Applied Surface Science 283 (2013) 759–763 Contents lists available at SciVerse ScienceDirect Applied Surface Science journal homepage: www.elsevier.com/locate/apsusc Electrical behaviors of c-axis textured 0.975Bi0.5 Na0.5 TiO3 –0.025BiCoO3 thin films grown by pulsed laser deposition Feifei Guo a , Bin Yang a,∗ , Shantao Zhang b,∗∗ , Danqing Liu c , Fengmin Wu a , Dali Wang c , Wenwu Cao a,d a Department of Physics, Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150080, China Department of Materials Science and Engineering & National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, China c School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150080, China d Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA b a r t i c l e i n f o Article history: Received 16 May 2013 Received in revised form 28 June 2013 Accepted 4 July 2013 Available online 12 July 2013 Keywords: Ferroelectric Thinfilm Pulsed laser deposition Local piezoelectric property Domain switching a b s t r a c t The thin films of 0.975Bi0.5 Na0.5 TiO3 –0.025BiCoO3 (BNT-BC) have been successfully deposited on (1 1 1) Pt/Ti/SiO2 /Si (1 0 0) substrates by pulse laser deposition and their ferroelectric, dielectric, local piezoelectric properties and temperature dependent leakage current behaviors have been investigated systematically. X-ray diffraction indicates the films are single phased and c-axis oriented. The thin films exhibit ferroelectric polarization–electric field (P–E) hysteresis loop with a remnant polarization (Pr ) of 10.0 C/cm2 and an excellent fatigue resistance property up to 5 × 109 switching cycles. The dielectric constant and dielectric loss are 500 and 0.22 at 1 kHz, respectively. The tunability of the dielectric constant is about 12% at 20 kV/mm. The piezo-phase response hysteresis loop and piezo-amplitude response butterfly curve are observed by switching spectroscopy mode of piezoelectric force microscope (SS-PFM) and the piezoelectric coefficient d33 is about 19–63 pm/V, which is comparable to other reports. The dominant leakage current conduction mechanisms are ohmic conduction at low electric field and Schottky emission at high electric field, respectively. Our results may be helpful for further work on BNT-based thin films with improved electric properties. © 2013 Elsevier B.V. All rights reserved. 1. Introduction Lead-based piezoelectric materials exemplified by Pb(Zr,Ti)O3 (PZT) are widely used for sensors, actuators, and ultrasonic motors in virtue of their excellent piezoelectric properties [1,2]. However, lead-pollution and environmental problems caused by the use of lead-containing piezoelectric materials have become increasingly serious because of the toxicity of lead oxides. Up to now, a lot of attention has been paid to lead-free piezoelectric materials due to increasing environmental and healthy concerns over the widely used lead-containing materials [2–4]. Among them, Bi0.5 Na0.5 TiO3 (BNT) and its solid solutions have good piezoelectric properties and thus BNT-based materials are considered to be the potential candidates for replacing PZT. In the past two decades, considerable attention has been focused on investigating the structure and electric properties of ∗ Corresponding author. Tel.: +86 13836127592. ∗∗ Corresponding author. Tel.: +86 13951976481. E-mail addresses: binyang@hit.edu.cn (B. Yang), stzhang@mail.nju.edu.cn (S. Zhang). 0169-4332/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.apsusc.2013.07.013 the BNT-based materials in bulk form, detecting that BNT can form morphotropic phase boundary with other ferroelectrics, thereby the electric properties can be dramatically improved [5–8]. Recently, as potential alternative to lead-based thin films in application, great efforts have been made to the growth and characterization of BNT-based thin films [9–18]. However, it should be noticed that the studying on BNT-based thin films is in an early stage compared with that on BNT-based ceramics. It is difficult to prepare high quality BNT-based films with high electric performances and there are limited reports on the local ferro/piezoelectric properties [11,15,18–23]. Therefore, it is highly required to seek for high-performance BNT-based thin films. In our previous work, it has been shown that BiCoO3 doped BNT ceramics with rhombohedral–tetragonal morphotropic phase boundary (MPB) components possess excellent electric properties [24]. However, the ferroelectric, dielectric, leakage current properties and nanoscale characterization of piezoresponse of BNT-BC thin films are still missing. In this study, we describe the ferroelectric, dielectric, piezoelectric properties and leakage current behaviors of the 0.975Bi0.5 Na0.5 TiO3 –0.025BiCoO3 , which corresponds to the MPB composition, thin films deposited on (1 1 1) Pt/Ti/SiO2 /Si (0 0 1) substrates by pulsed laser deposition (PLD). 