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Journal of Alloys and Compounds 461 (2008) 326330

SrBi2 (Ta0.5Nb0.5)2 O9:W thin lms obtained by chemical solution deposition: Morphological and ferroelectric characteristics
N.L. Amsei J unior a , A.Z. Sim oes b , L.S. Cavalcante c, , F. Moura a , E. Longo a , J.A. Varela a
a

Laborat orio Interdisciplinar em Cer amica, Departamento de F sico-Qu mica, Instituto de Qu mica, Universidade Estadual Paulista, P.O. Box 355, 14801-907 R. Francisco Degni, s/n, Bairro Quitandinha, Araraquara, SP, Brazil b Faculdade de Ci encias, Departamento de Qu mica, Universidade Estadual Paulista, Av. Luiz Edmundo Carrijo Coube, 14-01 Vargem Limpa, 17033-360 Bauru, SP, Brazil c Laborat orio Interdisciplinar de Eletroqu mica e Cer amica, Departamento de Qu mica, Universidade Federal de S ao Carlos, P.O. Box 676, 13565-905 S ao Carlos, SP, Brazil Received 5 May 2007; accepted 23 June 2007 Available online 27 July 2007

Abstract The effect of tungsten (W6+ ) ion substituting on dielectric and ferroelectric behavior in SrBi2 (Ta0.5 Nb0.5 )2 O9 (SBTN) thin lms prepared by polymeric precursor method was investigated at room temperature. The addition of W6+ ion in the SBTN lattice was evaluated by X-ray diffraction (XRD), microstructural and dielectrical properties. An increase in the grain size is evident when tungsten is introduced in the SBTN lattice. Substitution of tungsten until 10% on B site leads to introduce space charge polarization into the system, resulting in an appreciable decrease in both dielectric constant and tangent loss. The morphology of the thin lms investigated by atomic force microscopy leads to an increase in the grain size after tungsten addition. Fatigue resistance was noted with increase in tungsten addition. 2007 Elsevier B.V. All rights reserved.
Keywords: Thin lms; Ferroelectrics; Chemical synthesis; Atomic force microscopy; Dielectric response

1. Introduction Recently, ferroelectric thin lms have attracted considerable attention for use in nonvolatile memory applications, i.e., ferroelectric random-access memories [1]. In research of new materials, some can be promissory exhibit improves in dielectric and ferroelectric properties. Some of these materials could prove to be valuable because they are environment-friendly, lead free [2]. Bi-layered compounds are leading candidate materials for such optical devices and have been extensively studied [3]. The effect of doping and substituting on various physical and chemical properties of diverse materials is commonly known, and this effect has been extensively exploited in piezoelectrics and ferroelectrics to improve their performance. For example, there have been numerous papers that explain, the

Corresponding author. Tel.: +55 16 3361 5215, fax: +55 16 3351 8350. E-mail address: laeciosc@bol.com.br (L.S. Cavalcante).

effect of substitution of Ti by Zr in some ABO3 perovskites such as CaTiO3 [4], BaTiO3 [5] and PbTiO3 [6] promote improvements in the dielectric properties of these materials. Similar doping and substituting effects with tungsten were also found in bismuth layer-structured ferroelectrics (BLSFs), such as SrBi2 Nb2 O9 (SBN) and SrBi2 Ta2 O9 (SBT) [7,8]. Donor dopant, such as W6+ , induces cationic defects while occupying the B site of the perovskite lattice [9,10]. Such behavior may cause several effects on the dielectric behavior through interaction with domain walls [11,12]. Shimakawa et al. [13] has used high-resolution neutron diffraction to investigate precise crystal structures of the SrBi2 (Tax Nb1x )2 O9 (SBTN) solidsolution system and revealed that some of the (OTaONbO) bonds are shorter than the expected ionic bond length. These short bond lengths suggest a covalent character being this interaction plays an important role in the ferroelectric properties. In this form, we report the dielectric and ferroelectric behavior of SBTN:W thin lms prepared by the polymeric precursor method (PPM).

