Abstract
Highly oriented PbZr0.53Ti0.47O3/CoFe2O4 (PZT/CFO) multilayered nanostructures (MLNs) were grown on MgO substrate by pulsed laser ablation using La0.5Sr0.5CoO3 (LSCO) as conducting bottom electrode. The effect of various PZT/CFO (PC) sandwich configurations having three, five, and nine layers while maintaining total thickness of PZT and CFO be identical has been systematically investigated. X-ray diffraction (XRD) and micro-Raman spectra revealed the existence of pure PZT and CFO phases without any intermediate phase. Intact MLNs were observed by transmission electron microscopy (TEM) with little inter-diffusion near the interfaces at nano-metric scale without any impurity phase. Impedance spectroscopy, modulus spectroscopy, and conductivity spectroscopy were carry out over a wide range of temperatures (100–600 K) and frequencies (100 Hz–1 MHz) to investigate the grain and grain boundary effect on electrical properties of MLNs. Temperature dependent real dielectric permittivity and dielectric loss illustrated step-like behavior and relaxation peaks near the step-up characteristic, respectively. Cole–Cole plots indicate that most of the dielectric response came from the bulk (grain) MLNs below 300 K, whereas the grain boundary and the electrode–MLNs effects are prominent at elevated temperatures. The dielectric loss relaxation peak shifted to higher frequency side with increase in temperature, it was out of the experimental frequency window above 300 K. Our Cole–Cole fitting of dielectric loss spectra indicated marked deviation from the ideal Debye-type of relaxation, which is more at elevated temperature. Master modulus spectra supported the observation from the impedance spectra; it also indicated that the magnitude of the grain boundary compared to grain becomes more prominent with increase in number of layers. We have explained these electrical properties of MLNs by Maxwell–Wagner type contributions arising from the interfacial charge at the interface of the ML structures. Three different types of frequency dependent conduction processes were observed at elevated temperatures (>300 K), which fitted well with the double power law, \( \sigma \left( \omega \right) = \sigma \left( 0 \right) + A_{1} \omega^{{n_{1} }} + A_{2} \omega^{{n_{2} }} , \) indicating that the low frequency (<1 kHz) conductivity may be due to long-range ordering (frequency independent), mid frequency conductivity (<10 kHz) may be due to short-range hopping, and high frequency (<1 MHz) conduction due to the localized relaxation hopping mechanism. Ferroelectric polarization decreased slowly in reducing the temperature from 300 to 200 K, with complete collapse of polarization at ~100 K, but there was complete recovery of the polarization during heating, which was repeatable over many different experiments. At the same time, the temperature dependent remanent magnetization of the MLNs showed slow enhancement in the magnitude till 200 K with three-fold increase at 100 K compared to room temperature. This enhancement in remanent magnetization and decrease in remanent ferroelectric polarization on lowering the temperature indicate temperature dependent dynamic switching of ferroelectric polarization. The magnetic and ferroelectric properties of MLNs were quite different compared to individual layers suggesting its improper ferroelectric characteristics. The fatigue test showed almost 0–20% deterioration in polarization. Fatigue and strong temperature and frequency dependent magneto-electric coupling suggest MLNs utility for Dynamic Magneto-Electric Random Access Memory (DMERAM).
Similar content being viewed by others
References
Scott JF (2007) Science 315:954
Spaldin NA, Fiebig M (2005) Science 309:391
Eerenstein W, Mathur ND, Scott JF (2006) Nature 442:759
Spaldin NA, Pickett WE (2003) J Solid State Chem 176:615
Wang J, Neaton JB, Zheng H, Nagarajan V, Ogale SB, Liu B, Viehland D, Vaithyanathan V, Schlom DG, Waghmare UV, Spaldin NA, Rabe KM, Wuttig M, Ramesh R (2003) Science 299(14):1719
Ramesh R, Spaldin NA (2007) Nature 6:21
Zheng H, Wang J, Loand SE, Ma Z, Mohaddes-Ardabili L, Zhao T, Salamanca-Riba L, Shinde SR, Ogale SB, Bai F, Viehland D, Jia Y, Schlom DG, Wuttig M, Roytburd A, Ramesh R (2004) Science 303:661
