Materials Research Bulletin 42 (2007) 975981 www.elsevier.

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Ferroelectric and piezoelectric properties of bismuth titanate thin lms grown on different bottom electrodes by soft chemical solution and microwave annealing
A.Z. Simoes a,*, M.P. Cruz b,c,d, A. Ries a, E. Longo a, J.A. Varela a, R. Ramesh c,d
b

Chemistry Institute, Universidade Estadual Paulista (UNESP), Rua Prof. Francisco Degni s/n, 14801-970 Araraquara, SP, Brazil Centro de Ciencias de la Materia Condensada (CCMC), UNAM, Km 107, Carretera Tijuana-Ensenada, Ensenada, BC, C.P. 22800, Mexico c Department of Materials Science and Engineering, University of California, Berkeley, CA 94720, United States d Department of Physics, University of California, Berkeley, CA 94720, United States Received 1 June 2006; accepted 9 August 2006 Available online 11 September 2006

Abstract Bismuth titanate (Bi4Ti3O12, BIT) lms were evaluated for use as lead-free piezoelectric thin lms in micro-electromechanical systems. The lms were grown by the polymeric precursor method on LaNiO3/SiO2/Si (1 0 0) (LNO), RuO2/SiO2/Si (1 0 0) (RuO2) and Pt/Ti/SiO2/Si (1 0 0) (Pt) bottom electrodes in a microwave furnace at 700 8C for 10 min. The domain structure was investigated by piezoresponse force microscopy (PFM). Although the converse piezoelectric coefcient, d33, regardless of bottom electrode is around ($40 pm/V), those over RuO2 and LNO exhibit better ferroelectric properties, higher remanent polarization (15 and 10 mC/ cm2), lower drive voltages (2.6 and 1.3 V) and are fatigue-free. The experimental results demonstrated that the combination of the polymeric precursor method assisted with a microwave furnace is a promising technique to obtain lms with good qualities for applications in ferroelectric and piezoelectric devices. # 2006 Elsevier Ltd. All rights reserved.
Keywords: A. Thin lms; B. Chemical synthesis; D. Ferroelectricity

1. Introduction The superior ferroelectric properties of Bi4Ti3O12 (BIT) thin lms among bismuth-layer-structured ferroelectric compounds have attracted intense interest, making these lms some of the most competitive candidates for piezoelectric devices against lead containing materials [1]. Bismuth titanate is composed of a triple perovskite unit sandwiched between (Bi2O2)2+ layers. The pseudo-orthorhombic BIT unit possesses the lattice parameters of a = 0.5450, b = 0.54059, and c = 3.2832 nm, and exhibits the spontaneous polarizations Ps = 50 and 4 mC/cm2 along a- and c-axes, respectively [2]. Therefore, lms having a larger fraction of a-axis-oriented grains should exhibit better ferro- and piezoelectric properties. However, BIT lms prefer to grow with c-axis perpendicular to the lm surface when common Pt (1 1 1) electrodes are used. A suitable electrode with better lattice matching with the long c-axis is required in order to fabricate a- or a/b-axis orientation [3,4]. Because of their complex chemical composition and

* Corresponding author. Tel.: +55 16 3301 6600; fax: +55 16 3322 7932. E-mail address: alezipo@yahoo.com (A.Z. Simoes). 0025-5408/$ see front matter # 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.materresbull.2006.08.006