0925-8388/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2007.06.115

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2. Experimental details
Strontium carbonate, SrCO3 (Merck), niobium ammonium oxalate, NH4 H2 [NbO(C2 O4 )2 ] 3H2 O (CBMM, Arax a, Brazil), bismuth oxide, Bi2 O3 (Aldrich), tantalum ethoxide, Ta(OC2 H5 )5 (Alfa Aesar) and acid tungstic (Synth) were used as raw materials. The molar ratio among Sr2+ , Bi3+ , Ta5+ and Nb5+ was xed in 1:2:1:1. The W6+ was added in SrBi2 (Ta0.5 Nb0.5 )2 O9 by substitution of Nb5+ (5, 10 and 20%), respectively. Niobium hydroxide was formed by dissolution of niobium ammonium oxalate in water and precipitated as Nb(OH)5 . After ltration, niobium hydroxide was dissolved in aqueous solution of citric acid to form niobium citrate. The pH was adjusted to 78 adding ethylenediamine. In the preparation of tantalum citrate, tantalum ethoxide was dissolved in ethylene glycol under heating and stirring and then, citric acid was added. Citrate tungsten was prepared with the dissolution of acid tungstic in aqueous solution of citric acid. SrCO3 and Bi2 O3 were dissolved in nitric acid and then added in the appropriate amount of niobium, tantalum and tungsten citrate. Ethylenediamine was added into the solution until the pH reached 89. The citric acid/ethylene glycol ratio was xed as 60:40 (mass ratio). The viscosity of the resulting solution was adjusted to 20 cP by controlling the water content using a Brookeld viscosimeter. The SrBi2 (Tax Nb1x )2 O9 tungsten substituting (SBTNW) thin lms was spin coated on Pt(1 1 1)/Ti/SiO2 /Si(1 0 0) substrates by spinner (spin coater KW-4B, Chemat Technology) operating at 5000 rpm for 30 s. In previous work, we demonstrated that SBTN powders free of secondary phases can be formed at 700 C [14].

Fig. 1. X-ray diffraction for (a) SBTNW05, (b) SBTNW10 and (c) SBTNW20 thin lms annealed at 700 C for 2 h in oxygen atmosphere.

3. Characterizations Phase analysis of the lms was performed at room temperature by X-ray diffraction (XRD) using a Bragg-Brentano diffractometer (Rigaku-DMax 2500PC) and Cu K radiation. Microstructural characterization was performed by atomic force microscopy (AFM) using a DIGITAL, Nanoscope 3 A. The

thickness was obtained from SEM (Topcom SM-300) represents an average value of three measurements. Surface roughness was examined by AFM, using tapping mode technique 0.5 mm diameter top Au electrode was sputtered through a shadow mask at room temperature. The relative dielectric permittivity (r ) and dissipation factor (tan ) were carried out at room temperature as a function of frequency in the range of 10 kHz to 1 MHz using an impedance analyzer (model 4192 A, Hewlett-Packard). Ferroelectricity was investigated using a Sawyer-Tower circuit attached to a computer-controlled standardized ferroelectric test

Fig. 2. AFM micrographs for (a) SBTNW05, (b) SBTNW10 and (c) SBTNW20 thin lms annealed at 700 C for 2 h in oxygen atmosphere.

