temperatures on
charge-disproportionation of BaBiO3, arXiv (2023), https://doi.org/10.48550/
NTC characteristics of Cu-modified Ba–Bi–O-based perovskite-type thermistor thin
arXiv.2303.03656.
films, Mater. Sci. Semicond. Process. 121 (2021) 105375–105382, https://doi.org/
[29] S.B. Ogale, Dilute doping, defects, and ferromagnetism in metal oxide systems,
10.1016/j.mssp.2020.105375.
Adv. Mater. 22 (2010) 3125–3155, https://doi.org/10.1002/adma.200903891.
[2] J.M. Mora-Hernandez, A.L. Huerta-Flores, L.M. Torres-Martínez, Tailoring charge
[30] T. Dietl, A ten-year perspective on dilute magnetic semiconductors and oxides, Nat.
transport in BaBiO3/NaTaO3 heterojunction interface for enhanced photocatalytic
Mater. 9 (2010) 965–974, https://doi.org/10.1038/nmat2898.
and photoelectrochemical H2 generation, J. Photochem. Photobiol., A A 391
[31] J. Philip, et al., Carrier-controlled ferromagnetism in transparent oxide
(2020) 112363–112373, https://doi.org/10.1016/j.jphotochem.2020.112363.
semiconductors, Nat. Mater. 5 (2006) 298–304, https://doi.org/10.1038/
[3] D.S. Shtarev, N. Serpone, A new generation of visible-light-active
nmat1613.
photocatalysts—the alkaline earth metal bismuthates: syntheses, compositions,
[32] A. Sundaresan, R. Bhargavi, N. Rangarajan, U. Siddesh, C.N.R. Rao,
structures, and Properties, J. Photochem. Photobiol. C Photochem. Rev. 50 (2022)
Ferromagnetism as a universal feature of nanoparticles of the otherwise
100501–100551, https://doi.org/10.1016/j.jphotochemrev.2022.100501, 2022.
nonmagnetic oxides, Phys. Rev. B 74 (2006) 161306 1–4, https://doi.org/
[4] G.R. Portugal, R.M. Ronchi, S.F. Santos, et al., Composition-dependent
10.1103/PhysRevB.74.161306.
photocatalytic activity and high-mobility carrier gas in NaTaO3/BaBiO3
[33] B. Panigrahy, et al., Defect-related emissions and magnetization properties of ZnO
Heterojunctions, Surface. Interfac. 36 (2022) 102486–102496, https://doi.org/
Nanorods, Adv. Funct. Mater. 20 (2010) 1161–1165, https://doi.org/10.1002/
10.1016/j.surfin.2022.102486.
adfm.200902018.
[5] K.V. Shilna, S.Ch Sahoo, K.J. Thomas, Novel ferromagnetism and negative
[34] S. Qaseem, S.R. Ali, M. Naeem, S. Rizvi, Size induced ferromagnetism in pristine
magnetoresistance in BaBiO3 nanoparticles, Appl. Mater. Today 27 (2022)
indium oxide nanoparticles, Appl. Surf. Sci. 331 (2015) 87–91, https://doi.org/
101427–101435, https://doi.org/10.1016/j.apmt.2022.101427.
10.1016/j.apsusc.2015.01.012.
[6] O. Foyevtsov, S. Balandeh, S. Chi, G. Sawatzky, Structural electronic and magnetic
[35] M. Coey, K. Ackland, M. Venkatesan, S. Sem, Collective magnetic response of CeO2
properties of BaBiO3 single crystals, Phys. B+C: Condenser 570 (2019) 328–333,
nanoparticles, Nat. Phys. 12 (2016) 694–699, https://doi.org/10.1038/
https://doi.org/10.1016/j.physb.2019.06.010.
nphys3676.
[7] R.L. Bouwmeester, A. Brinkman, BaBiO3—from single crystals towards oxide
topological insulators, Rev. Phys. 6 (2021) 100056–100071, https://doi.org/
10.1016/j.revip.2021.100056.

