Journal of Physics: Condensed Matter

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Investigation of room temperature ferromagnetism in transition metal

doped BiFeO₃
To cite this article before publication: Vinay Sharma et al 2019 J. Phys.: Condens. Matter in press https://doi.org/10.1088/1361-648X/ab29d1

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Page 1 of 21 AUTHOR SUBMITTED MANUSCRIPT - JPCM-114037.R1

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Investigation of room temperature
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7 ferromagnetism in transition metal doped
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BiFeO3

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13 Vinay Sharma1, Ram Krishna Ghosh1, and Bijoy K. Kuanr1,*

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15 Special Centre for Nanoscience, Jawaharlal Nehru University, Delhi-110067, India
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17 *
Email:-bkkuanr@gmail.com, bijoykuanr@mail.jnu.ac.in
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20 Abstract

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Spintronic functionality in ferromagnetic materials is a next-generation technique, to be used in data storage,
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24 high-frequency communications, and logic devices with minimum energy consumption. Ultra-low energy
25 consumption in high-speed logic devices can be envisioned by inducing ferromagnetic behavior into room
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temperature multiferroic materials. However, there is a scarcity of room temperature multiferroic materials
which have a definite spin degree of freedom. To fully exploit these technological challenges, we introduce the

30 induced ferromagnetism in bismuth ferrite (BiFeO3, BFO) by doping transition metal (Cr, Ni, Co) elements. Our
31 investigation initiates with the experimental study on chemically synthesized BiFe (1-x)MxO3 samples where x=
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0.0625 (6.25%) and M= Cr, Ni and Co. Experimental findings are verified by theoretical simulation using
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34 density functional theory (DFT+U) and gauge including projector augmented wave (GIPAW) based calculation.
35 All the experimental studies are done at room temperature while the theoretical verification using DFT is carried
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37 to understand the underlying mechanism behind the magnetic behavior of doped BiFeO3. It is done by
38 optimizing the structural parameters comparable to the room temperature values. Microstructural and magnetic
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40 properties are studied using X-ray diffraction (XRD), transmission electron microscopy (TEM) and Vibrating
41 sample magnetometer (VSM). All these experimental studies confirm the structural changes and induced
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43 ferromagnetism with doping. X-ray Photoelectron Spectroscopy (XPS) verified the reason behind this
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44 ferromagnetic property on the basis of oxygen vacancy content. Electron paramagnetic resonance (EPR)
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spectroscopy shows the tuning of Δg values due to enhanced magnetization.
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48 The density of states (DOS) calculations were performed on BFO (band-gap 1.89 eV) after structural
49 optimization using DFT+U method, confirm our experimental findings. Magnetic moment values change
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drastically with doping elements (M), i.e. almost negligible for BFO (antiferromagnetic) to maximum (2.85
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52 μB/f.u.) for Ni-doped sample. We also compute the EPR g-tensor using GIPAW method to confirm the tuning of
53 Δg values due to enhanced magnetization. These results can highlight the impact and importance of suitable
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55 transition element doping to induce the room temperature ferromagnetism in BiFeO3.
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3 KEYWORDS: Ferromagnetism, Density functional theory, Density of states, X-ray photoelectron spectroscopy,
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5 Electron paramagnetic resonance.
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8

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9 1. INTRODUCTION
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Room temperature ferromagnetism is a physical phenomenon that comes under the branch of condensed matter
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physics and works mainly on the properties of electron spin, with a view to improve speed, efficiency, and

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15 functionalities of electronic devices. Researchers are exploiting the control of single localized spin at an atomic
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17 scale in a crystal such as spin qubits [1-3] for quantum computation. Moreover, there is continuous research
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19 going on to explore spin dynamics and its coupling to spin transport in macro-scale systems [4, 5] which
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21 provided fascinating phenomena like spin torque oscillator [6, 7], spin Hall effect [8, 9] and spin caloritronics
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23 [10, 11], etc. All these scientific achievements lead to conventional spintronic based devices like magnetic data
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25 storage, logic devices, and high-frequency communications. As these devices are continuously scaled to very
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narrow dimensions, they lead to significant energy dissipation in the form of heat. Taking advantage of the

