Solid State Sciences 6 (2004) 547551 www.elsevier.

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Characterisation of BaBi2 Nb2O9 powders and thin lms prepared by a solution synthesis technique
A. Ben an 1 , P. Boullay , J.P. Mercurio c
Laboratoire de sciences des procds cramiques et traitements de surface (CNRS UMR6638), 123, av. Albert Thomas, Universit de Limoges, 87060 Limoges cedex, France Received 2 December 2003; received in revised form 13 February 2004; accepted 10 March 2004 Available online 17 April 2004

Abstract Ba2 Bi2 NbO9 (BBN) powders with the order of magnitude of nanometer were prepared by a metal organic decomposition (MOD) method. The thermal decomposition of the air-stable BBN precursor solution was studied using a thermal analyser and X-ray diffraction (XRD). Thin lms of Ba2 Bi2 NbO9 (BBN) have been deposited on both alumina (-Al2 O3 ) and Pt/TiO2 /SiO2 /(100)Si substrates by spin-coating of the obtained BBN precursor solution. The phase formation, crystallite size and morphology of the thin lms were investigated by X-ray diffraction (XRD) and electron microscopy (EM). It is shown that a monophasic BBN phase with good crystallinity can be obtained in the form of thin lms on both substrates without excess of bismuth in the precursor solution. 2004 Elsevier SAS. All rights reserved.
Keywords: Aurivillius phases; Chemical synthesis; Films; Metalorganic decomposition method

1. Introduction The Aurivillius phases [1] are layered bismuth oxides of general formula Bi2 Am1 Bm O3m+3 (1 m 6) formed by the regular stacking of [Bi2 O2 ]2+ slabs and perovskite-like blocks [Am1 Bm O3m+1 ]2 , where A represents mono-, dior trivalent cations (K+ , Na+ , Ba2+ , Ca2+ , Sr2+ , Pb2+ or Bi3+ ) and B represents tetra-, penta- or hexavalent cations of a transition metal (Ti4+ , Nb5+ , Ta5+ or W6+ ). This family includes many ferroelectric materials at room temperature, which currently arouse a considerable interest because of their potential application in the realisation of nonvolatile random access memories (NV-RAMs) and other technical devices [2]. The Bi-layered structure compounds have been found to be the most suitable alternative material for Pb(ZrTi)O3 (PZT), which are known to have signicant polarisation loss at repetitive switching cycles on Pt electrodes [3]. In contrast, Aurivillius compounds with m = 2
* Corresponding author.

E-mail address: philippe.boullay@unilim.fr (P. Boullay).

1 On leave from: Jozef Stefan Institut, Jamova 39, Ljubljana 1000,

Slovenia. 1293-2558/$ see front matter 2004 Elsevier SAS. All rights reserved. doi:10.1016/j.solidstatesciences.2004.03.011

such as SrBi2 (Nb,Ta)2O9 exhibits a low dielectric constant, almost no fatigue on Pt electrodes, and low leakage currents [4,5]. For these compositions, when Ba is substituted for Sr, the FE-PE transition is broadened leading to a relaxor-like behaviour [6,7]. Although a considerable literature reports on the preparation of SrBi2 (Nb,Ta)2O9 ferroelectric thin lms with various lm deposition techniques including laser deposition and solgel spin coating technique, a few articles were devoted to the preparation of BaBi2 Ta2 O9 (BBT) and BaBi2 Nb2 O9 (BBN) precursors as well as to the fabrication of thin lms. Regarding BBN, precursors were obtained using an alkoxide solgel route [8], a tartaric solgel route [9] and a polymeric Pechini method [10]. Thin lms have been obtained either by pulsed-laser ablation [11] or by spin-coating of the alkoxide precursor solution [8]. In the present study, we report the preparation of BBN powders and the growth of thin lms by a metalorganic decomposition (MOD) process. The BBN lms were deposited by spin coating of the precursor solution on both alumina (-Al2 O3 ) and Pt/TiO2 /SiO2 /(100)Si substrates. The thermal decomposition of the air-stable BBN precursor solution as well as the phase formation, crystallite

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size and morphology of the thin lms will be presented and discussed.