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system (Radiant Technology 6000 A). The hysteresis loop was measured at a frequency of 100 Hz at an applied electric eld of 330 kV/cm. The leakage currentvoltage (I V ) characteristic was determined with a voltage source measuring unit (Radiant Technology 6000 A). 4. Results and discussion X-ray diffraction patterns of SBTNW thin lms is illustrated in Fig. 1. All peaks were indexed to the perovskite phase and no secondary phases were observed. The SBTNW thin lms presents a polycrystalline nature with the maximum intensity peak at (1 1 5) direction, and exhibits very weak (0 0 l) peaks with the c-axis oriented normal to the substrate. In addition, less intense peaks along the (2 0 0) and (2 2 0) directions were observed in the pattern. Characteristic peak for platinum-coated silicon (1 1 1) substrates was observed in the range of 38 < 2 < 44. These results are similar to that obtained by Zanetti et al. [15] for SBN thin lms. AFM micrographs on the 1000 nm 1000 nm scale of SBTNW thin lm evidence that the lm surface is dense and crack free (Fig. 2(a)(c)). The SBTNW05, SBTNW10 and SBTNW20 thin lms presents spherical bigger grains with size around 85, 95 and 110 nm, respectively. The surface roughness of SBTNW05, SBTNW10 and SBTNW20 thin lms are 2.6, 3.8 and 3.9 nm, respectively. The average grain size and surface roughness shows a dependence of tungsten content. This is due the larger ionic size of W6+ ion compared to Ta5+ and Nb5+ ions. This result is better compared to other chemical method (ranging from 10 to 43 nm) and similar to that obtained by physical method (nearly 4 nm) [16,18]. According to Moert et al. [19] the transformation of SBT thin lms from amorphous to perovskite phase is accomplished by a strong change in the polycrystalline microstructure. The phase transformation starts at 650 C from a smooth and ne-grained uorite matrix to Aurivillius phase at 700 C. Fig. 3 presents the dielectric permittivity (r ) and dissipation factor (tan ). The dielectric permittivity shows little dispersion with frequency indicating that our lms possess low defect concentrations at the interface lmsubstrate. The low dispersion and the absence of any relaxation peak in tan indicate that both, interfacial polarization of the Maxwell Wagner type and a polarization produced by the electrode barrier can be neglected. The r of SBTNW05, SBTNW10 and SBTNW20 thin lms at 100 kHz was of 148, 132 and 117 and tan for the lms was of 0.05, 0.04 and 0.03, respectively in the same applied frequency. Ferroelectric behavior is illustrated in Fig. 4(a)(c). The loops are saturated with a remnant polarization (Pr ) of the SBTNW05, SBTNW10 and SBTNW20 thin lms were 6.1, 6.8 and 8.9 C/cm2 and coercive eld (kV/cm) of the SBTNW05, SBTNW10 and SBTNW20 thin lms were 105, 82.5 and 68.2, respectively. The saturation of the loops at these low frequencies indicates that the losses are minimal, suggesting the SBTNW thin lms are highly resistive. The Pr and Dv values obtained in this work are agreement with the literature data evidencing the efciency of the deposition process [15]. Gonzales-Aguiar et al.

Fig. 3. Dielectric permittivity and dielectric loss in dependence of applied frequency for (a) SBTNW05, (b) SBTNW10 and (c) SBTNW20 thin lms annealed at 700 C for 2 h in oxygen atmosphere.

[20] have prepared SBT thin lm using a new procedure based on an ethanolic solution. The authors have found Pr value of 5.0 C/cm2 and Ec of 50 kV/cm for the lm heat treated at 720 C in static air. Some physical properties of SrBi2 Ta2 O9 (SBT), SrBi2 Nb2 O9 (SBN), SrBi2 (Ta0.5 Nb0.5 )2 O9 (SBT50N50) and SrBi2 Ta2 Nb2 O9 :W (SBTNW) thin lms prepared by different techniques are presented in Table 1.

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Fig. 5. Fatigue as a function of polarization cycles for SBTNW05, SBTNW10 and SBTNW20 thin lms annealed at 700 C for 2 h in oxygen atmosphere.

Fig. 4. P E hysteresis loop for (a) SBTNW05, (b) SBTNW10 and (c) SBTNW20 thin lms annealed at 700 C for 2 h in oxygen atmosphere.

