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Applied Surface Science 257 (2011) 96009605

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Applied Surface Science

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Lead-free ferroelectric BaTiO3 doped-(Na0.5 Bi0.5 )TiO3 thin lms processed by pulsed laser deposition technique
Cristina Dragoi a,b , Marin Cernea a, , Lucian Trupina a
a b

National Institute of Materials Physics, Bucharest-Magurele, 077125, Romania University of Bucharest, Faculty of Physics, Bucharest-Magurele, 077125, Romania

a r t i c l e

i n f o

a b s t r a c t
The difculties in synthesizing phase pure BaTiO3 doped-(Na0.5 Bi0.5 )TiO3 are known. In this work, we reporting the optimized pulsed laser deposition (PLD) conditions for obtaining pure phase 0.92(Na0.5 Bi0.5 )TiO3 0.08BaTiO3 , (BNTBT0.08 ), thin lms. Dielectric, ferroelectric and piezoelectric properties of BNTBT0.08 , thin lms deposited by PLD on Pt/TiO2 /SiO2 /Si substrates are investigated in this paper. Perovskite structure of BNTBT0.08 thin lms with random orientation of nanocrystallites has been obtained by deposition at 600 C. The relative dielectric constant and loss tangent at 100 kHz, of BNTBT0.08 thin lm with 530 nm thickness, were 820 and 0.13, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 22 C/cm2 and a coercive eld of 120 kV/cm. The piezoresponse force microscopy (PFM) data showed that most of the grains seem to be constituted of single ferroelectric domain. The as-deposited BNTBT0.08 thin lm is ferroelectric at the nanoscale level and piezoelectric. 2011 Elsevier B.V. All rights reserved.

Article history: Received 20 May 2011 Received in revised form 9 June 2011 Accepted 13 June 2011 Available online 21 June 2011 Keywords: Lead-free ferroelectrics Thin lms Pulsed laser deposition Dielectric and piezoelectric properties

1. Introduction The Pb(Zr,Ti)O3 (PZT) perovskite is the most used ferroelectric material in electronic devices (sensors, actuators, memories, etc.) [1]. Lead is considered as a source of pollution due to its volatilization at the conventional processing temperatures of the lead-containing ceramic materials. The processing and properties of ferroelectric lead-free thin lms have a high interest for the present microelectronic industry. Sodium bismuth titanate (Bi0.5 Na0.5 TiO3 ) (BNT) and its solid solutions are considered a good alternative lead-free material to the PZT perovskite ceramics [2]. BNT has a perovskite structure and shows strong ferroelectricity, a relatively large remnant polarization (Pr = 38 C/cm2 ), and high Curie temperature (Tc = 320 C) [3]. However, their electromechanical properties are much lower than those of PZT ceramics. It has been reported that BNT ceramics modied with BaTiO3 (BT) [2] or Bi0.5 K0.5 TiO3 [4] showed improved dielectric and piezoelectric properties. The solid solutions (1 x)BNTxBT, (abbreviated as BNTBTx ) of rhombohedral BNT with tetragonal BaTiO3 (BT) have an area of coexistence of the two phases (rhombohedral and tetragonal), named morphotropic phase boundary (MPB) for x = 0.060.10 where bulk ceramics show enhanced dielectric prop-

erties, ferroelectric, piezoelectric, and pyroelectric activities [57]. There is very scarce literature about BNTBTx thin lms [811]. These BNTBTx thin lms have been deposited by pulsed laser deposition onto LaAlO3 and MgO single crystal substrates. A slightly higher number of publications have reported on pure BNT lms prepared by different deposition techniques (RF magnetron sputtering [12], PLD [13] or chemical solution deposition [1423]). The aim of this work was the optimization of the PLD deposition parameters to prepare BNTBT0.08 thin lms and their characterization. We investigated the microstructure and the phase composition of the crystalline lms and, the dielectric, ferroelectric and piezoelectric properties of as-prepared BNTBT0.08 thin lms. In this paper, we report also on the pure BNTBT0.08 thin lm domainstructure images obtained by PFM.

