Abstract
Significant progress has been made in the enhancement of multiferroic properties with possibilities for energy harvesting and storage applications. In this study, BiFeO3 (BFO) thin films were doped with Ca, and the multiferroic, piezoelectric, and energy-storage properties of Bi1−xCaxFeO3−δ (x = 0.3, BCFO) thin films were compared with those of BFO to investigate the effects of the doping. The BCFO thin films were deposited on Pt/TiO2/SiO2/Si substrates using pulsed laser deposition. The BCFO thin films having a polycrystalline structure, exhibited improved crystallinity and larger grains, compared with the BFO thin films. The high crystallinity further resulted in the BCFO thin films exhibiting improved leakage current, ferroelectric, and ferromagnetic characteristics, compared with the BFO thin films. The morphotropic phase boundary formed in the mixed crystal phase, which was driven by the Ca doping, and it improved the piezoelectric coefficients of the BCFO thin films. Additionally, we found that the BCFO thin films have superior energy-storage characteristics, compared with the BFO thin films, owing to the improved ferroelectric properties. Our findings suggest that the Ca doping of the BFO thin films improves their multiferroic properties, piezoelectric response, and energy-storage characteristics.
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References
R. Ramesh, N.A. Spaldin, Multiferroics: progress and prospects in thin films. Nat. Mater. 6, 21–29 (2007)
S. Roy, S.B. Majumder, Recent advances in multiferroic thin films and composites. J. Alloys Compd. 538, 153–159 (2012)
M.M. Vopson, Fundamentals of multiferroic materials and their possible applications. Crit. Rev. Solid State Mater. Sci. 40, 223–250 (2015)
H. Palneedi, V. Annapureddy, S. Priya, J. Ryu, Status and perspectives of multiferroic magnetoelectric composite materials and applications. Actuators 5, 9 (2016)
J. Wu, Z. Fan, D. Xiao, J. Zhu, J. Wang, Multiferroic bismuth ferrite-based materials for multifunctional applications: ceramic bulks, thin films and nanostructures. Prog. Mater. Sci. 84, 335–402 (2016)
N.A. Spaldin, R. Ramesh, Advances in magnetoelectric multiferroics. Nat. Mater. 18, 203–212 (2019)
C.C. Lee, J.M. Wu, Effect of film thickness on interface and electric properties of BiFeO3 thin films. Appl. Surf. Sci. 253, 7069–7073 (2007)
J. Wang, J.B. Neaton, H. Zheng, V. Nagarajan, S.B. Ogale, B. Liu, D. Viehland, V. Vaithyanathan, D.G. Schlom, U.V. Waghmare, N.A. Spaldin, K.M. Rabe, M. Wuttig, R. Ramesh, Epitaxial BiFeO3 multiferroic thin film heterostructures. Science 299, 1719–1722 (2003)
D.C. Arnold, Composition-driven structural phase transitions in rare-earth-doped BiFeO3 ceramics: a review. IEEE Trans. Ultrason. Ferroelectr. Freq. Control 62, 62–82 (2015)
J. Rödel, W. Jo, K.T.P. Seifert, E.-M. Anton, T. Granzow, D. Damjanovic, Perspective on the development of lead-free piezoceramics. J. Am. Ceram. Soc. 92, 1153–1177 (2009)
P. Kharel, S. Talebi, B. Ramachandran, A. Dixit, V.M. Naik, M.B. Sahana, C. Sudakar, R. Naik, M.S.R. Rao, G. Lawes, Structural, magnetic, and electrical studies on polycrystalline transition-metal-doped BiFeO3 thin films. J. Phys. Condens. Matter 21, 036001 (2008)
V. Sharma, R.K. Ghosh, B.K. Kuanr, Investigation of room temperature ferromagnetism in transition metal doped BiFeO3. J. Phys. Condens. Matter 31, 395802 (2019)
