Abstract
The present work reports the influence of Lanthanum (La) substitution on the structural, optical, electrical, and magnetic properties of bismuth ferrite (BiFeO3) nanoparticles (NPs). The compositions of Bi1−xLaxFeO3 (0% < x < 20%) NPs, with 5% Bi-excess, were synthesized through sol–gel conventional route. The XRD results suggest the formation of rhombohedral perovskite structure (R3c space group) along with a minor secondary phase. The crystallite size calculated from XRD and FESEM was observed to decrease from 60.0 to 40.0 nm with an increase in La content. The bandgap calculated using UV–Vis spectroscopy was found to decrease with La doping, and PL spectroscopy infers formation of defects in La–BFO NPs. The P–E loop studies reveal that La-doped BFO exhibits ferroelectric behavior at room temperature. The various parameters such as spontaneous polarization, dielectric constant, and distribution parameter of relaxation time measured from the electrical investigation were found to increase up to 5% La doping BFO then start decreasing with further increase in the La content in BFO. The impedance spectra of La–BFO was fitted using the theory of Cole–Cole with R(C(R(QR)))(CR) model. It is observed that La-concentration above 5% generates excess space charge which might cross the threshold to start conduction resulting in degrading of multiferroic properties. The DC magnetization study revealed the ferromagnetic behavior of the samples at room temperature. It is observed that La substitution affects the shape of the magnetization hysteresis curve beyond 5% La-concentration, and transforming it to a neck-like formation providing evidence for the spin-canting effect in the samples. These results make La-doped BiFeO3 NPs a propitious candidate for the multiferroic applications like high-density data storage devices and supercapacitors.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abramov AS, Alikin DO, Yuzhakov VV et al (2019) Indentation induced local polarization reversal in La-doped BiFeO3 ceramics. Ferroelectrics 541:1–9. https://doi.org/10.1080/00150193.2019.1574634
Ahmad T, Jindal K, Tomar M et al (2021) Role of charge states and dopant site in governing electronic properties of Cr doped BiFeO3. Mater Chem Phys 263:124438. https://doi.org/10.1016/j.matchemphys.2021.124438
Arya A, Sharma AL (2018) Structural, electrical properties and dielectric relaxation in Na + ion conducting solid polymer electrolyte. J Phys Condens Matter 30:165402. https://doi.org/10.1088/1361-648X/aab466
Ates M, Sarac AS (2009) Capacitive behavior of polycarbazole- and poly (N-vinylcarbazole)-coated carbon fiber microelectrodes in various solutions. J Appl Electrochem 39:2043–2048. https://doi.org/10.1007/s10800-009-9882-6
Batoo KM, Kumar S, Lee CG (2009) Finite size effect and influence of temperature on electrical properties of nanocrystalline Ni–Cd ferrites. Curr Appl Phys 9:1072–1078. https://doi.org/10.1016/j.cap.2008.12.002
Bennett LH, Della TE (2005) Analysis of wasp-waist hysteresis loops. J Appl Phys 97:10E502. https://doi.org/10.1063/1.1846171
Burduhos-Nergis D-P, Vizureanu P, Sandu AV, Bejinariu C (2020) Evaluation of the corrosion resistance of phosphate coatings deposited on the surface of the carbon steel used for carabiners manufacturing. Appl Sci 10:2753. https://doi.org/10.3390/app10082753
Camayo CE, Gaona JS, Raigoza CFV (2021) Effect of La and Pr substitution on structure and magnetic properties of Pechini synthesized BiFeO3. J Magn Magn Mater 527:167733. https://doi.org/10.1016/j.jmmm.2021.167733
Carranza-Celis D, Cardona-Rodríguez A, Narváez J et al (2019) Control of multiferroic properties in BiFeO3 nanoparticles. Sci Rep 9:1–9. https://doi.org/10.1038/s41598-019-39517-3