multiferroic system, specifically the coupling between ferroelectric and magnetic ordering, ultra-low energy
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31 consumption devices can be envisioned [12, 13]. Perovskite multiferroic structures have long been an interesting
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33 topic because slight modifications of the atomic structures can lead to multiple functionalities [14, 15]. With this
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anticipation, we are intending our research to room temperature multiferroic system. Among all identified
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single-phase multiferroic, Bismuth Ferrite (BiFeO3, BFO) is an interesting candidate because it exhibits the
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38 coexistence of ferroelectric and G-type antiferromagnetic (AFM) ordering well above the room temperature
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40 (Curie temperature (TC)~ 1103 K and Neel temperature (TN)~ 643 K) [16-18]. BFO shows weak
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42 antiferromagnetism (wAFM) at room temperature and their spins form a cycloidal structure with wavelength λ=
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44 62 nm [19, 20]. This cycloidal structure exhibits the spin wave resonance at very high frequency (>100 GHz)
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46 [21-24]. As pristine phase BFO exhibits AFM ordering, no macroscopic magnetization have been identified in
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48 it. This has been confirmed by the previous electron paramagnetic resonance (EPR) studies at f= 9.86 GHz,
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50 which shows „g’ values correspond to a free electron value i.e. g ~ 2.0 [25, 26]. Despite the fact that tuning of g-
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52 values has been identified with the help of A and B site doping in BFO [25-27], there is no strong evidence
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54 present till date which can focus on their relationship with a change in magnetization, both experimentally and
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56 theoretically. Zhang et al. showed the enhanced magnetization in Holmium and Manganese doped BFO thin
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films [28] without any theoretical verification behind the underlying mechanism of the doping effect. Liu et al.
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discussed the structural and optical properties of BFO using first principle calculations but this study is lacking
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3 in experimental verification [29]. Mukherjee et al. discussed the role of Ni and Co doping in BFO but this
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5 review article just discussed the structural and dielectric properties without focussing on magnetic properties
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7 [30]. Recently few reports are devoted to identifying the spintronic behaviors in B site Ni-doped BFO on the
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9 basis of density functional theory (DFT+U) studies with the induced half-metallic nature [31-33]. But these
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11 studies are lacking in experimental analysis.
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In this paper, we analyze the ferromagnetic behaviors in transition metal (Cr, Ni, and Co) doped BFO, both

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15 experimentally and theoretically. Such an analysis, to the best of our knowledge, has not been previously
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17 reported. We initially carried out an experimental investigation on these samples at room temperature. All the
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19 samples have been carefully synthesized to study the change in magnetic properties. Pristine BFO and doped
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21 BFO samples are found to have rhombohedral symmetry with R3c space group [34, 35]. This has been
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23 confirmed by X-ray diffraction (XRD) studies. No drastic changes are observed after doping in the structure
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25 except in lattice parameters and cell volume. The enhanced magnetization property in the doped samples is
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probed by-vibrating sample magnetometry (VSM). X-ray photoelectron spectroscopy (XPS) studies confirm the

percentage change in valence states of Fe atoms which leads to the change in enhanced magnetization. EPR
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31 studies depict tuning of „g’ values due to the macroscopic magnetization in the doped samples.
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33 After the experimental study, we theoretically verified our findings using DFT+U study in the doped BFO
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35 structure (with constant doping of x= 0.0625 (6.25%) in BiFe1-xMxO3, where M= Cr, Ni, Co). A careful
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37 theoretical analysis depicts an enhanced magnetization in the doped samples. Ni-doped sample is also showing
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39 the property which moves the system towards the half-metallic nature which is a well-studied characteristic
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41 helpful in spintronic behavior [36-38]. Moreover, our gauge including projector augmented wave (GIPAW)
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43 calculations show that the change in g (i.e. Δg) increase with increasing magnetization in doped samples. Our
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45 finding opens a new paradigm in the field of multiferroic based perovskite structure with induced ferromagnetic
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47 properties.
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49 2. Experimental and calculational methods
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52 2.1 Synthesis of material

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55 Pure and transition metal (Cr, Ni, and Co) doped samples are synthesized by sol-gel chemistry. The starting
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57 materials used to synthesize are; bismuth nitrate pentahydrate (BiNO3.5H2O), ferric nitrate nonahydrate
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59 (Fe(NO3)3.9H2O), chromium nitrate nonahydrate (Cr(NO3)3.9H2O), nickel nitrate hexahydrate (Ni(NO3)2.6H2O)
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3 and cobalt nitrate hexahydrate (Co(NO3)2.6H2O) are all purchased from Sigma Aldrich with purity> 99.8%. All
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5 the compounds are initially dissolved in 2-methoxy ethanol with appropriate stoichiometry and stirred for 2
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7 hours at room temperature. After proper mixing of the individual sols, initially dried under Infra Red (IR)
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9 heating and then calcined at 600o C for 2 hours with increasing ramp rate at 2.5 0C/min to get the pure phase
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11 powder samples.
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2.2 Structural and magnetic characterizations

