Abstract
The films of (Bi0.5Na0.5)(Ti1-xMnx)O3-δ (BNTMx) were deposited on the substrates via the sol–gel method. The influence of the doping content of Mn on the microstructures and ferroelectric properties of the films were investigated. In addition, the valence states of Mn ions were analyzed. The results show that Mn ions have dissolved into the lattice of Bi0.5Na0.5TiO3 (BNT) without forming any secondary phase. When the doping content of Mn is 0.04, the film of BNTMx possesses a dense microstructure, maximum of remnant polarization (20.2 µC·cm−2), minimum value of leakage current density (3.31 × 10–5 A· cm−2), which shows good ferroelectric property and insulation performance. The results of XPS indicate that Mn ions exist in form of Mn2+, Mn3+ and Mn4+. The ratio of the amount of Mn4+ to that of Mn3+ and Mn2+ is 5.5:1. In this work, relationship between valence states of Mn ions and leakage current densities or ferroelectric property of the films were investigated in detail. The results will provide a new way for future applications of BNT-based multi-functional devices and an alternative for environmental-friendly ferroelectric materials.
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10854-021-05435-2/MediaObjects/10854_2021_5435_Fig1_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10854-021-05435-2/MediaObjects/10854_2021_5435_Fig2_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10854-021-05435-2/MediaObjects/10854_2021_5435_Fig3_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10854-021-05435-2/MediaObjects/10854_2021_5435_Fig4_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10854-021-05435-2/MediaObjects/10854_2021_5435_Fig5_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10854-021-05435-2/MediaObjects/10854_2021_5435_Fig6_HTML.png)
Similar content being viewed by others
References
G.T. Hwang, V. Annapureddy, J.H. Han, D.J. Joe, C. Baek, D.Y. Park, D.H. Kim, J.H. Park, C.K. Jeong, K.I. Park, J.J. Choi, D.K. Kim, J. Ryu, K.J. Lee, Self-powered wireless sensor node enabled by an aerosol-deposited PZT flexible energy harvester. Adv. Energy Mater. 6, 1600237 (2016)
X. Gao, J. Wu, Y. Yu, Z. Chu, H. Shi, S. Dong, Giant piezoelectric coefficients in relaxor piezoelectric ceramic PNN-PZT for vibration energy harvesting. Adv. Funct. Mater. 28, 1706895 (2018)
Y. Zhang, M. Xie, J. Roscow, Y. Bao, K. Zhou, D. Zhang, C.R. Bowen, Enhanced pyroelectric and piezoelectric properties of PZT with aligned porosity for energy harvesting applications. J. Mater. Chem. A 5, 6569–6580 (2017)
A. Datta, D. Mukherjee, S. Witanachchi, P. Mukherjee, Hierarchically ordered nano-heterostructured PZT thin films with enhanced ferroelectric properties. Adv. Funct. Mater. 24, 2638–2647 (2014)
M. Davies, E. Aksel, J.L. Jones, Enhanced high-temperature piezoelectric coefficients and thermal stability of Fe- and Mn-substituted Na0.5Bi0.5TiO3 Ceramics. J. Am. Ceram. Soc. 94, 1314–1316 (2011)
M. Tyagi, M. Kumari, R. Chatterjee, P. Sharma, Large magnetoelectric response in modified BNT based ternary piezoelectric [72.5(Bi1/2Na1/2TiO3)- 22.5(Bi1/2K1/2TiO3)-5(BiMg1/2Ti1/2O3)]-magnetostrictive (NiFe2O4) particulate (0–3) composites. Appl. Phys. Lett. 106, 202904 (2015)