2. Experimental procedure The target of BNTBT0.08 home-made was elaborated in two steps process. First, BNTBT0.08 nanopowder was prepared by solgel method [24]. This powder was cold isostatic pressed and sintered at 1150 C, 1 h in air. The BNTBT0.08 thin lms were deposited on Pt-coated silicon (Pt/Ti/SiO2 /Si) substrates by pulsed laser deposition using a KrF excimer laser (Lambda Physik COMPex

Corresponding author. Tel.: +40 21 369 01 70x130; fax: +40 21 369 01 77. E-mail addresses: mcernea@inm.ro, marincernea@yahoo.com (M. Cernea). 0169-4332/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2011.06.075

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205) with a wavelength of 248 nm, and a repetition rate of 10 Hz. The laser beam impacts the rotating target with an energy density of 1 J/cm2 . The distance between the target and the substrate was xed at 5 cm, while the substrate temperature was maintained at 600 C. The BNTBT0.08 lms of thickness 600 nm were prepared by a number of 15,000 pulses in an oxygen atmosphere of 0.2 mbar. After deposition, the as-grown thin lms were gradually cooled down to room temperature. The crystallographic structure of the lm was analyzed by X-ray diffraction at grazing incidence at 2 using a Bruker D8 Advance diffractometer. The microstructure of the samples was investigated using a FEI Quanta Inspect F scanning electron microscope (SEM). For electrical measurements Pt electrodes was deposited on top. Deposition of metallic contacts was made by sputtering, using a metal mask with dimensions of 0.2 mm2 . The ferroelectric hysteresis (PE) loop was measured using a TF Analyzer 2000 equipped with a FE-Module (aixACCT). Dielectric properties of Pt/BNTBT0.08 /Pt capacitor were measured at 100 kHz frequency, at room temperature, using a HIOKI LCR-meter. The leakage current through the Pt/BNTBT0.08 /Pt capacitors was measured at room temperature using a Keithley 6517A programmable electrometer. An atomic force microscope (AFM) (MFP 3D SA, Asylum Research) was employed to obtain high resolution images of the surface. Olympus AC240-TM cantilevers (l = 240 m, resonant frequency 70 kHz, spring constant = 2 N/m, Pt coated) were used for simultaneous acquisition of topographic views and domain imagining using a MFP-3D Piezo Force Module. DART (Dual AC Resonance Tracking) measurement technique was used for study of the local electromechanical activity at nanoscale size. The small displacement of the thin lm induced by the converse piezoelectric effect was measured applying a sequence of dc bias up to 13.2 V superimposed on a AC modulation bias via the PFM tip directly on the lm surface without the top electrodes. 3. Results and discussion 3.1. Structure The XRD pattern of BNTBT0.08 thin lm is given in Fig. 1. BNTBT0.08 thin lm is well crystallized and shows a polycrystalline structure without any preferred orientation. The lm exhibits a dominant ABO3 perovskite phase (rhombohedral Bi0.5 Na0.5 TiO3 ), similar results were reported also by Sanjose et al. [20]. The lm structure seems to be not textured, the relative intensities of the
Fig. 2. SEM micrographs of the BNTBT0.08 thin lm: (a) plan-view image and (b) cross-section image.

peaks agree well with those given in ICDD-PDF No 70-9850. The X-ray penetration depth (90% absorption) in BNTBT0.08 thin lm for an incidence angle of 2 and 40 scattering angle (2) is around 0.7 m (calculated with the BRUKERAbsorb DX v.1.1.4 software). Thus the beam reaches the substrate but the Pt peaks do not occurs because of the high degree of texturing of Pt(111). Crystallite size and microstrain were derived from the line broadening using the BRUKERTOPAS software. It was obtained a mean crystallite size of 44 nm and a microstrain value of 0.031. In order to correct for the instrumental line breadth, a heat-treated ceria powder proved to not produce measurable size and strain broadening, has been used.