H. Yan, H. Deng, N. Ding, J. He, L. Peng, L. Sun, P. Yang, J. Chu, Influence of transition elements doping on structural, optical and magnetic properties of BiFeO3 films fabricated by magnetron sputtering. Mater. Lett. 111, 123–125 (2013)
S. Yang, F. Zhang, X. Xie, X. Guo, L. Zhang, S. Fan, Effects of transition metal (Cu, Zn, Mn) doped on leakage current and ferroelectric properties of BiFeO3 thin films. J. Mater. Sci. Mater. Electron. 28, 14944–14948 (2017)
V.S. Puli, A. Kumar, N. Panwar, I.C. Panwar, R.S. Katiyar, Transition metal modified bulk BiFeO3 with improved magnetization and linear magneto-electric coupling. J. Alloys Compd. 509, 8223–8227 (2011)
Y. Yao, W. Liu, Y. Chan, C. Leung, C. Mak, B. Ploss, Studies of rare-earth-doped BiFeO3 ceramics. Int. J. Appl. Ceram. Technol. 8, 1246–1253 (2011)
S. Karimi, I.M. Reaney, Y. Han, J. Pokorny, I. Sterianou, Crystal chemistry and domain structure of rare-earth doped BiFeO3 ceramics. J. Mater. Sci. 44, 5102–5112 (2009)
P. Suresh, S. Srinath, Study of structure and magnetic properties of rare earth doped BiFeO3. Phys. B Condens. Matter 448, 281–284 (2014)
S.K. Singh, H. Ishiwara, Doping effect of rare-earth ions on electrical properties of BiFeO3 thin films fabricated by chemical solution deposition. Jpn. J. Appl. Phys. 45, 3194–3197 (2006)
S. Hussain, S.K. Hasanain, G.H. Jaffari, N.Z. Ali, M. Siddique, S.I. Shah, Correlation between structure, oxygen content and the multiferroic properties of Sr doped BiFeO3. J. Alloys Compd. 622, 8–16 (2015)
S. Layek, H.C. Verma, A. Garg, Enhancement in magnetic properties of Ba-doped BiFeO3 ceramics by mechanical activation. J. Alloys Compd. 651, 294–301 (2015)
L. Yao, X. Wu, S. Yang, Y. Zhang, Structural and optical properties of Ca doped BiFeO3 thin films prepared by a sol-gel method. Ceram. Int. 43, S470–S473 (2017)
Z. Fu, Z.G. Yin, N.F. Chen, X.W. Zhang, Y.J. Zhao, Y.M. Bai, Y. Chen, H.-H. Wang, X.L. Zhang, J.L. Wu, Tetragonal-tetragonal-monoclinic-rhombohedral transition: strain relaxation of heavily compressed BiFeO3 epitaxial thin films. Appl. Phys. Lett. 104, 052908 (2014)
R.J. Zeches, M.D. Rossell, J.X. Zhang, A.J. Hatt, Q. He, C.-H. Yang, A. Kumar, C.H. Wang, A. Melville, C. Adamo, G. Sheng, Y.-H. Chu, J.F. Ihlefeld, R. Erni, C. Ederer, V. Gopalan, L.Q. Chen, D.G. Schlom, N.A. Spaldin, L.W. Martin, R. Ramesh, A strain-driven morphotropic phase boundary in BiFeO3. Science 326, 977–980 (2009)
X. Yin, C. Chen, Z. Fan, M. Qin, M. Zeng, X. Lu, G. Zhou, X. Gao, D. Chen, J.-M. Liu, Coexistence of multiple morphotropic phase boundaries in strained La-doped BiFeO3 thin films. Mater. Today Phys. 17, 100345 (2021)
P.P. Biswas, S. Pal, V. Subramanian, P. Murugavel, Large photovoltaic response in rare-earth doped BiFeO3 polycrystalline thin films near morphotropic phase boundary composition. Appl. Phys. Lett. 114, 173901 (2019)
C.-J. Cheng, D. Kan, V. Anbusathaiah, I. Takeuchi, V. Nagarajan, Microstructure-electromechanical property correlations in rare-earth-substituted BiFeO3 epitaxial thin films at morphotropic phase boundaries. Appl. Phys. Lett. 97, 212905 (2010)
Y. Yamashita, Large electromechanical coupling factors in perovskite binary material system. Jpn. J. Appl. Phys. 33, 5328–5331 (1994)