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16 The structural phases of the samples were investigated using XRD. Powder XRD patterns were collected using
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18 miniflex Rigaku diffractometer with Cu Kα radiation (λ=1.5418 Å) with an accelerating voltage of 30 kV.
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20 Scanning was carried out in the angle range of 20 0 ≤ θ ≤ 600, with an increment of 0.0200 and a scanning speed of

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22 20/min at room temperature. JEOL (Model 1200F) transmission electron microscope (TEM) was used for
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24 observing the samples morphologies and crystal structure information. It uses an acceleration voltage of 200 kV.
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26 A 300 mesh copper grid with a carbon film deposited on a formvar backing, were used for preparing the TEM
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samples. A drop of the sample dispersion liquid was put on the former side of the TEM grid and the solvent

30 (Ethanol) was allowed to dry in air. Room temperature magnetic hysteresis loops were recorded using VSM form
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32 Cryogenics, UK. The measurements were done in the range of -4 Tesla to +4 Tesla. Saturation magnetization and
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34 coercivity were determined. The weight of the samples was carefully measured to normalize the moments in
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38 2.3 Spectroscopic technique
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41 2.3.1 X-Ray photoelectron spectroscopy
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44 XPS spectra were measured on Thermo scientific K-Alpha+ XPS spectrometer. K-Alpha+ dual beam charge
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46 compensation system was used. The XPS spectra were used to measure the Fe valence state, which provides
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48 information on the population of Fe2+ and Fe3+ ions. Oxygen vacancy contents have also been determined.
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2.3.2 EPR spectroscopy
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53 EPR measurements were done using Bruker EPR spectrometer Model- EMX MicroX at room temperature.
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55 Measurements were done at Frequency= 9.86 GHz inside an X-band cavity with a very high Q value of
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3 2.4 Theoretical calculations
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6 2.4.1 DFT based calculations of Electronic and magnetic properties:
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8 To calculate the structure, electronic and magnetic properties of doped BiFeO3, we used DFT within the local

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10 spin-density approximation (LSDA) and the LSDA+U method as implemented in the Quantum Wise, Atomistix
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12 Toolkit (ATK). All results are obtained by explicitly treating the valence band wave functions of different atoms
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14 (Bi: 6s26p3, Fe: 3d64s2, O: 2s22p4, Co: 3d74s2, Cr: 3d54s1, Ni: 3d84s2) as a linear combination of atomic orbitals
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16 (LCAO). Perdew and Zunger (PZ) approximation for the exchange-correlation function along with double-ζ-
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18 double-polarized (DZDP) basis on each atom has been used in the LCAO pseudopotential calculations which
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20 are usually comparable to well-converged plane wave basis sets. Moreover, the core electrons of all atoms have

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22 been described by norm-conserving Troullier-Martins pseudo-potentials. All the calculations are performed with
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24 a 7✕7✕7 Monkhorst–Pack k-point mesh centered at Γ and a 150 Ry mesh cut-off energy on a real space grid of
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26 charge density and potentials, both of which offers a good convergence of the computed ground-state properties.
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Before calculating the electronic properties, we optimized the geometrical structures in all cases by LSDA+U