760 F. Guo et al. / Applied Surface Science 283 (2013) 759–763 Fig. 1. XRD patterns of (a) BNT-BC thin films and (b) (1 1 1) Pt/Ti/SiO2 /Si (0 0 1) substrates. Fig. 2. (a)Room temperature P–E hysteresis loops; (b)The cross-section SEM micrograph of the BNT-BC thin films. 2. Experimental The 0.975Bi0.5 Na0.5 TiO3 –0.025BiCoO3 (BNT-BC) ceramics used as PLD target was prepared by the conventional solid state reaction with 20% excess Bi and Na for compensation of the volatility during ceramic sintering and thin film depositing. The BNT-BC thin films were deposited on (1 1 1) Pt/Ti/SiO2 /Si (1 0 0) substrates at 700 ◦ C in a flowing oxygen partial pressure of 25 Pa by PLD using a krypton fluoride (KrF) excimer laser with a wavelength of 248 nm. The laser energy and repetition rate were kept at 250 mJ and 5 Hz, respectively. The distance between the target and the substrate was about 40 mm. After deposition, the films were in situ annealed at 700 ◦ C under 0.5 atm oxygen pressure for 10 min and then cooled down to room temperature naturally. In order to investigate the electrical properties of the thin films, Pt top electrodes of 200 m in diameter were sputtered using a shadow mask by DC magnetron sputtering. The crystal structure of the films was characterized by X-ray diffraction (XRD) with a Cu K␣ radiation. The ferroelectric properties and leakage current were studied by precision premier II (Radiant Tech. USA). Dielectric characteristics were measured using a HP4294A impedance analyzer. Local ferroelectric and piezoelectric properties of thin films were evaluated by piezoelectric force microscope (PFM, Model MFP-3D, Asylum Research, USA) using switching spectroscopy mode (SS-PFM). During the SS-PFM measurement, the conductive Pt/Ir coated tip and the conductive Pt substrate are the top and bottom electrodes, respectively. 3. Results and discussion The X-ray diffraction (XRD) patterns of BNT-BC thin films and (1 1 1) Pt/Ti/SiO2 /Si (1 0 0) substrates are shown in Fig. 1(a) and (b) for comparison, respectively. It can be seen that the thin films are highly (0 0 1) oriented without detectable second phases. The average thin film thickness is 745 nm, observed from cross-section SEM measurements shown in Fig. 2(b). The room temperature polarization–electric field (P–E) hysteresis loops of the BNT-BC thin films are measured under different elelctric fields at a frequency of 2 kHz, typical results are shown in Fig. 2(a). As can be seen, the thin films have P–E hysteresis loops, indicating the ferroelectric nature. The saturation polarization (Ps ) and remnant polarization (Pr ) are 26.4 C/cm2 and 10.0 C/cm2 , respectively, while the average coercive field (Ec ) is 7.4 kV/mm. It should be noticed that the Pr of the films is much lower than that of BNT-BC ceramics, whereas the Ec is much higher, which may be attributed to the strong pinning of non-180◦ domain walls caused by size effect [25]. The difference between the absolute values of +Ec and −Ec is observed which arises from the imprint effect: trapped electronic charges near the ferroelectric-electrode interface can cause internal space charge field [12,25]. Normalized ferroelectric fatigues are measured with triangle wave with the amplitude of 8 V and the frequency of 100 kHz. The fatigure behavior is demonstrated in Fig. 3(a). Following the completion of 5 × 109 switching cycles, the polarization decreases approximately 10%, indicating the thin films possess a excellent fatigue resistance, which is further confirmed by the P–E loops measured before and after fatigue tests, as shown in Fig. 3 (b). Fig. 4 shows the dielectric constant (εr ) and loss tangent (tanı) of the BNT-BC thin films as a function of frequency. The εr decreases monotonously from 500 at 1 kHz to 290 at 1 MHz. On the other hand, the tanı decreases from 0.22 to 0.12 with the frequency from 1 kHz increasing to 100 kHz and then increases to 0.3 at 1 MHz. Clearly, the εr and tanı reveal significant frequency dispersion in the range of 1 kHz–1 MHz. This frequency dispersion in εr and tanı can be attributed to space charge [26]. Fig. 3. (a) Normalized ferroelectric fatigue as a function of polarization switching cycles; (b) P–E loops measured before and after 5 × 109 switching cycles. F. Guo et al. / Applied Surface Science 283 (2013) 759–763 Fig. 4. Relative dielectric constant and dielectric loss as a function of frequency. Fig. 5. Electric field dependence of the relative dielectric constant. The dielectric constant–electric field (εr –E) curves of the BNT-BC thin films measured at 100 kHz are shown in Fig. 5. As shown, the strongly nonlinear behavior is observed in εr –E, indicating typical ferroelectric capacitors. The reason for change of εr with applied electric field might be the contribution of domain wall motion 761 Fig. 6. Switching spectroscopy piezoresponse force microscopy (SS-PFM) results of the BNT-BC thin films, (a) phase–voltage hysteresis loop, (b) amplitude–voltage butterfly curve. during the ferroelectric domain switching to dielectric constant. The dielectric tunability measured with dc bias electric field of 20 kV/mm is calculated to be 12%, which can comparable to that of pure BNT and BNT-based lead free ferroelectric thin films [12,27]. To confirm the local ferroelectricity and piezoelectricity of the BNT-BC thin films, polarization switching was examined by SS-PFM, which is widely used to understand the local switching behavior in ferroelectrics. During the SS-PFM measurement, a DC bias voltage of ±20 V, corresponding to a field of 27 kV/mm, was applied through the conductive tip to the BNT-BC thin films, which is sufficiently large to switch the polarization below the tip since the coercive field is 7.4 kV/mm. Simultaneously, a small ac voltage with drive amplitude of 0.5 V and a contact resonance frequency of 290 kHz between the tip and the conductive substrate was superimposed on the top of DC switching signal, inducing a local surface vibration due to the piezoelectricity of the thin films. Fig. 6(a) and (b) show the standard phase–voltage hysteresis loop and amplitude–voltage butterfly curve, respectively. The phase response hysteresis loop is symmetric with respect to the applied Fig. 7. (a) Leakage current density J as a function of electric field E for the BNT-BC thin films measured at different temperatures. Analysis of the leakage current based on (b) SCLC/ohmic, (c) Schottky, and (d) Poole–Frenkel mechanisms, respectively. 762 F. Guo et al. / Applied Surface Science 283 (2013) 759–763 voltage, and extremely sharp polarization switching is observed in the hysteresis loop with the 180◦ phase reversal, indicating the existence of 180◦ domains in the BNT-BC thin films and the nature of ferroelectricity [28,29]. In the amplitude response butterfly curve, the maximum field induced displacement is measured to be approximately 0.95 nm for BNT-BC thin films. The longitudinal piezoelectric coefficients d33 can be calculate according to A = d33 Vac Q [29,30], where A is piezoresponse amplitude, Vac is AC driving voltage applied to the sample through the conductive cantilever tip, and Q is quality factor and typical ranges from 30 to 100 for contact resonances [31]. The d33 is estimated between 19 and 63 pm/V, which can comparable to other reported BNT-based thin films [11,15,18]. Fig. 7(a) shows the typical current density J of the BNT-BC thin films as a function of applied electric field E at different temperatures. As shown in Fig. 7(a), the J increases monotonically with increasing temperature and the J–E characteristics are symmetric under positive and negative bias voltage at all temperature. To analyze the leakage current mechanism, the study is focused on the case that the positive bias is applied to the bottom electrode. Based on the previous reports on lead free thin film, the predominant conduction mechanisms of Pt/ferroelectric film/Pt capacitor may be