The ferroelectric properties of our SBTNW thin lm are reported and compared with SBT, SBN and SBTN thin lms prepared by other methods and comparable with the values obtained in literature in Refs. [16,2227]. We can see that SBTN:W

thin lms obtained by polymeric precursor method presents ferroelectric properties compatible to others lms obtained by methods. Better results of ferroelectric properties are reported in literature. However, the lms were prepared by PLD technique and also heat treated at 700 C in oxygen. The treatment under oxygen ux is believed to improve the electrical properties of these materials [15]. As can be observed in Table 1, increasing tungsten addition decreases the dielectric permittivity of the lm due to the space charge polarization into the system, resulting in an appreciable changes in both dielectric permittivity and tangent loss [28]. The fatigue endurance for SBTNW05, SBTNW10 and SBTNW20 thin lms annealed in oxygen atmosphere was evaluated are illustrated in Fig. 5. In the gure, P is the switched and P is the nonswitched polarization between two opposite 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 109 cycles with an applied pulse voltage of 9 V for SBTNW20 thin lms in oxygen atmosphere suggesting a good potential for applications in ferroelectric memories. The SBTNW05 lm annealed in oxygen atmosphere showed no fatigue resistance due to the increase in local current around the nucleation sites which can destroy the lmelectrode inter-

Table 1 Electrical properties of SBT, SBN, SBT50N50 and SBTNW thin lms compared with the reported in literature Perovskite abbreviation SBT SBN SBN SBT50N50 SBT50N50 SBT25N75 SBT70N30 SBT50N50W05 SBT50N50W10 SBT50N50W20 Method PLD PLD MOD PLD PPM EMOD MOCVD PPM PPM PPM Temperature ( C) 400 750 700 750 700 800 800 700 700 700 Atmosphere Oxygen Oxygen Air Oxygen Air Air Oxygen Oxygen Oxygen Oxygen r 87 190 220 112 148 132 117 tan 0.02 0.02 0.04 0.05 0.04 0.03 2Pr (C/cm2 ) 1.5 4 5.9 7.6 10.2 12.8 17 6.1 6.8 8.2 Ec (kV/cm) 17 90 79 75 96 130 91 105 82.5 68.2 Thickness (nm) 500 440 200 330 400 400 400 Reference [16] [22] [23] [24] [25] [26] [27] This work This work This work