M. Ahart, M. Somayazulu, R.E. Cohen, P. Ganesh, P. Dera, H.-K. Mao, R.J. Hemley, Y. Ren, P. Liermann, Z. Wu, Origin of morphotropic phase boundaries in ferroelectrics. Nature 451, 545–548 (2008)
X.-H. Du, J. Zheng, U. Belegundu, K. Uchino, Crystal orientation dependence of piezoelectric properties of lead zirconate titanate near the morphotropic phase boundary. Appl. Phys. Lett. 72, 2421–2423 (1998)
K.-I. Kakimoto, H. Kakemoto, S. Fujita, Y. Masuda, Control of crystal orientation and piezoelectric response of lead zirconate titanate thin films near the morphotropic phase boundary. J. Am. Ceram. Soc. 85, 1019–1021 (2002)
D. Fu, H. Suzuki, T. Ogawa, K. Ishikawa, High-piezoelectric behavior of c-axis-oriented lead zirconate titanate thin films with composition near the morphotropic phase boundary. Appl. Phys. Lett. 80, 3572–3574 (2002)
L.V. Costa, L.S. Rocha, J.A. Cortés, M.A. Ramirez, E. Longo, A.Z. Simões, Enhancement of ferromagnetic and ferroelectric properties in calcium doped BiFeO3 by chemical synthesis. Ceram. Int. 41, 9265–9275 (2015)
W. Xing, Y. Ma, Z. Ma, Y. Bai, J. Chen, S. Zhao, Improved ferroelectric and leakage current properties of Er-doped BiFeO3 thin films derived from structural transformation. Smart Mater. Struct. 23, 085030 (2014)
Y. Han, W. Mao, C. Quan, X. Wang, J. Yang, T. Yang, X.A. Li, W. Huang, Enhancement of magnetic and ferroelectric properties of BiFeO3 by Er and transition element (Mn, Co) co-doping. Mater. Sci. Eng. B 188, 26–30 (2014)
Q. Yun, W. Xing, J. Chen, W. Gao, Y. Bai, S. Zhao, Effect of Ho and Mn co-doping on structural, ferroelectric and ferromagnetic properties of BiFeO3 thin films. Thin Solid Films 584, 103–107 (2015)
S. Riaz, F. Majid, S.M.H. Shah, S. Naseem, Enhanced magnetic and structural properties of Ca doped BiFeO3 thin films. Indian J. Phys. 88, 1037–1044 (2014)
C.H. Yang, J. Seidel, S.Y. Kim, P.B. Rossen, P. Yu, M. Gajek, Y.H. Chu, L.W. Martin, M.B. Holcomb, Q. He, P. Maksymovych, N. Balke, S.V. Kalinin, A.P. Baddorf, S.R. Basu, M.L. Scullin, R. Ramesh, Electric modulation of conduction in multiferroic Ca-doped BiFeO3 films. Nat. Mater. 8, 485–493 (2009)
J.-Z. Huang, Y. Shen, M. Li, C.-W. Nan, Structural transitions and enhanced ferroelectricity in Ca and Mn co-doped BiFeO3 thin films. J. Appl. Phys. 110, 094106 (2011)
L.V. Costa, R.C. Deus, C.R. Foschini, E. Longo, M. Cilense, A.Z. Simões, Experimental evidence of enhanced ferroelectricity in Ca doped BiFeO3. Mater. Chem. Phys. 144, 476–483 (2014)
J. Wu, J. Wang, BiFeO3 thin films of (111)-orientation deposited on SrRuO3 buffered Pt/TiO2/SiO2/Si(100) substrates. Acta Mater. 58, 1688–1697 (2010)
F.L. McCrackin, E. Passaglia, R.R. Stromberg, H.L. Steinberg, Measurement of the thickness and refractive index of very thin films and the optical properties of surfaces by ellipsometry. J. Res. Natl. Bur. Stand. A Phys. Chem. 67A, 363–377 (1963)
F.-C. Chiu, A review on conduction mechanisms in dielectric films. Adv. Mater. Sci. Eng. 2014, 578168 (2014)
H. Zhang, R. Jia, Y. Lei, X. Tang, Y. Zhang, Y. Zhang, Leakage current conduction mechanisms and electrical properties of atomic-layer-deposited HfO2/Ga2O3 MOS capacitors. J. Phys. D Appl. Phys. 51, 075104 (2018)
T. Mihara, H. Watanabe, Electronic conduction characteristics of sol-gel ferroelectric Pb(Zr0.4Ti0.6)O3 thin-film capacitors: Part I. Jpn. J. Appl. Phys. 34, 5664–5673 (1995)