30 until the structures reached configurations with energy differences of 1×10 −5eV/atom, and forces less than 0.01
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32 eV/Å. All the optimized structures are shown in a 2x2x2 supercell (Fig. 1) with 16 formula units of BFO and a
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total of 80 atoms. 6.25% doping is observed by replacing a Fe atom with a transition metal atom (Cr, Ni, and
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Co) in the supercell (as shown in Fig. 1(b), (c) and (d)).
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Fig 1Structural models of (a) pristine BFO and transition metal doped BFO (b) Cr doped BFO, (c) Co-doped BFO and (d)
37 Ni-doped BFO. 80 atoms are present in the supercell. One Fe element out of 16 is replaced by the transition element to
38 realize 6.25% doping in the supercell.
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40 2.4.2 Calculations of EPR g-tensor using GIPAW calculation:
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42 The calculation of the change in „g‟ tensor (Δg) is based on the GIPAW method as implemented in Quantum
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44 Espresso [39, 40]. We have used PZ functional to describe the electron-electron interaction within the local
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46 spin-density approximation (LSDA). To describe the electron-ion interaction, we have also considered the
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48 Norm-conserving Troullier-Martins pseudopotentials along with plane-wave basis, ideally suited for periodic
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50 boundary conditions. Moreover, we have used a 4x4x4 supercell of the structures for all these calculations, as
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52 GIPAW relies on the supercell approach to determine the Δg. We have also performed the convergence test of
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54 atomic forces (< 10-3), energies (< 10-4), Brillouin zone (BZ) sampling (4x4x4), and plane-wave energy cutoff
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56 (35 Ry) to obtained converged g tensors in doped BFO. It should be noted that the GIPAW method exclusively
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relies on the occupied states; therefore the underestimation of the unoccupied-states energies (i.e. the DFT band-
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gap problem) is irrelevant for our g-tensor calculations. We also want to mention that the values of the magnetic
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3 moment obtained in these QE-GIPAW calculations are comparable to the values obtained in Quantumwise
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7 3. Results and discussion
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10 3.1 Phase identification and structural analysis
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Fig 2 (a) XRD graphs of all the doped samples in the 2θ range of 20 0 to 600 at room temperature, (b) magnified version of
30 red encircled part in “(a)” 2θ range of 310 to 340 to show the shifting of peaks and also transformation towards pseudo-cubic
phase in Ni-doped BFO and (c) Fe-O-M (where M= Fe (Green), Cr (Yellow), Co (Blue) and Ni (Magenta) and O= Oxygen
31 (red) atom) bond angles change due to doping in BFO.
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33 Fig. 2(a) shows the room temperature XRD pattern of pristine BFO and doped BFO structures. It can be seen
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35 that all the four perovskite structures show the characteristic peaks of R3c space group with rhombohedral
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37 symmetry well matched with the JCPDS card no 71-2494 [41]. The doped transition metal ions preferentially
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39 substitute the B-site (Fe atom) of BFO. Due to the difference in transition metal ions radii, there is a shifting
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41 observed in the XRD peaks as shown in Fig. 2(b). It can be observed from Fig. 2(b), that crystal structure
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43 slightly lowers it symmetry towards the pseudo-cubic nature and it leads to the increase in d-spacing for Ni and
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45 Co-doped BFO structures. Change in tilting angle of Fe-O-Fe/M (shown in Fig. 2(c)) confirms these doping
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levels. BFO exhibits the tilting of FeO6 octahedrons and results in wAFM ordering due to the superexchange
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interaction between Fe3+-O2--Fe3+ bonding [42, 43]. However, doping of transition metals (Cr, Ni, and Co)
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50 deforms this tilting. This deformation leads to a direct change in the electronic and magnetic structure of the
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52 system. Fe-O-Fe/M (M= Cr, Ni, and Co) bond angles increased from 150.94 o for BFO to 153.56o for Ni-doped
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54 samples. This increase of bond-angles (towards 180o) is expected to increase the bandwidth of occupied and
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56 unoccupied bands, hence reducing the band gap of doped BFO structures. If doped BFO structures move to the
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58 tilt free or less tilt pseudo-cubic symmetry then the band gap reduced which will be further verified in the
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60 theoretical study. Hence ground state becomes ferromagnetic rather than the G type AFM [44, 45], which will

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3 be experimentally demonstrated using VSM study. We have also done the structural characterization of higher
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5 doping percentage of Ni in BFO (See supplementary figure S1). It clearly shows that with higher doping of Ni
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Fig 3 (a) TEM image and particle size distribution (inset) of BFO Nanoparticles, (b) HR-TEM image of BFO NPs
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corresponds to <104> plane, (c) SAED pattern of BFO NPs, (d) TEM image and particle size distribution (inset) of Ni-doped
25 BFO NPs, (e) HR-TEM image of Ni-doped BFO NPs correspond to <104> plane which shows increase in d-spacing due to
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Ni doping and (f) SAED pattern of Ni-doped BFO NPs.
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Fig. 3 shows the TEM images for pristine BFO and Ni-doped BFO samples. It can be seen from Fig. 3(a) and

30 3(d) that synthesized samples shows the spherical shape morphology. Inset in Fig. 3(a) and 3(d) shows the
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32 particle size distribution which clearly reflects that due to Ni doping particle size increased to 35.6 nm. Clear
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34 fringes in Fig. 3(b) and 3(e) show that synthesized samples are well crystalline. High-resolution TEM (HRTEM)
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36 image in Fig. 3(b) and 3(e) verified the increase in d- spacing due to transition metal doping in BFO. Diffraction
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ring pattern in Fig. 3(c) and 3(f) confirm the polycrystalline nature of doped and pristine BFO structures.
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Fig 4 VSM graphs of all the doped samples at room temperature in the magnetic field range of -4 Tesla to +4 Tesla. The
inset shows the magnified version near the origin to show the coercivity change in the doped samples, Co-doped sample
shows the maximum coercivity.
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33 Magnetic properties are studied by VSM characterization. M-H hysteresis curves for all the powder samples are
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35 individually measured by VSM at room temperature and their corresponding magnetization values are plotted
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37 after normalization by their weight (Fig. 4). Table 1 shows the observed magnetic parameters extracted from
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39 VSM plots. Ni-doped sample shows the highest value of magnetization followed by Cr and Co respectively.
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41 Table.1 Measured magnetization parameters of all the doped samples.
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44 Sample Ms (emu/gm) Hc (Oe)