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crystallographical structure, single crystals of these materials are difcult to be grown. Thus, most of the current studies are focused on the applications of thin lms [5]. Ferroelectric thin lms are constrained by substrates and therefore their properties can be affected by many factors, such as orientation, properties of the substrate (lattice parameters and thermal expansion coefcient), and lm thickness. For some applications, as for example in ferroelectric memories, large remanent polarization and good fatigue-free characteristics are required [6]. Unfortunately, lms of BIT grown over common platinum coated silicon substrates do not satisfy these requirements. This might be due to an interfacial reaction between platinum and bismuth which can lead to undesired electrical properties [7]. Therefore, the substitution of metallic electrodes based on noble metals, like platinum, with conductive oxides is an alternative to reach better electrical properties caused by the high oxygen afnity of these electrodes [8]. For this purpose, it is essential to understand the ferroelectric properties of the BIT lms deposited on electrodes based on metallic oxides such as LNO and RuO2. Some attempts have been made to enhance the crystallization ability of ferroelectric thin lms and metallic oxide electrodes [3,9]. For obtaining good crystallized lms by chemical solution deposition, heat treatments at high temperatures for a long time, $2 h, are normally necessary. These long heat treatments can cause several damages to the stack, leading to interdiffusion between the lm and the substrate, and sometimes loss of stoichiometry (due to the loss of volatile cation). So, it is important to decrease the temperature and time of thermal treatment. Recently, the use of a domestic microwave furnace has been developed as a way to process materials and has opened an opportunity to enhance crystallization with a lower annealing processing time. This leads to a decrease the interfacial reactions between ferroelectric thin lms and electrodes and also improves the control over the crystallographic orientation of the thin lms [10]. Among various methods such as metal-organic chemical vapour deposition, pulsed laser deposition and solgel, the polymeric precursor method has its advantages over the other production techniques include its low cost, good compositional homogeneity, relatively low processing temperatures and the ability to coat large substrate areas [11,12]. In this work, we present our ndings on the preparation of piezoelectric BIT lms on LaNiO3, RuO2 and Pt/Ti/SiO2/ Si substrates by the polymeric precursor method combined with the domestic microwave oven with the advantage of reducing the time of thermal treatment. 2. Experimental The bottom electrodes thin lms (LNO and RuO2) were spin-coated on SiO2/Si (1 0 0) substrates by a commercial spinner at 5000 revolutions/min for 30 s (spin coater KW-4B, Chemat Technology). Bottom electrodes of commercial platinum coated silicon substrates were also used. Each deposited layer was pre-red at 400 8C for 2 h in a conventional oven. After the pre-ring, each layer was crystallized in a microwave oven at 700 8C for 10 min using a SiC susceptor, which absorbs the microwave energy and rapidly transfers the heat to the lm. No post-annealing treatment was performed after crystallization. Using the same procedure, BIT thin lms were deposited by spinning the precursor solution on the desired substrates. Through this process, we obtained thicknesses of about 150 nm for the bottom electrodes and about 300 nm for BIT, by repeating the spin-coating and heating treatment cycles. The microwave oven used here was a simple domestic model similar to that described in literature [10]. Phase analysis was performed at room temperature by X-ray diffraction (XRD) in BraggBrentano geometry (Rigaku 2000) at Cu Ka radiation. Furthermore, topography and thickness were examined using atomic force microscopy (AFM) (Digital Instruments, Nanoscope IIIa) and scanning electron microscopy (Topcom SM-300), respectively. The top Pt electrodes were prepared by photolithography with 8 104 mm2 dot area. The ferroelectric properties of the capacitors were measured by a Radiant Technology Tester RT6000 A in a virtual ground mode. The piezoelectric measurements were done using a setup based on an atomic force microscope [13] in a Multimode Scanning Probe Microscope with Nanoscope IV controller. 3. Results and discussion Fig. 1 shows the XRD results for BIT lms deposited on different bottom electrodes. All peaks were assigned to a BIT-type structure. No reections were detected that would be indicative of second phases. Film orientations depend in general on surface and interface energies. The (1 1 7) and (2 0 0) orientations for the lms deposited on LNO and RuO2 bottom electrodes are expected to be due to good lattice matching. In contrast, the predominant c-oriented

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Fig. 1. X-ray diffraction patterns of Bi4Ti3O12 lms deposited at 700 8C for 10 min on: (a) LaNiO3, (b) RuO2 and (c) Pt.