2. Experimental BBN powders and thin lms were prepared using a metalorganic decomposition according to the ow chart depicted in Fig. 1. A stoichiometric BBN precursor solution was prepared by dissolving barium 2-ethyl-hexanoate in 2ethylhexanoic acid at 80 C and followed by the addition of bismuth 2-ethylhexanoate. The niobium ethoxide, previously diluted in propan-2-ol in a glove box, is added to the solution and after the stirring of the mixture for 30 min, an homogeneous clear sol was obtained. The BBN thin lms were prepared by spin-coating of the precursor solution on both -Al2 O3 and Pt/TiO2 /SiO2 /(100)Si substrates, mounted on a Sulzer photoresist spinner at a rotation speed of 4000 rpm for 30 s. Each coating was dried at 250 C, for 2 min to remove organic compounds. Deposition and drying steps were repeated up to 10 cycles in order to prepare thicker lms. A BBN phase was obtained after ring at 700 C.

The thermal decomposition of the precursor solution was monitored by TG/DSC analysis using Netzsch STA 409 device in air and in He. The crystallisation process and phase identication was followed with temperature X-ray diffraction program at various temperatures, ranging from room temperature up to 900 C, in air, using a Siemens D5000 diffractometer, tted with an Anton Paar HTK variable temperature attachment. The powder as well as the thin lms were characterised by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) using, respectively, a Philips XL30 and a JEOL 2010 electron microscope. Simulated selected area electron diffraction (SAED) ring patterns were calculated using the EMS program package [12]. As a result of the calculations, a listing of the positions of the Bragg reections and their intensities were created. The intensities were calculated from the structure factors and corrected using a shape factor that depends on the crystal size. Dynamical effects were not considered in the calculations. To be able to compare the experimental and simulated SAED patterns, images were constructed from the intensity distributions as described in [13].

3. Results and discussion 3.1. BaBi2 Nb2 O9 powder The X-ray powder diffraction (XRPD) patterns representing the thermal evolution of the BBN precursor powder obtained after drying of the precursor solution at 250 C for 10 h are shown in Fig. 2. The powder was heated up to 900 C with a heating rate of 5 C min1 and the XRPD patterns were recorded every 50 C with a temporisation of 10 min at each temperature. As shown by the broad continuum in the XRPD patterns recorded at 400 C the starting precursor powder was primarily amorphous. BBN phase starts to form between 600 and 650 C with XRPD pat-

Fig. 1. Flow chart of the fabrication process of BBN powders and thin lms.

Fig. 2. In situ XRD patterns of the BaBi2 Nb2 O9 powder precursor (obtained from the solution dried at 250 C for 10 h in air).

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Fig. 3. SEM micrograph of BaBi2 Nb2 O9 powder (thermal annealing: 700 C for 10 h).

Fig. 5. X-ray powder diffraction patterns obtained after a deposit of (a) 1, (b) 6 and (c) 10 layers of the BBN precursor solution on a -Al2 O3 substrate (thermal annealing: 700 C for 30 min). Marked peaks belong to the BaBi2 Nb2 O9 phase, others can be attributed to the substrate.

room temperature (RT) to 1000 C in air (see Fig. 4). The TG curve indicates a change in mass of approximately 3% between RT and 550 C, accompanied with two exothermic peak and further weight loss of 4.4% up to 700 C. Since the rst and the second exothermic peaks disappeared after a TG/DSC measurement in inert atmosphere (He), the weight loss up to 550 C was assigned to the reaction of residual organic in the sample with the oxygen in air. The exothermic peak at 650 C corresponds to the crystallisation of the BBN phase, which is in agreement with the above XRD analysis. The last weight loss (4.4%) between 550 and 700 C may be due to the elimination of residual carbon, as has also been observed for a solgel derivated (Pb,La)(Zr,Sn,Ti)O3 powders [15].
Fig. 4. TG/DSC curves of the BaBi2 Nb2 O9 powder precursor (obtained from the solution dried at 250 C for 10 h in air).

3.2. BaBi2 Nb2 O9 thin lms In the MOD process, the lms deposited by spin-coating are amorphous and post deposition annealing of the lms have to be carried out. Regarding the synthesis of these BBN thin lms, the thermal conditions were obtained according to the crystallisation behaviour of the BBN powder precursor. In a rst step a dense alumina (-Al2 O3 ) substrate was used. After ring at 700 C, for 30 min, a polycrystalline thin lm of pure BBN phase is obtained independently of the numbers of coatings as indicated by the XRPD patterns given in Fig. 5. Marked peaks belongs to the tetragonal BaBi2 Nb2 O9 phase (SG: I 4/mmm), all other peaks can be attributed to the substrate. In Fig. 6, the SEM micrograph showing the surface of a BBN thin lm (10 layers deposited) allows to estimated the obtained grain size as being less than 100 nm, after ring 30 min at 700 C. In a second step, Pt/TiO2 /SiO2 /(100)Si substrates were used. After ring at 750 C for 30 min, crack-free lms of a monophasic BBN phase were obtained independently on