45 (BFO) BiFeO3 0.01 15
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48 (BFCoO) BiFe0.9375Co0.0625O3 1.1 2000
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50 (BFCrO) BiFe0.9375Cr0.0625O3 2.6 120
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52 (BFNO) BiFe0.9375Ni0.0625O3 3.2 125

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3 153.56o, followed by Cr (153.12o) and then Co (151.60o) in comparison to BFO (150.94o). The bond-angle plays
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5 a major role in controlling the magnetic exchange and orbital overlap between Fe-O atoms. Secondly, doping of
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7 transition metals induces the Dzyaloshinskii-Moriya (D-M) interaction, which can play a significant role in
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9 enhancing the ferromagnetism in these samples [46, 47]. D-M interaction causes the anti-symmetric magnetic
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11 exchange and hence creates the noncollinear spin states including canted AFM states (Inset in Fig. 4). D-M
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15 octahedra and hence increases the net magnetization. The Co-doped sample exhibits the highest value of
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17 coercivity which may be due to increased defect concentrations in the doped structure. Cobalt is a hexagonal
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enhanced the magnetic anisotropy and hence the coercivity also increased in BFCoO samples. Large coercivity
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22 in Co-doped samples is also observed in previous studies [48, 49]. To confirm the change in magnetization, we
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supplementary sheet). It clearly shows that with increase in Ni doping magnetization increases.

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3.3 Spectroscopic analysis using XPS spectroscopy
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53 Fig 5 High Resolution XPS spectra of; (a) Bi4f, (b) Fe2p and (c) O1s for Pristine BFO and (d) Bi4f, (e) Fe2p and (f) O1s for
54 Ni-doped BFO NPs. (Black dots shows experimental data and Red line shows the fitting data)
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58 To elucidate the finding of enhanced magnetization, we have further performed the XPS analysis of pristine
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3 cation in the samples. This technique is used to identify the variation of saturation magnetization (Ms) on the
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5 basis of Fe valence state. Bi3+ 4f peaks are resolved in 4f7/2 and 4f5/2 [50] and have a spacing of approximately
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7 5.3 eV in both pristine BFO and Ni-doped BFO (Figure 5(a) and (d)). On the basis of the careful analysis, Fe2+:
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9 Fe3+ concentration can be revealed. After Ni doping, this concentration ratio is increased to 2.71 from 2.21 in
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11 pristine BFO (Figure 5(b) and (e)). O1s spectra are resolved in cation-oxygen bond and oxygen vacancies [51].
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13 It is found that after Ni doping cation oxygen bonds increased to 87.5% as compared to 78% in BFO (Figure

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15 5(c) and (f)). This confirms that Ni doping prevents oxygen vacancies formation. XPS analysis confirms the
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17 doping of transition elements which restricts the formation of defects and oxygen vacancies in BFO structure.
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19 3.4 Theoretical study
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22 3.4.1 DFT+U study for electronic and magnetic properties
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25 To verify the stable phase and magnetic properties of BFO, we utilize DFT to model the crystal structure based
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on atomic positions extracted from the optimized geometry. As discussed in earlier reports [32, 52], R3c

symmetry is more appropriate to describe the structure of BFO. We utilized this approach to calculate the
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31 density of states (DOS) and the band gap of our optimized structures. Since it is already predicted that DFT
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orbitals [53], and wrongly predicts the metallic behavior of insulating materials [54].
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41
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43
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44
45
46
47
48
49
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52
Fig 6 Model of BFO structure used for DFT+U calculation (a) Hubbard parameter (Ueff) was taken according to the change
53
in band gap and was chosen as Ueff = 4 eV, Optimized crystal structure of BFO used for DFT+ U calculation in R3c
54 geometry (inset), (b) Calculated DOS for optimized BFO structure, confirming the antiferromagnetic nature.
55
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1
2
3 Therefore, we included the DFT+U framework by adding a Hubbard like term to correctly predict the electronic
4
5 and magnetic properties of BFO. Based on the optimized structure and desired Ueff values (Fig. 6(a)), we have
6
7 calculated DOS of the pristine BFO structures with both spin channels as shown in Fig. 6(b). Optimized
8