Petrov VM, Srinivasan G, Laletsin U, Bichurin MI, Tuskov DS, Paddubnaya N (2007) Phys Rev B 75:174422
Srinivasan G, Rasmussen ET, Gallegos J, Srinivasan R, Bokhan YI, Laletin VM (2001) Phys Rev B 64:214408
Dong S, Li J-F, Viehland D (2006) J Mater Sci 41:97. doi:https://doi.org/10.1007/s10853-005-5930-8
Zhang JX, Dai JY, Lu W, Chan WHL (2009) J Mater Sci. doi: https://doi.org/10.1007/s10853-009-3512-x
Duan Ch-G, Jaswal SS, Tsymbal EY (2006) Phys Rev Lett 97:047201
Niranjan M-K, Velev JP, Duan Ch-G, Jaswal SS, Tsymbal EY (2008) Phys Rev B 78:104405
Zhou JP, He H, Shi Z, Nan CW (2006) Appl Phys Lett 88:013111
Murugavel P, Singh MP, Prellier W, Mercey B, Simon Ch, Raveau B (2005) J Appl Phys 97:103914
Ortega N, Bhattacharya P, Katiyar RS, Dutta P, Manivannan A, Seehra MS, Takeuchi I, Majumder SB (2006) J Appl Phys 100:126105
Raymond O, Font R, Suarez-Almodovar N, Portelles J, Siqueiros JM (2005) J Appl Phys 97:084108
Srinivas K, Sarah P, Suryanarayana SV (2003) Bull Mater Sci 26:2–274
Ortega N, Kumar A, Bhattacharya P, Majumder SB, Katiyar RS (2008) Phy Rev B 77:014111
Liu J, Duan Ch-G, Mei WN, Smith RW, Hardy JR (2005) J Appl Phys 98:093703
Ni WQ, Zheng XH, Yu JC (2007) J Mater Sci 42:1037. doi:https://doi.org/10.1007/s10853-006-1431-7
Catalan G (2006) Appl Phys Lett 88:102902
Catalan G, Scott JF (2007) Nature 448:E4. doi:https://doi.org/10.1038/nature06156
Catalan G, O`Neill D, Bowman RM, Gregg JM (2000) Appl Phys Lett 77:3078
Ortega N, Kumar A, Katiyar RS, Scott JF (2007) Appl Phys Lett 91:102902
Sinclair DC, Adams TB, Morrison FD, West AR (2002) Appl Phys Lett 80:2153
Yang P, Carroll DL, Robert JB, Schwartz W (2002) Appl Phys Lett 81:4583
Bousquet E, Dawber M, Stucki N, Lichtensteiger C, Hermet P, Gariglio S, Triscone J-M, Ghosez P (2008) Nature 452:732
Kundys B, Simon Ch, Martin Ch (2008) Phys Rev B 77:172402
Cole KS, Cole RH (1941) J Chem Phys 9:341
Schmidt R, Eerenstein W, Winiecki T, Morrison FD, Midgley PA (2007) Phys Rev B 75:245111
Jiang AQ, Scott JF, Dawber M, Wang C (2002) J Appl Phys 92:6756
Liu J, Duan Ch-G, Yin W-G, Mei WN, Smith RW, Hardy JR (2004) Phys Rev B 70:144106
Victor P, Bhattacharyya S, Krupanidhy SB (2003) J Appl Phys 94:5135
Macedo PB, Moynihan CT, Bose R (1972) Phys Chem Glasses 13:171
Provenzano V, Boesch LP, Volterra V, Macedo PB, Moynihan CT (1972) J Am Ceram Soc 55:492
Kohlrausch R (1847) Ann Phys. (Leipzig) 12:393
Williams G, Watts DC (1970) Trans Faraday Soc 66:80
Moynihan CT, Boesch LP, Laberge NL (1973) Phys Chem Glasses 14:122
Baskaran N (2002) J Appl Phys 92:825
Patel HK, Martin SW (1992) Phys Rev B 45:10292
Ngai KL, Greaves GN, Moynihan CT (1998) Phys Rev Lett 80:1018
Funke K (1993) Prog Solid State Chem 22:111
Jonscher AK (1977) Nature 264:673
Murugaraj R (2007) J Mater Sci 42:10065. doi:https://doi.org/10.1007/s10853-007-2052-5
Almond AP, West AR, Grant RJ (1982) Solid State Commun 44:277
Pelaiz-Barramco A, Gutierrez-Amador MP, Huanosta A, Valenzuela R (1998) Appl Phys Lett 73:2039
Calderon MJ, Brey L, Guinea F (1999) Phys Rev B 60:6698
Kimura T, Kawamoto S, Yamada I, Azuma M, Takano M, Tokura Y (2003) Phys Rev B 67:180401 (R)
Yang Y, Liu JM, Huang HB, Zou WQ, Bao P, Liu ZG (2004) Phys Rev B 70:132101
Al-Shareef HN, Kingon AI, Chen X, Bellur KR, Auciello O (1994) J Mater Res 9:2968
Yoo IK, Desu SB (1992) Mater Sci Eng B 13:319
Warren WL, Dimos D, Tuttle BA, Nasby RD, Pike GE (1994) Appl Phys Lett 65:1018
Ramesh R, Chan WK, Wilkens B, Gilchrist H, Sands T, Tarascon JM, Keramidas VG, Fork DK, Lee J, Safari A (1992) Appl Phys Lett 61:1537
Dat R, Lichtenwalner DJ, Auciello O, Kingon AI (1994) Appl Phys Lett 64:2673
Bao D, Wakiya N, Shinozaki K, Mizutani N (2002) J Phys D Appl Phys 35:L1
Acknowledgements
This work was supported in parts by DOE DE-FG02- 08ER46526, DoD-HIS W911NF-06-1-0030 and DEPSCoR W911NF-06-1-0183 grants. One of us (N. Ortega) was supported by a NSF-IFN-EPSCOR Fellowship.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Ortega, N., Kumar, A., Katiyar, R.S. et al. Dynamic magneto-electric multiferroics PZT/CFO multilayered nanostructure. J Mater Sci 44, 5127–5142 (2009). https://doi.org/10.1007/s10853-009-3635-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-009-3635-0