crystallites in the lm deposited on Pt are thought to be driven by their low surface energies [14]. In the case of the (2 0 0) oriented lm, the lattice mismatch between bottom electrode and the peculiar long c-axis of BIT-type structure is proposed to have its origin in the different OO bond lengths along the c-axis and other (h k l) directions [15]. From the application point of view, random-oriented BIT lms are more favourable than (0 0 l) oriented lms. Therefore, this suggest that the lms deposited on oxides electrodes have a suitable orientation to reach excellent ferroelectric and piezoelectric properties. Fig. 2 shows polarization hysteresis loops of the BIT lms deposited on different bottom electrodes. Remanent polarizations (Pr) of 10 and 15 mC/cm2 with drive voltages of 2.3 and 1.6 V were observed in the lms deposited on LNO and RuO2 bottom electrodes, respectively. For the lms deposited on Pt substrates the remanent polarization is reduced to 8.5 mC/cm2 due the stronger contribution of the crystallites grown in the c-axis direction. These results clearly demonstrate that controlling the orientation of grains in a lm is a key point to improve the ferroelectric properties. Another factor can be the inhibition of domain wall movement caused by a high concentration of dipole complexes at the lmsubstrate interface. This can originate from the thermal shock caused by the rapid heating of the SiC susceptor on platinum which favours the accumulation of the static charges at the interface lmsubstrate. It is supposed that the real temperature in the susceptor may be some degrees higher, which, allied to the effect of the microwave energy may cause degradation of the lmelectrode interface and hence a loss of the ferroelectric properties [16]. This effect is more evident in the lms deposited on platinum since it does not act as sink for oxygen vacancies compared to the oxides which accommodate relatively large concentration of oxygen defects [16]. For this lm the drive voltage is around 4 Vand is considered large for use as ferroelectric memories. From hystereses curves, it is clear that the remanent polarization of (1 1 7)- and (2 0 0)-oriented lm is larger than that of (0 0 l)- and (1 1 7)oriented lms. Since LNO and RuO2 electrodes give better ferroelectric properties, it is believed that if oxygen vacancies accumulate near the lmelectrode interface, the conductive oxide can consume the vacancies by changing its nonstoichiometry. Therefore, the accumulation of oxygen vacancies near the interface is reduced. This implies less

Fig. 2. PV hystereses loops of Bi4Ti3O12 lms deposited on LaNiO3, RuO2 and Pt bottom electrodes at 700 8C for 10 min.

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Fig. 3. (P* P^) as a function of polarization cycles for Bi4Ti3O12 lms deposited on different bottom electrodes at 700 8C for 10 min: (*) LaNiO3, (&) RuO2 and (~) Pt.