Y.M. Liu, Y.J. Wang, M.J. Chow, N.Q. Chen, F.Y. Ma, Y.H. Zhang, J.Y. Li, Glucose suppresses biological ferroelectricity in aortic elastin. Phys. Rev. Lett. 110, 168101 (2013)
V.S. Bystrov, E. Paramonova, I. Bdikin, S. Kopyl, A. Heredia, R.C. Pullar, A.L. Kholkin, Bioferroelectricity: diphenylalanine peptide nanotubes computational modeling and ferroelectric properties at the nanoscale. Ferroelectrics 440, 3–24 (2012)
J.J. Zhu, J.Z. Zhang, K. Jiang, H.W. Zhang, Z.G. Hu, H.S. Luo, J.H. Chu, Coexistence of ferroelectric phases and phonon dynamics in relaxor ferroelectric Na0.5Bi0.5TiO3 based single crystals. J. Am. Ceram. Soc. 99, 2408–2414 (2016)
X. Jia, J. Zhang, Y. Gao et al., Enhanced bipolar fatigue-resistance and optical temperature sensing in Er-modified 0.94(Bi0.5Na0.5)TiO3–0.06(K0.5Na0.5)NbO3 lead-free ceramics. Mater. Res. Bull. 89, 11–15 (2017)
B. Sun, P. Han, W.X. Zhao, Y.H. Liu, P. Chen, White-light-controlled magnetic and ferroelectric properties in multiferroic BiFeO3 square nanosheets. J. Phys. Chem. C 118, 18814–18819 (2014)
L.J. Wei, B. Sun, W.X. Zhao, H.W. Li, P. Chen, Light regulated I-V hysteresis loop of Ag/BiFeO3/FTO thin film. Appl. Surf. Sci. 393, 325–329 (2017)
P.P. Zheng, B. Sun, Y.Z. Chen et al., Photo-induced negative differential resistance in a resistive switching memory device based on BiFeO3/ZnO heterojunctions. Appl. Mater. Today. 14, 21–28 (2019)
W. Sakamoto, N. Makino, B.Y. Lee, T. Iijima, M. Moriya, T. Yogo, Influence of volatile element composition and Mn doping on the electrical properties of lead-free piezoelectric (Bi0.5Na0.5)TiO3 thin films. Sensor. Actuat. A: Phys. 200, 60–67 (2013)
J. Chen, Z. Tang, R. Tan, Y. Bai, S. Zhao, H. Zhang, Domain switching contribution to the ferroelectric, fatigue and piezoelectric properties of lead-free Bi0.5(Na0.85K0.15)0.5TiO3 films. RSC Adv. 6, 33834–33842 (2016)
B.N. Rao, R. Datta, S.S. Chandrashekaran et al., Local Structural Disorder and Its Influence on the Average Global Structure and Polar Properties in Na0.5Bi0.5TiO3 (Rev. B, Phys, 2013). https://doi.org/10.1103/PhysRevB.88.224103
E. Birks, M. Dunce, R. Ignatans et al., Structure and dielectric properties of Na0.5Bi0.5TiO3-CaTiO3 solid solutions. J. Appl. Phys. 119, 074102 (2016)
Z.G. Gao, Z.R. Jia, K.K. Wang, X.H. Liua, L. Bi, G.L. Wu, Simultaneous enhancement of recoverable energy density and efficiency of lead-free relaxor-ferroelectric BNT-based ceramics. Chem. Eng. J. 402, 125951 (2020)
M.S. Mirshekarloo, L. Zhang, K. Yao, T. Sritharan, Electromechanical properties and fatigue of antiferroelectric (Pb, La)(Zr, Sn, Ti)O3 thin film cantilevers fabricated by micromachining. Sensor. Actuat. A: Phys. 187, 127–131 (2012)
S.A. Dargham, F. Ponchel, N. Abboud, M. Soueidan, A. Ferry, R. Desfeux, J. Assaad, D. Remiens, D. Zaouk, Synthesis and electrical properties of lead-free piezoelectric Bi0.5Na0.5TiO3 thin films prepared by sol-gel method. J. Eur. Ceram. Soc. 38, 1450–1455 (2018)
M. Bousquet, J.R. Duclère, C. Champeaux, A. Boulle, P. Marchet, A. Catherinot, A. Wu, P.M. Vilarinho, S. Députier, M. Guilloux-Viry, A. Crunteanu, B. Gautier, D. Albertini, C. Bachelet, Macroscopic and nanoscale electrical properties of pulsed laser deposited (100) epitaxial lead-free Na0.5Bi0.5TiO3 thin films. J. Appl. Phys. 107, 034102 (2010)