11
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

[36] X. Guan, et al., Defect-rich dopant-free ZrO2 nanoclusters and their size-dependent J. Photochem. Photobiol. Chem. 368 (2018) 70–77, https://doi.org/10.1016/j.
ferromagnetism, ACS Appl. Mater. Interfaces 12 (2020) 48998–49005, https://doi. jphotochem.2018.09.025.
org/10.1021/acsami.0c14706. [63] G. Fan, Z. Gu, L. Yang, F. Li, Nanocrystalline zinc ferrite photocatalysts formed
[37] I. Sugiyama, et al., Ferromagnetic dislocations in antiferromagnetic NiO, Nat. using the colloid mill and hydrothermal technique, Chem. Eng. J. 155 (2009)
Nanotechnol. 8 (2013) 266–270, https://doi.org/10.1038/nnano.2013.45. 534–541, https://doi.org/10.1016/j.cej.2009.08.008.
[38] E. Tirosh, G. Markovich, Control of defects and magnetic properties in colloidal [64] B. Men, J. Zhang, C. Diao, et al., Photoluminescence, surface photovoltage and
HfO2 nanorods, Adv. Mater. 19 (2007) 2608–2612, https://doi.org/10.1002/ photocatalytic properties of BaBiO3 powders, J. Mater. Sci. Mater. Electron. 29
adma.200602222. (2018) 12729–12734, https://doi.org/10.1007/s10854-018-9390-8.
[39] S. Wang, et al., Titanium-defected undoped anatase TiO2 with p-type conductivity, [65] J. Singh, V. Verma, R. Kumar, R. Kumar, Influence of Mg2+-substitution on the
room-temperature ferromagnetism, and remarkable photocatalytic performance, optical band gap energy of Cr2− xMg2− xO3 nanoparticles, Results Phys. 13 (2019)
J. Am. Chem. Soc. 137 (2015) 2975–2983, https://doi.org/10.1021/ja512047k. 1–8, https://doi.org/10.1016/j.rinp.2019.02.042, 102106.
[40] S. Hébert, et al., Induced ferromagnetism in LaMnO3 by Mn-site substitution: the [66] A.C. Gandhi, S.Y. Wu, Strong deep-level-emission photoluminescence in NiO
major role of Mn mixed valency, Phys. Rev. B Condens. Matter 65 (2002) 104420 nanoparticles, Nanomaterials 7 8 (2017) 231–243, https://doi.org/10.3390/
1–7, https://doi.org/10.1103/PhysRevB.65.104420. nano7080231.
[41] T. Nakamura, T. Sata, S. Kose, Paramagnetism and semiconductivity in a triclinic [67] X. Liang, J. Dai, Prominent ferroelectric properties in Mn-doped BiFeO3 spin-
perovskite BaBiO3, J. Phys. Soc. Jpn. 31 (1971) 1284, https://doi.org/10.1143/ coated thin films, J. Alloys Compd. 886 (2021) 161168–161178, https://doi.org/
JPSJ.31.1284. 10.1016/j.jallcom.2021.161168.
[42] I. Shiozaki, Magnetic properties of perovskite-type oxide BaBiO3 and of BaBi1- [68] A.J. Hauser, J. Zhang, L. Mier, R.L. Ricciardo, P.M. Woodward, et al.,
xMxO3 with M identical to In, Mo or La, J. Phys. Condens. Matter 5 (1993) Characterization of electronic structure and defect states of thin epitaxial BiFeO3
6761–6766, https://doi.org/10.1088/0953-8984/5/36/031. films by UV-visible absorption and cathodoluminescence spectroscopies, Appl.
[43] M. Shizuya, et al., Magnetic susceptibility of electron-doped BaBiO3, Phys. C Phys. Lett. 92 (2008), https://doi.org/10.1063/1.2939101, 222901-222901.
Supercond. 357–360 (2001) 169–172, https://doi.org/10.1016/S0921-4534(01) [69] A. Priya, D. Geetha, Ș. Ţălu, Advanced micromorphology study of the Mn-doped
00218-0. bismuth ferrite thin films, Mater. Lett. 281 (2020) 128615–128620, https://doi.