3.2. Microstructure Fig. 2 shows the surface morphology and cross-section micrographs of the BNTBT0.08 thin lm. It can be seen that the lm possesses homogeneous microstructure with ne grains of 90 nm average size and uniform grain size distribution (Fig. 2(a)). Cluster aggregation has not been observed. The grains are more or less polyhedral shape. The lm

Fig. 1. XRD patterns (Cu K coated silicon.

radiation) of BNTBT0.08 thin lm deposited on Pt-

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Fig. 3. PE hysteresis loop of a BNTBT0.08 thin lm under various electrical elds.

deposited at 600 C exhibits a dense structure, with few pores being observed at the grain boundaries and junctions. Fig. 2(b) shows a cross-sectional SEM image of a typical columnar thin lm. The tilted columnar morphology of the columnar thin lm is clearly evident in the image, with the cross-sectional diameter of the columns roughly 90 nm. The BNTBT0.08 lm is uniform in thickness (Fig. 2(b)) and its thickness is about 530 nm. Similar value of thickness was measured by ellipsometry (not shown here).

3.3. Dielectric and piezoelectric characterization Fig. 3 shows the PE loops of the BNTBT0.08 thin lm measured under different electric elds at a frequency of 10 kHz. Well-dened PE hysteresis loops are observed and the saturation of the hysteresis loop as a function of voltage is key evidence of intrinsic ferroelectricity in the BNTBT0.08 thin lm. The observed remnant polarization 2Pr and coercive eld Ec , are 22 C/cm2 and 120 kV/cm, respectively. These values are comparable to that reported for BNTBT0.06 thin lms deposited by solgel [25,26]. Fig. 4 demonstrates the small-signal (100 kHz) dielectric constant and loss tan dependence on dc bias eld in the lm. Dielectric constant exhibits a signicant change with applied electric eld (Fig. 4(a)). This indicates that ferroelectric domain structure, in addition to ionic and electronic polarizations, contributes to the polarizabilty of the thin lm. The dielectric constant and loss vs. electric eld plots appear symmetric with a hysteresis behavior typical of ferroelectric capacitors. The maximum dielectric constant occurs at a eld of 20 kV/cm, in both directions. The dielectric constant and loss were measured as function of frequency at room temperature, as shown in Fig. 4(b). The typical values of dielectric constant and loss of the BNTBT0.08 thin lm, measured at 100 kHz, are 820 and 0.13, respectively. Fig. 5 shows the current density (J) as a function of electric eld for the BNTBT0.08 thin lm measured at room temperature. Current density has a value of about 1.5 109 A/cm2 at low electric eld but present an exponential increase with electric eld. The value of the current density is 4.7 105 A/cm2 , at an electric eld of 100 kV/cm. This value is comparable to those reported for BNT thin lm deposited by RF-sputtering and by solgel (6 105 A/cm2 [12], respectively, 1.6 105 A/cm2 [22] at 100 kV/cm). The localized oxygen vacancies trapped at grains boundaries can pin domains and result in leakage current and polarization degradation, common phenomenon for the ferroelectric thin lms.
Fig. 4. Electrical eld dependence of the dielectric constant and loss, at room temperature (a) and frequency dependences of dielectric constant and loss (b).

Vertical piezoresponse force microscopy (VPFM) employs the converse piezoelectric effect to measure small surface displacements resulting from the application of an external AC eld at the contact between a conducting tip and the sample surface. The tip follows the expansion and contraction of the surface allowing the voltage-dependent piezoelectric response to be mapped simultaneously with topography using a lock-in technique. A more comprehensive description is provided elsewhere [23]. Fig. 6(a) and (b) are topography and amplitude VPFM images, respec-

Fig. 5. Current density as a function of electric eld for the Pt/BNTBT0.08 /Pt thin lm capacitor at room temperature.