R. Ding, D. Wang, D. Chu, S. Li, Crystallographic orientation dependence on electrical properties of (Bi, Na)TiO3-based thin films. J. Am. Ceram. Soc. 96, 3530–3535 (2013)
Z.S. Xu, X.H. Hao, An, Structure and dielectric properties of (Na0.5Bi0.5)TiO3-SrTiO3 thick films derived from polyvinylpyrrolidone-modified chemical solution. J. Mater. Sci. Mater. Electron. 26, 4318–4324 (2015)
C.C. Diao, C.F. Yang, J.J. Lin, Crystallization and electrical characteristics of 0.95(Na0.5Bi0.5)TiO3–0.05BaTiO3 thin films under different annealing temperature and atmosphere. J. Nanosci. Nanotechnol. 11, 10562–10566 (2011)
M. Zannen, M. Dietze, H. Khemakhem, M. Es-Souni, Ferroelectric (Na1/2Bi1/2)TiO3 thin films showing photoluminescence properties. Appl. Phys. A 117, 1485–1490 (2014)
S.K. Acharya, B.G. Ahn, C.U. Jung, J.H. Koh, I.H. Choi, S.K. Lee, Effect of Rb doping on ferroelectric and piezoelectric properties of Bi0.5Na0.5TiO3-BaTiO3 thin films. J. Alloy. Compd. 603, 248–254 (2014)
C.H. Yang, Y.J. Han, X.S. Sun, J. Chen, J. Qian, L.X. Chen, Effects of Nd3+-substitution for Bi-site on the leakage current, ferroelectric and dielectric properties of Na0. 5Bi0. 5TiO3 thin films. Ceram. Int. 44, 6330–6336 (2018)
M. Zannen, H. Khemakhem, A. Kabadou, M. Es-Souni, Structural, Raman and electrical studies of 2 at. % Dy-doped NBT. J. Alloy. Compd. 555, 56–61 (2013)
W. Huang, S. He, A. Hao, N. Qin, M. Ismail, J. Wu, D. Bao, Structural phase transition, electrical and photoluminescent properties of Pr3+-doped (1–x)Na0.5Bi0.5TiO3-xSrTiO3 lead-free ferroelectric thin films. J. Eur. Ceram. Soc. 38, 2328–2334 (2018)
F.J. Geng, C.H. Yang, P.P. Lv et al., Effects of Zn2+ doping content on the structure and dielectric tunability of non-stoichiometric [(Na0.7K0.2Li0.1)0.45Bi0.55]TiO3+δ thin film. J. Mater. Sci.: Mater Electron. 27, 2195–2200 (2016)
J. Qian, C.H. Yang, Y.J. Han, X.Q. Hu, S.X. Li, F.Y. Jiao, X.B. Du, The crystallization and dielectric tunability of Zn doped Na0.5Bi0.5TiO3 thin films. Ceram. Int. 42, 976–981 (2016)
J. Wang, Y. Li, N. Sun, Q. Zhang, L. Zhang, X. Hao, X. Chou, Effects of Fe3+ doping on electrical properties and energy-storage performances of the (Na0.85K0.15)0.5Bi0.5TiO3 thick films prepared by sol-gel method. J. Alloy. Compd. 727, 596–602 (2017)
Effect of precursor solution concentration, J. Q. Sun, C. H. Yang, J. H. Song, Y. Y. Zhou, Q. Yao, X. S. Sun, The microstructure, ferroelectric and dielectric behaviors of Na0.5Bi0.5(Ti, Fe)O3 thin films synthesized by chemical solution deposition. Ceram. Int. 43, 2033–2038 (2017)
D. Do, J.W. Kim, S.S. Kim, Effects of Dy and Mn co-doping on ferroelectric properties of BiFeO3 thin films. J. Am. Ceram. Soc. 94, 2792–2795 (2011)
Y.Z. Wang, R.R. Liu, J. Qian, X.S. Sun, Y.J. Han, C.H. Yang, Reduced leakage current, enhanced ferroelectric and dielectric properties in Mn-doped BiFeO3 thin film composited with TiO2 layers. Ceram. Int. 45, 12285–12289 (2019)
Y. Shuai, S. Zhou, D. Bürger, H. Reuther, I. Skorupa, V. John, M. Helm, H. Schmidt, Decisive role of oxygen vacancy in ferroelectric versus ferromagnetic Mn-doped BaTiO3 thin films. J. Appl. Phys. 109, 084105 (2011)