J. Sun, X.J. Zheng, W. Yin, M.H. Tang, W. Li, Space-charge-limited leakage current in high dielectric constant and ferroelectric thin films considering the field-dependent permittivity. Appl. Phys. Lett. 97, 242905 (2010)
K. Abe, N. Sakai, J. Takahashi, H. Itoh, N. Adachi, T. Ota, Leakage current properties of cation-substituted BiFeO3 ceramics. Jpn. J. Appl. Phys. 49, 09MB01 (2010)
Y. Ahn, J. Seo, D. Lim, J.Y. Son, Ferroelectric domain structures and polarization switching characteristics of polycrystalline BiFeO3 thin films on glass substrates. Curr. Appl. Phys. 15, 584–587 (2015)
C.H.P.L.H. Bennett, L.J. Swartzendruber, Comments on units in magnetism. J. Res. Natl. Bur. Stand. 83, 9–12 (1978)
G. Catalan, J.F. Scott, A. Schilling, J.M. Gregg, Wall thickness dependence of the scaling law for ferroic stripe domains. J. Phys. Condens. Matter 19, 022201 (2006)
G. Catalan, H. Béa, S. Fusil, M. Bibes, P. Paruch, A. Barthélémy, J.F. Scott, Fractal dimension and size scaling of domains in thin films of multiferroic BiFeO3. Rhys. Rev. Lett. 100, 027602 (2008)
J.Y. Son, S. Song, J.-H. Lee, H.M. Jang, Anomalous domain periodicity observed in ferroelectric PbTiO3 nanodots having 180° stripe domains. Sci. Rep. 6, 26644 (2016)
J. Wang, H. Zheng, Z. Ma, S. Prasertchoung, M. Wuttig, R. Droopad, J. Yu, K. Eisenbeiser, R. Ramesh, Epitaxial BiFeO3 thin films on Si. Appl. Phys. Lett. 85, 2574–2576 (2004)
L. You, N.T. Chua, K. Yao, L. Chen, J. Wang, Influence of oxygen pressure on the ferroelectric properties of epitaxial BiFeO3 thin films by pulsed laser deposition. Phys. Rev. B 80, 024105 (2009)
Y.K. Kim, S.S. Kim, H. Shin, S. Baik, Thickness effect of ferroelectric domain switching in epitaxial PbTiO3 thin films on Pt(001)/MgO(001). Appl. Phys. Lett. 84, 5085–5087 (2004)
K. Zou, Y. Dan, H. Xu, Q. Zhang, Y. Lu, H. Huang, Y. He, Recent advances in lead-free dielectric materials for energy storage. Mater. Res. Bull. 113, 190–201 (2019)
Y. Zhang, L. Bellaiche, B. Xu, Ultrahigh energy storage density in lead-free antiferroelectric rare-earth-substituted bismuth ferrite. Phys. Rev. Mater. 6, L051401 (2022)
H. Pan, Y. Zeng, Y. Shen, Y.-H. Lin, J. Ma, L. Li, C.-W. Nan, BiFeO3–SrTiO3 thin film as a new lead-free relaxor-ferroelectric capacitor with ultrahigh energy storage performance. J. Mater. Chem. A 5, 5920–5926 (2017)
H. Pan, Y. Zeng, Y. Shen, Y.-H. Lin, C.-W. Nan, Thickness-dependent dielectric and energy storage properties of (Pb0.96La0.04)(Zr0.98Ti0.02)O3 antiferroelectric thin films. J. Appl. Phys. 119, 124106 (2016)
N.D. Quan, N.V. Hong, T.Q. Toan, V.N. Hung, Enhanced ferroelectric properties and energy storage density in PLZT/BNKT heterolayered thin films prepared by sol-gel method. Eur. Phys. J. B 91, 316 (2018)
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This work was supported by National Research Foundation of Korea (NRF) Grants funded by the Korean Government (NRF-2021R1F1A1048693 and NRF-2019R1A2C1010927).
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Ahn, Y., Son, J.Y. Multiferroic and energy-storage characteristics of polycrystalline Ca-doped BiFeO3 thin films on Si substrates. J. Korean Ceram. Soc. 60, 301–309 (2023). https://doi.org/10.1007/s43207-022-00265-2
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DOI: https://doi.org/10.1007/s43207-022-00265-2