[44] O. Foyevtsov, S. Balandeh, S. Chi, G. Sawatzky, Structural electronic and magnetic org/10.1016/j.matlet.2020.128615.
properties of BaBiO3 single crystals, Phys. B Condens. Matter 570 (2019) 328–333, [70] T. Taniguchi, K. Yamaguchi, A. Shigeta, et al., Enhanced and engineered d0
https://doi.org/10.1016/j.physb.2019.06.010. ferromagnetism in molecularlythin zinc oxide nanosheets, Adv. Funct. Mater. 23
[45] Z. Zeng, J. Feng, X. Zheng, et al., Emergent ferromagnetism with tunable (2013) 3140–3145, https://doi.org/10.1002/adfm.201202704.
perpendicular magnetic anisotropy in short-periodic SrIrO3/SrRuO3 superlattices, [71] O. Petracic, Superparamagnetic nanoparticle ensembles, Superlattice. Microst. 47
Appl. Phys. Lett. 116 (2020) 142401–142407, https://doi.org/10.1063/ (2010) 569–578, https://doi.org/10.1016/j.spmi.2010.01.009.
1.5144643. [72] D. Jiles, in: Introduction to Magnetism and Magnetic Materials, third ed., CRC
[46] P. Kumar, S. Pathak, A. Singh, et al., Optimization of cobalt concentration for Press, Boca Raton, 2015.
improved magnetic characteristics and stability of CoxFe3-xO4 mixed ferrite [73] S. Orrego, J.A. Cortés, R.A.C. Amoresi, A.Z. Simões, M.A. Ramírez,
nanomagnetic fluids, Mater. Chem. Phys. 265 (2021) 124476–124493, https://doi. Photoluminescence behavior on Sr2+ modified CaCu3Ti4O12 based ceramics,
org/10.1016/j.matchemphys.2021.124476. Ceram. Int. 44 9 (2018) 10781–10789, https://doi.org/10.1016/j.
[47] N. Thenmozhi, R. Saravanan, High-temperature synthesis and electronic bonding ceramint.2018.03.116.
analysis of Ca-doped LaMnO3 rare-earth manganites, Rare Met. 41 (2022) [74] V. Kaushik, V. Kumar, D. Kumar, et al., Effect of aging on microstructural and
3932–3942, https://doi.org/10.1007/s12598-017-0964-z. optical properties of sol-gel dip coated BaTiO3 thin films, Appl. Surf. Sci. Adv. 16
[48] G. Acero, H. Moreno, P.P. Ortega, M.A. Ramirez, et al., Unveiling the polar (2023) 100418–100426, https://doi.org/10.1016/j.apsadv.2023.100418.
properties on barium bismuthate perovskite thin films with distinct Ba/Bi ratios, [75] A.R. Chavan, M.K. Babrekar, A.C. Nawle, et al., Impact of trivalent metal ion
J. Alloys Compd. 974 (2024) 172871–172882, https://doi.org/10.1016/j. doping on structural, photoluminescence and electric properties of NiFe2O4 thin
jallcom.2023.172871. films, J. Electron. Mater. 48 (2019) 5184–5194, https://doi.org/10.1007/s11664-
[49] M.P. Pechini, Method of Preparing Lead and Alkaline Earth Titanates and Niobates 019-07329-w.
and Coating Method Using the Same to Form a Capacitor, 1967. Patent [76] D. Karfaridis, L. Mihalceanu, S. Keller, et al., Influence of the Pt thickness on the
US3330697. structural and magnetic properties of epitaxial Fe/Pt bilayers, Thin Solid Films 694
[50] L.F. Gonçalves, L.S. Rocha, E. Longo, A.Z. Simões, Calcium doped BiFeO3 films: (2020) 137716–137725, https://doi.org/10.1016/j.tsf.2019.137716.
Rietveld analysis and piezoelectric properties, J. Mater. Sci. Mater. Electron. 29 [77] H.J. Albert, L.R. Rubin, Magnetic properties of the platinum metals and their
(2018) 784–793, https://doi.org/10.1007/s10854-017-7973-4. alloys, Adv. Chem. 98 (1971) 1–16, https://doi.org/10.1021/ba-1971-0098.
[51] R.C. Deus, L.F. Gonçalves, C.C. Cavalcanti, L.S.R. Rocha, E. Longo, A.Z. Simões, ch001.