Channei D, Inceesungvorn B, Wetchakun N et al (2014) Photocatalytic degradation of methyl orange by CeO2 and Fe-doped CeO2 films under visible light irradiation. Sci Rep. https://doi.org/10.1038/srep05757
Choe H, Lee H, Ismail MA, Hussin MW (2015) Evaluation of electrochemical impedance properties of anti- corrosion films by arc thermal metal spraying method. Int J Electrochem Sci 10:9775–9789
Coondoo I, Panwar N, Rafiq MA et al (2014) Structural, dielectric and impedance spectroscopy studies in (Bi0.90R0.10)Fe0.95Sc0.05O3 [R = La, Nd] ceramics. Ceram Int 40:9895–9902. https://doi.org/10.1016/j.ceramint.2014.02.084
Dai W, Li Y, Jia C et al (2020) High-performance ferroelectric non-volatile memory based on La-doped BiFeO3 thin films. RSC Adv 10:18039–18043. https://doi.org/10.1039/d0ra02780d
Dong G, Fan H, Cheng Z, Zhang S (2020) Enhanced magnetic performance of BiFeO3 by cerium substitution. Ceram Int 46:26205–26209. https://doi.org/10.1016/j.ceramint.2020.06.306
Elliott SR (1987) A. c. conduction in amorphous chalcogenide and pnictide semiconductors. Adv Phys 36:135–217. https://doi.org/10.1080/00018738700101971
Faia PM, Furtado CS, Ferreira AJ (2005) AC impedance spectroscopy: a new equivalent circuit for titania thick film humidity sensors. Sens Actuators B 107:353–359. https://doi.org/10.1016/j.snb.2004.10.021
Farea AMM, Kumar S, Batoo KM et al (2008) Structure and electrical properties of Co0.5CdxFe2.5−xO4 ferrites. J Alloys Compd 464:361–369. https://doi.org/10.1016/j.jallcom.2007.09.126
Feldman Y, Puzenko A, Ryabov Y (2006) Fractals, diffusion, and relaxation in disordered complex systems. In: Feldman Y (ed) A special volume of advances in chemical physics, chapter 1, vol 133. Wiley, pp 1–126. https://doi.org/10.1002/0471790265.ch
Fujino S, Murakami M, Anbusathaiah V et al (2008) Combinatorial discovery of a lead-free morphotropic phase boundary in a thin-film piezoelectric perovskite. Appl Phys Lett 92:202904. https://doi.org/10.1063/1.2931706
Gao R, Qin X, Wu H et al (2019) Effect of Ti doping on the dielectric, ferroelectric and magnetic properties of Bi0.86La0.08Sm0.14FeO3 ceramics. Mater Res Express 6:106317. https://doi.org/10.1088/2053-1591/ab3fee
Ge W, Rahman A, Cheng H et al (2018) Probing the role of cation vacancies on the ferromagnetism of La-doped BiFeO3 ceramics. J Magn Magn Mater 449:401–405. https://doi.org/10.1016/j.jmmm.2017.10.082
Ghosh A, Trujillo DP, Choi H et al (2019) Electronic and magnetic properties of lanthanum and strontium doped bismuth ferrite: a first-principles study. Sci Rep 9:1–10. https://doi.org/10.1038/s41598-018-37339-3
Gupta S, Tomar M, Gupta V (2014) Enhanced magnetic and electric properties of nanocrystalline Ce modified BFO thin films. Ferroelectrics 470:272–279. https://doi.org/10.1080/00150193.2014.923735
Hatt AJ, Spaldin NA, Ederer C (2010) Strain-induced isosymmetric phase transition in BiFeO3. Phys Rev B 81:054109. https://doi.org/10.1103/PhysRevB.81.054109
Havriliak S, Negami S (1966) A complex plane analysis of a-dispersions in some polymer systems. J Polym Sci Part C 14:99–117. https://doi.org/10.1002/polc.5070140111
Heikes RR, Johnston WD (1957) Mechanism of conduction in Li substituted transition metal oxides. J Chem Phys 26:582–587. https://doi.org/10.1063/1.1743350
Hussain S, Khan FA, Hasanain SK et al (2018) Investigation of dielectric and complex impedance spectroscopic studies of Bi1−xBaxFeO3 (0 ≤ x ≤ 0.30) system. J Mater Sci Mater Electron. https://doi.org/10.1007/s10854-018-8842-5
Irvine BJTS, Sinclair DC, West AR (1990) Electroceramics: characterization by impedance spectroscopy. Adv Mater 2:132–138. https://doi.org/10.1002/adma.19900020304