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Fig. 6. Large-scale maps of piezoresponse (a) topography and (b) amplitude without external biasing of BNTBT0.08 thin lm exhibiting spontaneous polarization.

tively. The topographic image of the sample shows a grained microstructure with average roughness Rms = 20.4 nm and, average grain size of approximately 90 nm (Fig. 6(a)). The feature sizes in topography and VPFM images are comparable and, the boundaries of uniformly polarized regions coincide with topographic features. Regions of bright contrast can be seen in the amplitude VPFM image [indicated with a black arrow in Fig. 6(b)], showing high piezoelectric response. These regions are outlined by narrow unpolarized regions which are intergrain boundaries separating two grains. Since the vertical PFM technique is sensitive only to the component of polarization normal to the lm surface, grains with in-plane polarization (with vanishing out-of-plane polarization) exhibit an intermediate contrast (dark contrast in the amplitude PFM image). One such region is indi-

cated with a white arrow in Fig. 6(b). It can also be observed that a large proportion of grains have a multidomain structure. For switching spectroscopy PFM (SS-PFM) measurement, an additional function generator applies the switching bias to the scanning tip to obtain piezoelectric switching loops. The switching bias is a series of voltage pulses that are combined with the small AC piezoresponse bias. The pulse polarizes the local area when it is on, and then the piezoresponses from the local area are recorded when the dc pulse is off or on. The resulted piezoresponse when the dc pulse is off corresponds to the piezoelectricity of the BNTBT0.08 microstructure at remnant state after polarization. The amplitude of the AC bias was 4 V, and the maximum dc pulse for to the switching loop measurement was 20 V.

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prepared by PLD is a good candidate for lead-free piezoelectric applications. Acknowledgement This work was supported by Romanian National Program PNCDI II, Contract no. 72-153/2008 and Contract No. POSDRU/6/1.5/S/24. References
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Fig. 7. Remnant piezoresponse (a) amplitude and (b) phase measured as a function of applied dc voltage.

Fig. 7(a) and (b) shows typical remnant piezoresponse amplitude and phase measurements, respectively, measured as a function of applied dc voltage. The polarization switching and hysteresis show clearly that as deposited the BNTBT0.08 thin lm is ferroelectric at the nanoscale level. The average coercive voltage for the well-behaved loops is approximately 9 V. From this, the determined coercive eld is 150 kV/cm. These results demonstrate the existence of local piezoelectric and ferroelectric responses, in BNTBT0.08 thin lms on Pt/TiO2 /SiO2 /Si substrates synthesized by pulsed laser deposition at 600 C. 4. Conclusions In summary, this study investigated the dielectric and piezoelectric properties of MPB lead free BNTBT0.08 thin lms, grown on Pt/Ti/SiO2 /Si substrate, in optimized pulsed laser deposition conditions. The results show that the BNTBT0.08 thin lm exhibits a well-dened ferroelectric hysteresis loop at room temperature with a remnant polarization 2Pr of 22 C/cm2 and a coercive eld Ec of 120 kV/cm. The leakage current density in BNTBT0.08 thin lm is relatively low. We have demonstrated also the existence of local piezoelectric and ferroelectric responses, in BNTBT0.08 thin lms on Pt/TiO2 /SiO2 /Si substrates obtained by pulsed laser deposition at 600 C. The results indicate that the BNTBT0.08 thin lm

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[26] G. Yiping, A. Daisuke, S. Kazauki, I. Makoto, Dielectric and ferroelectric properties of highly (1 0 0)-oriented 0.94(Na0.5 Bi0.5 )TiO3 0.06BaTiO3 thin lms grown on LaNiO3 / Al2 O3 /Si substrates by chemical solution deposition, Solid State Sci. 10 (2008) 928933.