pt
9 structures are shown with FeO6 octahedrons with their corresponding tilt as shown in the inset of Fig. 6(a). It
10
11 was observed that LSDA calculations yield a better description of the AFM multiferroic structure [53, 55]. It can
12
13 be seen from Fig. 6(a) that the bandgap is increasing significantly with the increasing U. However, J. K. Shenton

cri
14
15 et al. has shown that the t2g/eg ordering at the conduction band minimum inverts for U values larger than 4 eV in
16
17 BiFeO3 [56, 57]. Therefore, Ueff = 4eV is a good choice to predict the correct band gap values of BFO which is
18
well below the limiting condition. The identical spin population in Fig. 6(b) for both spin up and spin down
19
20

us
electrons confirms the AFM structure of BFO. BFO structure is insulating with an approximate band gap of E g =
21
22 1.89 eV. Mulliken population is calculated to predict the magnetic moment of BFO which shows that it has
23
24 approximately zero magnetic moments (1.04 x 10-9 µB/f.u.). 6.25% transition metal doped structures with
25
26
27
28
29
an
optimized geometry are used to calculate the change in electronic and magnetic properties. Ni, Cr and Co-doped

structures with the same percentage of doping have also shown R3c symmetry. All the lattice parameters and

30 bond angles of the optimized structures are given in Table 2.

31
32
dM
Table 2. Lattice parameters and bond angles of all the doped samples
33
34 Sample α β γ a b c Unit cell Experimental Bond angle,
35 (degrees) (degrees) (Å) (Å) (Å) volume lattice Fe-O-M
36 (degrees) (Å3) constant M=
37 (Å) (Fe/Cr/Ni/Co)
38 degrees
39 BiFeO3 60.9862 60.8392 60.9802 5.463 5.461 5.461 117.754 5.564 150.94
40 BiFe0.9375Co0.0625O 60.9921 60.8728 60.9854 5.458 5.456 5.457 117.480 5.538 151.60
41 3
42 BiFe0.9375Cr0.0625O 60.9735 60.8835 60.9665 5.460 5.459 5.459 117.572 5.544 153.12
43
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3
44 BiFe0.9375Ni0.0625O 61.0170 60.9465 61.0114 5.450 5.449 5.450 117.063 5.535 153.56
45 3
46
47
48
49 Table 3. Calculated and experimental energy band-gap values of all the doped samples.
50
51 Sample Bandgap (Eg, eV) Bandgap (Eg, eV)
ce

52 (Theoretical) (Experimental)
53 BiFeO3 1.891 2.322
54 BiFe0.9375Co0.0625O3 1.885 2.215
55 BiFe0.9375Cr0.0625O3 1.861 2.205
56 BiFe0.9375Ni0.0625O3 1.814 2.166
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1
2
3 Change in electronic band gap with transition metal doping is shown in Table 3. Experimental band gaps are
4
5 calculated using Ultra violet-Visible (UV-Vis) spectroscopy. UV-Vis spectrums are given in supplementary
6
7 sheet (See supplementary figure S3). The observed changes in the bonding environment due to transition metal
8

pt
9 doping results in the lowering of lattice symmetry from rhombohedral to pseudo-cubic. It is a matter of fact that
10
11 low doping (6.25 %) of transition metals does not change the R3c lattice symmetry but only change the lattice
12
13 constants and cell volume [58]. Our calculations showed that doped BFO structures show slightly smaller lattice

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14
15 constants and cell volume as compared to BFO. This can be explained by the following analogy; Ni 2+ has an
16
17 ionic size of 0.69 Å and is smaller than Fe2+ (0.74Å) but slightly larger than Fe3+ (0.64Å).
18
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20

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52
53
54 Fig 7 Calculated DOS (U = 4eV) of doped BFO structures for different doped transition elements (a) Co, (b) Cr and (c) Ni
with Zoomed part near to the Fermi level.
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1
2
3 The calculated DOS for both spin channels are found to be asymmetric in our calculation and hence give rise to
4
5 increased magnetic moments in doped BFO structures as shown in Fig. 7. This finding has also been confirmed
6
7 experimentally in the magnetization study in the previous section. Increased magnetic moments and Mulliken
8

pt
9 population for pristine and doped BFO structures are shown in Table 4.
10
11
12
13

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14 Table 4. Calculated Mulliken population and magnetic moment for different - dopants
15
16 Sample Σ Fe (Total Fe Σ Cr (Total Cr Σ Ni (Total Ni Σ Co (Total Co Mnet (net
17
population) population) population) population) magnetic
18
19 moments)(μB/f.u.)
20