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N.L. Amsei J unior et al. / Journal of Alloys and Compounds 461 (2008) 326330 [5] J. Zhai, X. Yao, J. Shen, L. Zhang, H. Chen, J. Phys. D: Appl. Phys. 37 (2004) 748. [6] N. Tohge, S. Takahashi, T. Minami, J. Am. Ceram. Soc. 74 (1991) 67. [7] E.C. Subbarao, J. Phys. Chem. Solids 23 (1962) 665. [8] R.E. Newnham, R.W. Wolfer, R.S. Horsey, F.A. Diaz-Colong, M.I. Kay, Mater. Res. Bull. 8 (1973) 1183. [9] A. Carg, T.C. Goel, Mater. Sci. Eng. B 60 (1999) 128. [10] R. Shannigrahi, R.N.P. Choudhary, N. Acharya, Mater. Sci. Eng. B 56 (1999) 31. [11] D. Bolten, U. Bouger, T. Schneller, M. Grossnam, O. Lose, R. Waser, Appl. Phys. Lett. 77 (2000) 3830. [12] S. Takahashi, Ferroelectrics 41 (1982) 143. [13] Y. Shimakawa, Y. Kubo, Y. Tauchi, T. Kamiyama, H. Asano, F. Izumi, Appl. Phys. Lett. 77 (2001) 2749. [14] N.L. Amsei J unior, A.Z. Sim oes, A.A. Cavalheiro, S.M. Zanetti, E. Longo, J.A. Varela, J. Alloys Compd. (2007), in press. [15] S.M. Zanetti, E.B. Araujo, E.R. Leite, E. Longo, J.A. Varela, Mater. Lett. 40 (1999) 33. [16] Y. Zhu, S.B. Desu, T. Li, S. Ramanathan, M. Nagata, J. Mater. Res. 12 (1997) 783. [18] A. Furuya, J.D. Cuchiaro, J. Appl. Phys. 84 (12) (1998) 6788 6794. [19] M. Moert, G. Schindler, T. Mikolajick, N. Nagel, W. Hartner, C. Dehm, H. Kohlstedt, R. Waser, Appl. Surf. Sci. 249 (2005) 23. [20] G. Gonzalez-Aguilar, I.M.M. Salvado, M.E.V. Costa, Mater. Lett. 60 (2006) 28. [22] S. Bhattacharyya, S.S.N. Bharadwaja, S.B. Krupanidhi, Integ. Ferroelec. 31 (2000) 57. [23] S.B. Desu, D.P. Vijay, Mater. Sci. Eng. B 32 (1995) 83. [24] S. Bhattacharyya, S.S.N. Bharadwaja, S.B. Krupanidhi, Solid State Commun. 114 (2005) 585. [25] N.L. Amsei J unior, A.Z. Sim oes, R.F.C. Pianno, S.M. Zanetti, E. Longo, J.A. Varela, J. Alloys Compd. (2007), in press. [26] A. Furuya, J.D. Cuchiaro, J. Appl. Phys. 84 (1998) 6788. [27] M. Mitsuya, K. Ishikawa, N. Nukaga, H. Funakubo, Jpn. J. Appl. Phys. 39 (2000) 620. [28] Y. Wu, S.J. Limmer, T.P. Chou, C. Nguyen, G. Cao, J. Mater. Sci. Lett. 21 (2002) 947. [29] A.Z. Sim oes, M.A. Ram rez, A.H.M. Gonzalez, C.S. Riccardi, A. Ries, E. Longo, J.A. Varela, J. Solid State Chem. 179 (2006) 2206.

face and suppress the nucleation of oppositely oriented domains at the surface. In this lm an increase in switching polarization leads to a local increase in conductivity at the lmelectrode interface region [29]. 5. Conclusions SBTNW05, SBTNW10 and SBTNW20 thin lms free of cracks were obtained by polymeric precursor method on Pt(1 1 1)/Ti/SiO2 /Si(1 0 0) substrates. The dielectric permittivity at 100 kHz were 148, 132 and 117, and dissipation factor at 100 kHz were 0.05, 0.04 and 0.03, respectively for SBTNW05, SBTNW10 and SBTNW20 thin lms. The remnant polarization of 6.1, 6.8 and 8.2 C/cm2 and coercive eld of 105, 82.5 and 68.3 kV/cm, respectively. Fatigue resistance was observed with increase of tungsten addition. SBTNW10 thin lms obtained by chemical method is a promising material for random access memories applications. Acknowledgements The authors thank the nancial support of the Brazilian research nancing institutions: CAPES, FAPESP and CNPq. References
[1] C.A.-P. de Araujo, J.D. Cuchiaro, L.D. McMillan, M.C. Scott, J.F. Scott, Nature 374 (1995) 627. [2] I.A. Souza, A.Z. Sim oes, S. Cava, L.S. Cavalcante, M. Cilense, E. Longo, J.A. Varela, J. Solid State Chem. 179 (2006) 2972. [3] D.P. Volanti, L.S. Cavalcante, E.C. Paris, A.Z. Sim oes, D. Keyson, V.M. Longo, A.T. de Figueiredo, E. Longo, J.A. Varela, F.S. De Vicente, A.C. Hernandes, Appl. Phys. Lett. 99 (2007) 261913. [4] L.S. Cavalcante, A.Z. Sim oes, L.P.S. Santos, M.R.M.C. Santos, E. Longo, J.A. Varela, J. Solid State Chem. 179 (2006) 3739.