Jesús FS-D, Bolarín-Miró AM, Cortés-Escobedo CA et al (2020) Enhanced ferromagnetic and electric properties of multiferroic BiFeO3 by doping with Ca. J Alloys Compd. https://doi.org/10.1016/j.jallcom.2020.153944
Koops CG (1951) On the dispersion of resistivity and dielectric constant of some semiconductors at audiofrequencies. Phys Rev 83:1–4
Kumar A, Varshney D (2012) Crystal structure refinement of Bi1−xNdxOFeO3 multiferroic by the Rietveld method. Ceram Int 38:3935–3942. https://doi.org/10.1016/j.ceramint.2012.01.046
Kumar S, Alimuddin A, Kumar R et al (2007) Electrical transport, magnetic, and electronic structure studies of Mg0.95Mn0.05Fe2−2xTi2xO4 ± δ (0 < x < 05) ferrites. J Phys Condens Matter 19:476210. https://doi.org/10.1088/0953-8984/19/47/476210
Kumar P, Panda C, Kar M (2015) Effect of rhombohedral to orthorhombic transition on magnetic and dielectric properties of La and Ti co-substituted BiFeO3. Smart Mater Struct 24:045028. https://doi.org/10.1088/0964-1726/24/4/045028
Kumari K, Naji R, Katharria YS et al (2019) Study the contribution of surface defects on the structural, electronic structural, magnetic, and photocatalyst properties of Fe: CeO2 nanoparticles. J Electron Spectros Relat Phenomena 235:29–39. https://doi.org/10.1016/j.elspec.2019.06.004
Kumari K, Naji R, Chawla AK et al (2020) Engineering the optical properties of Cu doped CeO2 NCs for application in white LED. Ceram Int 46:7482–7488. https://doi.org/10.1016/j.ceramint.2019.11.246
Lima AF (2020) Optical properties, energy band gap and the charge carriers’ effective masses of the R3c BiFeO3 magnetoelectric compound. J Phys Chem Solids 144:109484. https://doi.org/10.1016/j.jpcs.2020.109484
Makosz JJ, Urbanowicz P (2002) Relaxation and resonance absorption in dielectrics. Zeitschrift für Naturforsch A 57:119–125. https://doi.org/10.1515/zna-2002-3-402
Maria Č, Zagorac D, Batalovi K et al (2017) BiFeO3 perovskites: a multidisciplinary approach to multiferroics. Ceram Int 43:1256–1264. https://doi.org/10.1016/j.ceramint.2016.10.074
Martínez-Aguilar E, Hmok H, Siqueiros JM (2019) Effect of la doping on the ferroelectric and optical properties of BiFeO3: a theoretical-experimental study. Mater Res Express. https://doi.org/10.1088/2053-1591/aafd60
Matin MA, Hossain MN, Ali MA et al (2019) Enhanced dielectric properties of prospective Bi0.85Gd0.15Fe1−xCrxO3 multiferroics. Results Phys 12:1653–1659. https://doi.org/10.1016/j.rinp.2019.01.079
Meng J, Chen K, Mijiti Y et al (2019) Charge-transfer-induced interfacial exchange coupling at the Co/BiFeO3 interface. Phys Rev Appl 12:044010. https://doi.org/10.1103/PhysRevApplied.12.044010
Miao JH, Fang TT, Chung HY, Yang CW (2009) Effect of la doping on the phase conversion, microstructure change, and electrical properties of Bi2Fe4O9 ceramics. J Am Ceram Soc 92:2762–2764. https://doi.org/10.1111/j.1551-2916.2009.03238.x
Morales MP, Serna CJ, Bødker F, Mørup S (1997) Spin canting due to structural disorder in maghemite. J Phys Condens Matter 9:5461–5467
Moubah R, Schmerber G, Rousseau O et al (2012) Photoluminescence investigation of defects and optical band gap in multiferroic BiFeO3 single crystals. Appl Phys Express 5:035802. https://doi.org/10.1143/APEX.5.035802
Naji R, Rahman F, Batoo KM (2014) Effect of grain size and grain boundary defects on electrical and magnetic properties of Cr doped ZnO nanoparticles. J Mol Struct 1065–1066:199–204. https://doi.org/10.1016/j.molstruc.2014.02.056
Pandey DK, Modi A, Pandey P, Gaur NK (2017) Variable excitation wavelength photoluminescence response and optical absorption in BiFeO3 nanostructures. J Mater Sci Mater Electron 017:7655. https://doi.org/10.1007/s10854-017-7655-2