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21 BiFeO3 ~0 - - - ~0
22
23 BiFe0.9375Co0.0625O3 4.300 - - -3.13 1.17
24
25
26 BiFe0.9375Cr0.0625O3 4.388 -2.985 - - 1.403
27
28
29
BiFe0.9375Ni0.0625O3 4.298 -
an -1.658 - 2.64

30
31
32
dM
33 Despite the fact that all doped transition elements (Co, Cr, and Ni) reduce band gap but Ni-doped sample
34
exhibits a property in which Ni doping shifts the system towards half-metallic nature. The change in up-spin and
35
36
down-spin energy level in both conduction and valence bands are far away in energy with respect to Fermi level
37
38 in case of pristine BFO, Cr and Co-doped BFO samples (see Fig. 7(a)-(b)). In the Ni-doped sample, the spin
39
40 population in the valence band increased drastically with an asymmetric spin channel population and shifts very
41
42 close to the Fermi level (Figure. 7(c)).
43
pte

44
45 Even though it is not a true half-metallic in nature but the valence band up spin population shifted towards the
46
47 Fermi level (↑EF-EV= 0.06eV) due to the Ni doping (Zoom part of Fig 7) and this indicates that system tends
48
49 towards the half-metallic nature for Ni-doped sample. Hence, we can conclude that Ni doping can be a good
50
candidate for efficient ferromagnetic properties in BFO structure and can be helpful for spintronics applications.
51
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52
53 3.4.2 EPR g tensor study using experimental and theoretical calculation (GIPAW)
54
55
56 We have performed experimental EPR study to further confirm the finding of enhanced magnetization and
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58 ferromagnetic nature in transition metal doped BFO structures.
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30 Fig 8 EPR plots of the synthesized samples at f=9.86 GHz showing (a) differential intensity versus applied magnetic field
31 (H). (b) Variation of Δg (both experimental and theoretical) with enhanced magnetization, and (c) Spin quantification
32 obtained after the integration of experimentally observed EPR differential curves. (d) There is a spin density that increases
dM
33 with the increase in Δg values as shown in the increment in the area under the curve.
34
35
36
37 The experimental EPR plots in Fig. 8(a) identifies the effect of enhanced macroscopic magnetization in the
38
39 doped BFO samples. This spectroscopy is very sensitive to the surface phase transitions including electronic
40
41 charges and magnetic spin wave dynamics [59]. The area under the EPR curves is helpful in determining the
42
43
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spin density in the samples (Fig. 8(c, d)). As can be seen in Fig. 8(a), Cr and Ni doping have remarkable effects
44
45 on the EPR spectra as compared to the Co doping. Co-doping deteriorates the EPR signal intensity without any
46
47 significant shift of resonance position in comparison to BFO. This may be due to cobalt‟s high microwave loss
48
49 and large coercivity. The EPR spectra for Ni and Cr doped samples show significant enhancement in the „g‟
50
51 values. This is due to the distinct magnetization of Ni and Cr doped samples. Corresponding g- values (Fig.
ce

52
53 8(a)) in experimental EPR graphs were calculated by the following equation:
54
55 hf = gµBH (1),
56
Ac

57
58 where, h is Planck‟s constant, f is the operating EPR frequency, µB is Bohr magneton for electrons and H is the
59
60 applied external magnetic field. The EPR linewidth is (ΔH epr) associated with the spin-spin relaxation time and

15
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1
2
3 spin-phonon relaxation time. ΔHepr for Cr and Ni-doped BFO are narrower than pristine BFO and Co-doped
4
5 BFO. This suggests that spin-lattice interaction is larger in Cr and Ni-doped samples.
6
7
8 To verify our experimental finding of EPR we have performed theoretical g tensor calculations for BFO based

pt
9
10 perovskites structures by using the GIPAW method. There is no previous evidence of theoretical g-tensors in this
11
material, particularly for the doped cases. Therefore, this is one of our important finding in the present
12
13
investigation. EPR is helpful in identifying effective „g‟ tensor values. In GIPAW method, the g values have

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14
15 been calculated using EPR g tensor (the methodology is given in supplementary sheet), where g values are given
16
17 by, [60],
18
19
20 g= ge + Δg (2)

us
21
22
ge corresponds to the free electron value approximated to 2.0 and Δg is computed using the GIPAW method.
23
24
25 Where Δg= ΔgZ-KE + ΔgSO+ ΔgSOO (3)
26
27
28
29
an
where ΔgZ-KE is the electron Zeeman kinetic energy correction which is a relativistic correction, Δg SO is the spin-

orbit correction and ΔgSOO is the spin other orbit correction.