Magnetocoupling and domain structure of BiFeO3/LaFeO3 heterostructures [78] Md R. Islam, et al., Evidence of superparamagnetism and improved electrical
deposited on LaSrCoO3/Pt/TiO2/SiO2/Si (100) substrates by the soft chemical properties in Ba and Ta co-doped BiFeO3 ceramics, J. Alloys Compd. 735 (2018)
method, J. Mater. Sci. Mater. Electron. 28 (2017) 8630–8642, https://doi.org/ 2584–2596, https://doi.org/10.1016/j.jallcom.2017.11.323.
10.1007/s10854-017-6587-1. [79] P.P. Mohapatra, P. Dobbidi, Thickness tuneable dielectric, optical and magnetic
[52] P.P. Ortega, L.S.R. Rocha, C.C. Silva, M. Cilense, R.A.C. Amoresi, E. Longo, A. response of lithium ferrite thin films deposited by pulsed laser deposition, Thin
Z. Simões, Multiferroic behavior of heterostructures composed of lanthanum and Solid Films 774 (2023) 139845–139857, https://doi.org/10.1016/j.
bismuth ferrite, Ceram. Int. 42 (2016) 16521–16528, https://doi.org/10.1016/j. tsf.2023.139845.
ceramint.2016.07.070. [80] H. Yao, X. Ning, H. Zhao, A. Hao, M. Ismail, Effect of Gd-doping on structural,
[53] E.C. Aguiar, M.A. Ramirez, J.A. Cortes, L.S. Rocha, E. Borsari, A.Z. Simões, optical, and magnetic properties of NiFe2O4 as-prepared thin films via facile sol-gel
Magnetoelectric coupling of LaFeO3/BiFeO3 heterostructures, Ceram. Int. 41 approach, ACS Omega 6 (2021) 6305–6311, https://doi.org/10.1021/
(2015) 13126–13134, https://doi.org/10.1016/j.ceramint.2015.07.043. acsomega.0c06097.
[54] L.F. Gonçalves, J.A. Cortés, M.G.A. Ranieri, F. Destro, M.A. Ramirez, A.Z. Simões, [81] K. Bala, R.K. Kotnala, N.S. Negi, Magnetically tunable dielectric, impedance and
Fabrication and structural characterization of bismuth niobate thin films grown by magnetoelectric response in MnFe2O4/(Pb1− xSrx)TiO3 composites thin films,
chemical solution deposition, J. Mater. Sci. Mater. Electron. 26 (2015) 1142–1150, J. Magn. Magn Mater. 424 (2017) 256–266, https://doi.org/10.1016/j.
https://doi.org/10.1007/s10854-014-2518-6. jmmm.2016.10.059.
[55] H.M. Rietveld, A profile refinement method for nuclear and magnetic structures, [82] L. Kumar, P. Kumar, M. Kar, Cation distribution by Rietveld technique and
J. Appl. Crystallogr. 2 (1969) 65–71, https://doi.org/10.1107/ magnetocrystalline anisotropy of Zn substituted nanocrystalline cobalt ferrite,
S0021889869006558. J. Alloys Compd. 551 (2013) 72–81, https://doi.org/10.1016/j.
[56] A.A. Coelho, Topas and topas-academic: an optimization program integrating jallcom.2012.10.009.
computer algebra and crystallographic objects written in C++, J. Appl. Crystallogr. [83] T. Watanabe, et al., Grain boundary engineering by magnetic field application,
51 (1) (2018) 210–218, https://doi.org/10.1107/S1600576718000183. Scripta Mater. 54 (6) (2006) 969–975, https://doi.org/10.1016/j.
[57] Ch Kittel, P. McEuen, in: Introduction to Solid State Physics, ninth ed., John Wiley scriptamat.2005.11.036.
& Sons, New Jersey, 2018. [84] D.C. Dunand, P. Müllner, Size effects on magnetic actuation in Ni-Mn-Ga shape-
[58] B.D. Cullity, S.R. Stock, in: Elements of X-Ray Diffraction, third ed., Prentice-Hall, memory alloys, Adv. Mater. 23 (2011) 216–232, https://doi.org/10.1002/
New York, 2001. adma.201002753.