charge trapping and domain wall pinning in the interface region. Therefore, the effect of the LNO and RuO2 electrodes may be attributed to their function as an oxygen vacancy sink [17,18]. As a consequence of oxygen vacancies accumulated at the lmelectrode interface, a shift of the hysteresis loop along the electric eld axis towards the positive side was observed and may lead to a failure of the capacitor. These charges may originate during the heat treatment process due to the decomposition of the polymeric precursor [12]. According to the electrostatic model proposed by Robels et al. [19], this horizontal shift of the curve represents the internal bias, which is closely connected to the electrode/lm interface. These ndings suggest that the slightly higher voltage shift observed in the lms deposited on Pt substrates resulted from the nature of the bottom electrode, since the only difference in the lm preparation is the type of substrate used. In our case it is observed that microwave crystallization with platinum as bottom electrode induces a permanent voltage shift in the hysteresis loops of the BIT lms due to the generation of trapped charges at the defect sites near the electrodelm interface. These results indicate the unsuitability of the lms for use as memories owing to the signicant difference between +Vc and Vc, respectively. Fig. 3 presents the fatigue endurance of the BIT thin lms as a function of switching cycles. P* is the switched polarization between two opposite polarity pulses and P^ is the nonswitched polarization between the same two polarity pulses. The P* P^ or P* (P^) denote the switchable polarization, which is an important variable for nonvolatile memory application. Fatigue resistance was observed up to 1010 cycles with oxide electrodes indicating that the conductive oxide can consume the oxygen vacancies accumulated near the lmelectrode interface. On the other hand, for the lms deposited on platinum coated silicon substrates no fatigue resistance was observed indicating that the sparks formed by the high electric eld in the microwave environment damaged the lmelectrode interface and therefore affect the switching characteristics of BIT lms. Fig. 4 shows the out-of-plane (OP) and in-plane (IP) piezoresponse images of the as-grown lms after applying a bias of 12 V, on an area of 2 mm 2 mm, and then an opposite bias of +12 V in the central 1 mm 1 mm area. To obtain the domain images of the BIT lms, a high voltage that exceeds the coercive eld was applied during scanning. The contrast in these images is associated with the direction of the polarization [13]. The white regions in the out-of-plane PFM images correspond to domains with the polarization vector oriented toward the bottom electrode hereafter referred to as down polarization (Fig. 4a, d and g) while the dark regions correspond to domains oriented upward referred to as up polarization. Grains which exhibit no contrast change is associated with zero outof-plane polarization. Although the lms have a certain degree of preferred orientation as indicated by the XRD spectra in Fig. 1, they still preserve their polycrystalline nature. This can be concluded from the piezo-contrast given by the as-grown state. After a negative bias was applied, grains labeled A did not change their contrast. However in most cases, such as in grains labeled B and C (Fig. 4a), a polarization pointing predominantly out-of-plane was observed. A similar situation was observed when a positive bias was applied to the lm. We noticed that some of the grains exhibit a white contrast associated to a component of the polarization pointing toward the bottom electrode. On the other hand, in the in-plane PFM images (Fig. 4b, e and h) the contrast changes were associated with changes of the in-plane polarization components. In this case, the white contrast indicates polarization, e.g. in the positive direction of the y-axis while dark contrast are given by in-plane polarization components pointing to the negative part of the y-axis. The d33(V) hysteresis loops are shown in Fig. 4c, f and i. The maximum d33 value, $40 pm/V, is

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Fig. 4. Out-of-plane (OP) and in-plane (IP) PFM images, as well as piezoresponse loops of Bi4Ti3O12 lms deposited on different bottom electrodes at 700 8C for 10 min: (a) LaNiO3 (OP), (b) LaNiO3 (IP) and (c) LaNiO3 hysteresis loop; (d) RuO2 (OP), (e) RuO2 (IP) and (f) RuO2 hysteresis loop; (g) Pt (OP), (h) Pt (IP) and (i) Pt hysteresis loop.

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Fig. 4. (Continued ).

similar for all samples and approaches the reported value for a BIT single crystal [19]. The enhancement of polarization could be caused by the microwave annealing whose role is to avoid interfacial reactions and increase the lms crystallization. As can be seen, the hysteresis loop for the lm deposited on the Pt substrate (Fig. 4i) shows an offset in the vertical direction which can be probably caused by clamping effect due to the substrate and the generation of trapped charges at the defect sites near the electrodelm interface caused by strong interaction between microwave energy with platinum electrode [20]. Although the PZT lms still have higher d33 values, ranging from 40 to 110 pm/V [21], the presented values reported for our BIT lms suggest that this material can be considered as a viable alternative for lead-free piezo-ferroelectric devices. Also, the microwave annealing for the processing of materials provides the advantages of low investment, rapid and uniform heating, low sintering temperatures and times and improved product quality. In comparison with other lead-free ferroelectrics, 40 pm/V is much higher than the d33 value of SrBi2Ta2O9 lms (17 pm/V) and close to the reported value of Nd-doped Bi4Ti3O12 (38 pm/V) [22]. 4. Conclusions In conclusion, BIT thin lms were successfully crystallized using a low power microwave oven, with no postannealing treatment. The electrical measurements indicate that the use of platinum substrate as bottom electrode is inappropriate to obtain good BIT lms. This effect was not observed for lms deposited on oxide electrodes. Regularly shaped hysteresis is observed for the lms deposited on the LaNiO3 and RuO2 electrodes. Furthermore, high fatigue resistance was observed for lms deposited on LaNiO3 and RuO2 electrodes which shows that our lms are promising