Pattnaik SP, Behera A, Martha S et al (2018) Synthesis, photoelectrochemical properties and solar light-induced photocatalytic activity of bismuth ferrite nanoparticles. J Nanopart Res 20:1–15. https://doi.org/10.1007/s11051-017-4110-5
Pedro-García F, Sánchez-De Jesús F, Bolarín-Miró AM et al (2021) Magnetodielectric coupling tuning through domain wall charge accumulation in co-doped BiFeO3 with Sr2+ and Mn3+. J Alloys Compd. https://doi.org/10.1016/j.jallcom.2020.157549
Psarras GC (2018) Fundamentals of dielectric theories. William Andrew Publishing
Puhan A, Nayak AK, Bhushan B et al (2019) Enhanced electrical, magnetic and optical behaviour of Cr doped Bi0.98Ho0.02FeO3 nanoparticles. J Alloys Compd 796:229–236. https://doi.org/10.1016/j.jallcom.2019.05.025
Ranjith KS, Saravanan P, Chen S-H et al (2014) Enhanced room-temperature ferromagnetism on Co-doped CeO2 nanoparticles: mechanism and electronic and optical properties. J Phys Chem C 118:27039–27047. https://doi.org/10.1021/jp505175t
Rao TD, Karthik T, Asthana S (2013) Investigation of structural, magnetic and optical properties of rare earth substituted bismuth ferrite. J Rare Earths 31:370–375. https://doi.org/10.1016/S1002-0721(12)60288-9
Satpathy SK, Mohanty NK, Behera AK, et al (2014) Effect of electrical properties on Gd modified BiFeO3–PbZrO3. arXiv:1405.0104
Seidel J, Maksymovych P, Batra Y et al (2010) Domain wall conductivity in La-doped BiFeO3. Phys Rev Lett 105:197603. https://doi.org/10.1103/PhysRevLett.105.197603
Sinha AK, Bhushan B, Jagannath J et al (2019) Enhanced dielectric, magnetic and optical properties of Cr-doped BiFeO3 multiferroic nanoparticles synthesized by sol–gel route. Results Phys 13:102299. https://doi.org/10.1016/j.rinp.2019.102299
Soni S, Vats VS, Kumar S et al (2018) Structural, optical and magnetic properties of Fe-doped—CeO2 samples probed using X-ray photoelectron spectroscopy. J Mater Sci Mater Electron 29:10141–10153. https://doi.org/10.1007/s10854-018-9060-x
Spaldin NA, Ramesh R (2019) Advances in magnetoelectric multiferroics. Nat Mater. https://doi.org/10.1038/s41563-018-0275-2
Tamura R, Lim E, Manaka T, Iwamoto M (2006) Analysis of pentacene field effect transistor as a Maxwell–Wagner effect element. J Appl Phys 100:114515. https://doi.org/10.1063/1.2372433
Wang N, Luo X, Han L et al (2020) Structure, performance, and application of BiFeO3 nanomaterials. Nano Micro Lett 12:81. https://doi.org/10.1007/s40820-020-00420-6
Wei Y, Sridhar S (1993) A new graphical representation for dielectric data. J Chem Phys 99:3119. https://doi.org/10.1063/1.465165
Yan X, Tan G, Liu W et al (2015) Studies on structural, electrical and magnetic properties of Dy-doped BiFeO 3 thin films. J Mater Sci Mater Electron 26:6232–6239. https://doi.org/10.1007/s10854-015-3208-8
You L, Caesario P, Fang L et al (2014) Effect of lanthanum doping on tetragonal-like BiFeO3 with mixed-phase domain structures. Phys Rev B 90:134110. https://doi.org/10.1103/PhysRevB.90.134110
Yuan P, Li D, Wu L, Shi L (2020) Synthesis and growth mechanism of monodispersed BiFeO3 nanorods with controllable aspect ratio and magnetic/optical properties. Ceram Int 46:1243–1247. https://doi.org/10.1016/j.ceramint.2019.09.060
Acknowledgements
One of the authors (Shalendra Kumar) is grateful to UGC-DAE Consortium for Scientific Research for financial support through project CSR-IC-MSRSR-08/CSR-216/2017-18/1297.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Kumari, A., Kumari, K., Aljawfi, R.N. et al. Role of La substitution on structural, optical, and multiferroic properties of BiFeO3 nanoparticles. Appl Nanosci 13, 3161–3180 (2023). https://doi.org/10.1007/s13204-021-01844-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13204-021-01844-1