W. Xu, X. Li, Q. Li, Q. Deng, J.Z. Zhang, K. Jiang, J. Chu, Spectroscopic study of phase transitions in ferroelectric Bi0.5Na0.5Ti1-xMnxO3-δ films with enhanced ferroelectricity and energy storage ability. J. Alloy. Compd. 768, 377–386 (2018)
Y. Wu, X. Wang, C. Zhong, L. Li, Effect of Mn doping on microstructure and electrical properties of the (Na0.85K0.15)0.5Bi0.5TiO3 thin films prepared by sol-gel method. J. Am. Ceram. Soc. 94, 3877–3882 (2011)
C.C. Jin, F.F. Wang, C.M. Leung, Q.R. Yao, Y.X. Tang, T. Wang, W.Z. Shi, Enhanced ferroelectric and piezoelectric response in Mn-doped Bi0.5Na0.5TiO3-BaTiO3 lead-free film by pulsed laser deposition. Appl. Surf. Sci. 283, 348–351 (2013)
Y. Guo, H. Fan, C. Long, J. Shi, L. Yang, S. Lei, Electromechanical and electrical properties of Bi0.5Na0.5Ti1−xMnxO3−δ ceramics with high remnant polarization. J. Alloy. Compd. 610, 189–195 (2014)
M.K. Niranjan, T. Karthik, S. Asthana, J. Pan, U.V. Waghmare, Theoretical and experimental investigation of Raman modes, ferroelectric and dielectric properties of relaxor Na0.5Bi0.5TiO3. J. Appl. Phys. 113, 194106 (2013)
H. Lidjici, B. Lagoun, M. Berrahal, M. Rguitti, M.A. Hentatti, H. Khemakhem, XRD, Raman and electrical studies on the (1–x)(Na0.5Bi0.5)TiO3-xBaTiO3 lead free ceramics. J. Alloy. Compd. 618, 643–648 (2015)
J. Suchanicz, I.J. Sumara, T.V. Kruzina, Raman and infrared spectroscopy of Na0.5Bi0.5TiO3-BaTiO3 ceramics. J. Electroceram. 27, 45–50 (2011)
Y.Y. Wu, X.H. Wang, C.F. Zhong, L.T. Li, Effect of Na/K excess on the electrical properties of Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3 thin films prepared by sol-gel processing. Thin Solid Films 519, 4798–4803 (2011)
I.G. Siny, E. Husson, J.M. Beny, S.G. Lushnikov, E.A. Rogacheva, P.P. Syrnikov, Raman scattering in the relaxor-type ferroelectric Na1/2Bi1/2TiO3. Ferroelectrics 248, 57 (2000)
N. Pradhani, P.K. Mahapatra, R.N.P. Choudhary, A.K. Jena, J. Mohanty, Investigation on the effect of Mn substitution on the structural, electrical and ferroelectric characteristics of Bi0.5Na0.5TiO3 ceramic. Mater. Res. Bull. 119, 110566 (2019)
M.M. Hejazi, E. Taghaddos, A. Safari, Reduced leakage current and enhanced ferroelectric properties in Mn-doped Bi0.5Na0.5TiO3-based thin films. J. Mater. Sci. 48, 3511–3516 (2013)
Z.H. Zhou, J.M. Xue, W.Z. Li, J. Wang, H. Zhu, J.M. Miao, Ferroelectric and electrical behavior of (Na0.5Bi0.5)TiO3 thin films. Appl. Phys. Lett. 85, 804–806 (2004)
V.D. Castro, G. Polzonetti, XPS study of MnO oxidation. J. Electron Spectrosc. Relat. Phenom. 48, 117–123 (1989)
S. Sharma, S. Chaudhary, S.C. Kashyap, S.K. Sharma, Room temperature ferromagnetism in Mn doped TiO2 thin films: electronic structure and Raman investigations. J. Appl. Phys. 109, 083905 (2011)
Acknowledgements
The authors will acknowledge support from Joint Fund of National Natural Science Foundation of China (U19A2087).
Author information
Authors and Affiliations
Corresponding author
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
Shi, M., Si, Z., Men, E. et al. Mn-doped (Bi0.5Na0.5) TiO3 thin film with low leakage current density and high ferroelectric performance. J Mater Sci: Mater Electron 32, 7249–7258 (2021). https://doi.org/10.1007/s10854-021-05435-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10854-021-05435-2