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candidates for nonvolatile random access memories. Our results indicate that the BIT lms exhibit a good piezoelectric response of (40 pm/V). BIT lms crystallized in the microwave oven using conductor oxides as bottom electrodes present good ferroelectric properties and piezoelectric coefcients and can be used for ferroelectric random access memories and piezoelectric devices. Acknowledgments The authors gratefully acknowledge the nancial support of the Brazilian agencies FAPESP, CNPq, CAPES. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] M. Chu, M. Ganne, M.T. Caldes, E. Gautier, L. Brohan, Phys. Rev. B 68 (2003) 014102. S.E. Cummins, L.E. Cross, J. Appl. Phys. 39 (1968) 22682274. H.N. Lee, D. Hesse, N. Zahharov, U. Gosele, Science 296 (2003) 20062009. H. Matsuda, S. Ito, T. Iijima, Appl. Phys. Lett. 83 (2003) 50235025. J.K. Lee, C.H. Kim, H.S. Suh, K.S. Hong, Appl. Phys. Lett. 80 (2002) 35933595. K. Kim, C. Kim, Surf. Coat. Technol. 177 (2004) 770773. D.H. Bao, X. Yao, N. Wakiya, K. Shinozaki, N. Mizutani, J. Phys. D 36 (2003) 12171221. R. Ramesh, H. Gilchrist, T. Sands, V.G. Keramidas, R. Haakenaasen, D.K. Fork, Appl. Phys. Lett. 63 (1993) 35923594. R. Ramesh, D.G. Schlom, Science 296 (2002) 19751976. N.S.L.S. Vasconcelos, J.S. Vasconcelos, V. Bouquet, M. Guilloux-Viry, M.I. Bernardi, J.A. Varela, Thin Solid Films 436 (2003) 213219. A.Z. Simoes, B.D. Stojanovic, A. Tangastev, N. Setter, J.A. Varela, Integrated Ferroelectrics 43 (2002) 123135. A.Z. Simoes, A. Ries, F.M. Filho, J.A. Varela, E. Longo, Appl. Phys. Lett. 85 (2004) 59625964. A. Gruverman, O. Auciello, H. Tokumoto, Annu. Rev. Mater. Sci. 28 (1998) 101123. Y.M. Sun, Y.C. Chen, J.Y. Gan, J.C. Hwang, Jpn. J. Appl. Phys. (Part 2) 41 (2002) L892L894. W.J. Takei, N.P. Formigoni, M.H. Francombe, Appl. Phys. Lett. 15 (1969) 256258. S.M. Zanetti, J.S. Vasconcelos, N.S.L.S. Vasconcelos, E.R. Leite, E. Longo, J.A. Varela, Thin Solid Films 466 (2004) 6268. H.N. Al-Shareef, D. Dimos, W.L. Warren, B.A. Tuttle, J.A. Voigt, R.D. Nasby, J. Appl. Phys. 79 (1996) 10131016. F.M. Pontes, E.R. Leite, E. Longo, J.A. Varela, J.A. Eiras, Appl. Phys. Lett. 76 (2000) 24332435. U. Robels, J.H. Calderwood, G. Arlt, J. Appl. Phys. 77 (1995) 40024008. A.L. Kholkin, K.G. Brooks, N. Setter, Appl. Phys. Lett. 71 (1997) 20442046. P. Muralt, IEEE Trans. Ultrason. Ferroelectr. Freq. Control. 47 (2000) 903915. L. Kholkine, C. Wuetchrich, D.V. Taylor, N. Setter, Rev. Sci. Instrum. 67 (1996) 19351941.