the Ohmic conduction or space charge limited current (SCLC) conduction at low electric field and Poole–Frenkel (PF) emission or interface-limited Schottky emission (SE) at high electric field [32–34]. The Ohmic and SCLC conduction can be expressed by Eqs. (1 and 2) [32–34], respectively. between optical-frequency dielectric constants ε∞ ≈ 4.4–6.25 and static dielectric constant of the BNT films [34]. In Fig. 7(d), the leakage current characteristics except for at 223k satisfy the PF equation at high electric field. Using this model, the values of εr obtained from the slopes are 1.57 × 104 –2.08 × 104 exceeding the range of relative dielectric constant. Therefore, Schottky emission is the dominant conduction mechanism in BNT-BC thin films at high electric field. 4. Conclusion J = neE, (1) In summary, single phase 0.975Bi0.5 Na0.5 TiO3 –0.025BiCoO3 thin films were deposited on (1 1 1) Pt/Ti/SiO2 /Si (1 0 0) substrates by pulse laser deposition and their ferroelectric, dielectric, local piezoelectric properties and temperature dependent leakage current behaviors were investigated systematically. The thin films exhibit ferroelectric P–E hysteresis loops with a Pr of 10 C/cm2 and excellent fatigue resistance. The typical dielectric constant and dielectric loss are 500 and 0.22 at 1 kHz, respectively, with dielectric tunability of 12% at 20 kV/mm. The piezo-phase response hysteresis loop and piezo-amplitude response butterfly curve are observed by SS-PFM, and the piezoelectric coefficient d33 is about 19–63 pm/V, which is comparable to other reported BNT-based thin films. The dominant leakage current conduction mechanisms in the thin films are Ohmic conduction at low electric field and Schottky emission at high electric field, respectively. Our results may be helpful for searching for lead-free ferroelectric thin films with improved electric properties. J = 9ε0 εr E 2 /8d, (2) Acknowledgments Where n is the density of free electrons, e is the magnitude of the electronic charge, is the electronic mobility, ε0 is the permittivity of free space, εr is the dielectric constant of thin films and d is the thickness of the films. The Schottky and Poole-Frenkel (PF) emissions obey Eq. (3) and Eq. (4) [32–34], respectively. J = AT 2 exp J = 0 E exp ˇS E 1/2 − ˚S kB T ˇPF E 1/2 − E1 kB T (3) , (4) where ˇS = e3 /4ε0 εr 1/2 , 1/2 is the Schottky coefficient, ˇPF = e3 /ε0 εr is the Poole-Frenkel coefficient, A is the Richardson constant, ˚S is the barrier height in the interface, 0 is the sampledependent zero-field conductivity, E1 is the trap ionization energy, kB is the Boltzmann’s constant, T is the absolute temperature, and εr is dielectric constant of the films. To further explore the conduction mechanisms of the BNT-BC films at low electric, according to the Eqs. (1 and 2), the ln(J) as functions of ln(E) at different temperature are plotted in Fig. 7(b). At all measured temperatures, the ln(J)−ln(E) can be fitted well by the function ln(J) = ˛ln(E)+ˇ. The coefficients ˛ obtained from the linear fiting are approximately equal to one instead of two implying that the dominant conductivity mechanism of BNT-BC thin films is ohmic conduction rather than SCLC at low electric field. In view of the Eqs. (3 and 4), to investigate the possibilities of Schottky and Poole-Frenkel mechanism, ln(J/T2 ) versus E1/2 and ln(J/E) versus E1/2 are shown in Fig. 7(c) and (d), respectively. As shown in the inset of Fig. 7(c), the date at all temperature fit well to the Schottky emission at high electric field with slope values falling in the range of 5.35 × 10−4 to 6.25 × 10−4 . The relative dielectric constant values can be determined to be 9.98–24.38 by calculating the slope values and ˇS . These values are located on the range This research was supported by the Key Technologies R&D Program of China under Grant No. 2013BAI03B06, the National Nature Science Foundation of China (10704021, 51102062, and 11174127), the Key Scientific and Technological Project of Harbin (Grant No. 2009AA3BS131), the Postdoctoral Foundation of Heilongjiang Province (Grant No. LBH-Z10147), and the Fundamental Research Funds for the Central Universities (Grant No. HIT. NSRIF. 2011011). References [1] G.H. 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