terns presenting characteristics of a sample with a low degree of crystallinity whereas after 700 C, the XRPD patterns show sharp peaks. After cooling down to room temperature, the XRPD patterns can be indexed using a tetragonal unit cell (SG: I 4/mmm, ICDD-PDF le number 40-0355) in agreement with the most recent results obtained on the crystal structure of BBN [14]. The cell parameters obtained from the whole pattern matching of the XRPD patterns are a = 3.9176(4) and c = 25.623(3). From this XRD study it is shown that BBN powders, without phase impurities, can be obtained after the calcination of a BBN precursor powder, without Bi excess, at 700 C. As shown with the SEM micrograph in Fig. 3, after 10 h at 700 C, a well crystallised BBN powder with a grain size in the range 250300 nm is obtained. The thermal evolution of the BBN precursor powder was also examined using thermal analysis (TG/DSC) from

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Fig. 8. Thermal evolution of the X-ray powder diffraction patterns obtained from a BBN thin lm (7 coatings) on Pt/TiO2 /SiO2 /(100)Si substrate. After 800 C, secondary phase is observed.

Fig. 6. SEM micrograph showing the surface of the lm obtained after 10 coatings of the BBN solution on a -Al2 O3 substrate (thermal annealing: 700 C for 30 min).

Fig. 9. Surface of a BBN thin lm (7 coatings) on a Pt/TiO2 /SiO2 /(100)Si substrate as observed by SEM.

Fig. 7. Cross-section of a BBN thin lm (10 coatings) on Pt/TiO2 / SiO2 /(100)Si substrate as observed in TEM.

the numbers of coatings. In Fig. 7 TEM cross-section of 10 layers of a BBN thin lm on a Pt/TiO2 /SiO2 /(100)Si substrate is represented. From the observed thickness, one can estimate that the average thickness is around 130 nm for one deposited layer. As shown in the XRPD patterns Fig. 8, at higher temperatures (above 800 C) a secondary phase appears, most probably, due to the vaporisation of bismuth, which is known to have a high vapour pressure. Despite the fact that only one diffraction peak is visible on the XRPD patterns, it is compatible with the BaNb2 O6 phase (ICDD-PDF le number 77-0589), which possesses the same Ba:Nb ratio as the one of the precursor solution. Using electron microscopy, the surface of the BBN lms was analysed from micro-scale (SEM) down to nano-scale (TEM). In Fig. 9, a SEM plane-view of a BBN lm deposited on a platinised Pt/TiO2 /SiO2 /(100)Si substrate (750 C for 30 min) is shown. The SEM reveals a relatively dense surface built up from the agglomeration of nanometer sized grains. This is conrmed by the TEM picture (Fig. 10) ob-

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techniques, it is shown that the obtained BBN lms are polycrystalline with nanometer sized randomly oriented grains. Further investigation will be concerned with the optimisation of nal annealing of BBN lms on Pt/TiO2 /SiO2 /Si substrates in order to obtain preferred orientation and the associated electrical properties.

Acknowledgements The authors thank Dr. P. Thomas and Dr. P. Marchet for their help in temperature X-ray powder diffraction and TG/DSC experiments. Dr. A. Ben an thanks the regional c council of Limousin for nancial support.
Fig. 10. TEM plane-view of a BBN thin lm (7 coatings) on a Pt/TiO2 / SiO2 /(100)Si substrate (thermal annealing: 750 C for 30 min). The inserted window shows the corresponding experimental SAED patterns together with a simulated one.

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tained from the same lm which appears clearly polycrystalline. The grain size can be estimated around 200 nm.

4. Conclusion Powder and thin lms of the m = 2 BaBi2 Nb2 O9 Aurivillius phase have been successfully prepared by a metal organic decomposition route using a stoichiometric precursor solution. After a calcination at 700 C of the air-stable metalorganic solution, a BBN powder with grains in the order of magnitude of nanometer is obtained. Crack-free lms of the BBN phase can also be obtained on both alumina (Al2 O3 ) and Pt/TiO2 /SiO2 /(100)Si substrates by spin-coating of this BBN precursor solution. The lowest post-deposition annealing temperature necessary to obtain a lm with a good crystallinity have been determined as 700 C for 30 min and 750 C for 30 min, respectively for the (-Al2 O3 ) and Pt/TiO2 /SiO2 /(100)Si substrates. Using both XRD and EM