[59] A.Z. Simões, B.D. Stojanovic, M.A. Ramirez, Lanthanum-doped Bi4Ti3O12 prepared [85] L. Tauxe, H.N. Bertram, C. Seberino, Physical interpretation of hysteresis loops:
by the soft chemical method: Rietveld analysis and piezoelectric Properties, Ceram. micromagnetic modeling of fine particle magnetite, G-cubed 3 10 (2002) 1055,
Int. 34 (2008) 257–261, https://doi.org/10.1016/j.ceramint.2006.09.019. https://doi.org/10.1029/2001GC000241.
[60] A.Z. Simões, R.F. Pianno, E.C. Aguiar, et al., Effect of niobium dopant on fatigue [86] G. Koplovitz, et al., Single domain 10 nm ferromagnetism imprinted on
characteristics of BiFeO3 thin films grown on Pt electrodes, J. Alloys Compd. 479 superparamagnetic nanoparticles using chiral molecules, Small 15 (1) (2019)
(2009) 274–279, https://doi.org/10.1016/j.jallcom.2009.01.074. 1804557–1804564, https://doi.org/10.1002/smll.201804557.
[61] C. Ferreyra, F. Guller, F. Marchini, et al., Tuning the electronic properties at the [87] A. Tamm, et al., Atomic layer deposition of superparamagnetic ruthenium-doped
surface of BaBiO3 thin films, AIP Adv. 6 (2016) 065310, https://doi.org/10.1063/ iron oxide thin film, RSC Adv. 11 (13) (2021) 7521–7526, https://doi.org/
1.4954037. 10.1039/d1ra00507c.
[62] A.M. Huerta-Flores, D. Sánchez-Martínez, R. del Rocío Hernández-Romero, M. [88] M. Chithra, C.N. Anumol, B. Sahu, S.C. Sahoo, Exchange spring like magnetic
E. Zarazúa-Morín, L.M. Torres-Martínez, Visible-light-driven BaBiO3 perovskite behavior in cobalt ferrite nanoparticles, J. Magn. Magn Mater. 401 (2016) 1–8,
photocatalysts: effect of physicochemical properties on the photoactivity towards https://doi.org/10.1016/j.jmmm.2015.10.007.
water splitting and the removal of rhodamine B from aqueous systems,

12
G. Acero et al. Materials Chemistry and Physics 322 (2024) 129523

[89] M.N. Rahaman, in: Ceramic Processing and Sintering, second ed., Marcel Dekker, [92] R. Zalecki, W.M. Woch, M. Kowalik, A. Kołodziejczyk, G. Gritzner, Bismuth valence
New York, 2003. in a Tl0.7Bi0.3Sr1.6Ba0.4CaCu2Oy superconductor from X-ray photoemission
[90] S. Banerjee, M. Mandal, N. Gayathri, M. Sardar, Enhancement of ferromagnetism spectroscopy, Acta Phys. Pol. 118 (2010) 393–395, https://doi.org/10.12693/
upon thermal annealing in pure ZnO, Appl. Phys. Lett. 91 (2007) 1–3, https://doi. APhysPolA.118.393.
org/10.1063/1.2804081, 182501. [93] P. Wang, C. Jin, P. Li, et al., Oxygen vacancies induced ferromagnetic behaviors in
[91] M. Chithra, C.N. Anumol, V. Argish, B. Sahu, S.C. Sahoo, Tailoring magnetic Co3O4–δ: an experimental and first-principles study, Thin Solid Films 660 (2018)
properties of cobalt ferrite nanoparticles by different divalent cation substitution, 287–293, https://doi.org/10.1016/j.tsf.2018.06.022, 2018.
J. Mater. Sci. Mater. Electron. 29 (2018) 813–822, https://doi.org/10.1007/ [94] K.S. Sivaranjani, et al., Comprehensive law-of-approach-to-saturation for the
s10854-017-7976-1. determination of magnetic anisotropy in soft magnetic materials, Phys. Status
Solidi B (2022) 2200050–2200060, https://doi.org/10.1002/pssb.202200050.

13