30
31 It is worth mentioning here that g tensor deviates from its value in vacuum due to the above-mentioned
32
dM
33 correction terms. Like, the spin other orbit correction explains the screening of the external magnetic field ⃗ by
34
35 the induced electronic currents accomplished by unpaired electrons. Unpaired electrons are not at rest and in
36
37 their reference frame; the electric field generated due to the ions and other electrons is Lorentz transformed
38
39 which appear as a magnetic field. The interaction between the spin of unpaired electrons and this magnetic field
40
41 results in the spin-orbit correction ΔgSO..
42
43
pte

ΔgSO can be further subdivided into three parts;

44
45
46 ΔgSO= ΔgSObare + ΔgSOdia + ΔgSOpara (4)
47
48
49 All these terms are carefully evaluated using GIPAW method and explained in the supplementary sheet.
50
The calculated EPR g tensor (in parts per billion) for BFO, Co-doped BFO and Ni-doped BFO is given in
51
ce

52 supplementary sheet (GIPAW type pseudo-potential for Cr is not available so we have not calculated for Cr
53
54 doped BFO). It is clear from the calculations that the major contribution of the Δg comes from the principal
55
56 directions. Therefore, all the tensors are diagonalized using coordinate transformation to get the values in the
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57
58 principal directions only as shown below,
59
60

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1
2
3
4
5
6 BFO (pristine)
7
8

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9 [ ]
10
11
12
13

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14
15 BFCoO (Co doped BFO)
16
17
18
19
20

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21 [ ]
22
23
24
25 BFNO (Ni doped BFO)
26
27
28
29
[
an ]

30
31
32
dM
33
34 Moreover, we have shown the theoretically computed Δg in the principal directions (Δgx, Δgy, and Δgz) in Table
35
36 5.
37
38
Table 5. Calculated and experimental g tensor values of EPR.
39
40
41 Sample | |
42 (Theoretical) (Experimental)
43 BFO -0.033885 -0.036771 -0.039440 0.036698 0.108
pte

44
45 BFCoO -0.1798 -0.2061 -0.2315 0.205838 0.144
46
47
48 BFCrO* - - - - 0.182
49
BFNiO -0.234770 -0.275344 -0.309380 0.273165 0.299
50
51
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52
53
54
55 The change in g tensor both experimentally and theoretically with enhanced magnetization is shown in Fig. 8(b).
56
Ac

57 This may further be explained on the basis of enhanced magnetization as compared to the pristine BFO sample
58
and can be governed by the following equation [61]:
59
60

17
 AUTHOR SUBMITTED MANUSCRIPT - JPCM-114037.R1 Page 18 of 21

1
2
3
| |= | ⃗ ⃗⃗ | (5),
4
5
6
where α is the spin-orbit structure factor, S is the total spin, ⃗ is the spin direction and ⃗⃗ is the total
7
8
magnetization. Eq. 5 shows that with an increase in magnetization (as shown in VSM) Δg increased as shown in

pt
9
10 Fig. 8(b).
11
12
13 Conclusion

cri
14
15
16 In conclusion, we have performed a detailed analysis of the structural and magnetic properties of transition
17
18 metal doped BFO structures. The effect of various transition metals doped BFO has been studied experimentally
19
20 and verified theoretically. All the perovskite structures have been synthesized successfully with pure R3c

us
21
symmetry verified by XRD study. Enhanced magnetization has been observed in doped BFO structures with Ni
22
23
doping shows the highest magnetization. Reduced oxygen vacancy content in Ni-doped structure is verified by
24
25 XPS study. EPR results suggest a strong spin-lattice interaction in Ni and Cr doped samples. The DOS
26
27
28
29
an
calculations of all the optimized structures suggest an R3c symmetry in all four samples and there is no drastic

change in the structure except the lattice parameters and cell volume. The DOS calculations also indicate the
30
31 enhanced magnetic properties in all the doped samples. Tuning of g tensor has been theoretically studied using
32
dM
33 GIPAW calculation. Such a detailed experimental and theoretical study might be helpful in the future prospect
34
35 of multiferroic devices.
36
37
38
39
40 Acknowledgments
41
42 This work is supported by DST-PURSE, DST-AMT, DST-SERB and MHRD-IMPRINT grant of Govt. of India.
43
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44 UGC grant under UPOE-II project is highly acknowledged. One of the authors is highly grateful to UGC for
45
46 providing financial assistance as SRF.
47
48
49 ORCID
50
51
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52 Vinay Sharma https://orcid.org/0000-0003-4735-1003

53
54 Ram Krishna ghosh https://orcid.org/0000-0003-0150-5126
55
56
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57 Bijoy Kumar Kuanr https://orcid.org/0000-0001-9879-0335

58
59
60

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