FABRICATION OF PZT BY SOL-GEL METHOD

Bing-Huei Chen1*, Long Wu2, Ming-Cheng Chure2, Yeong-Chin Chen3

1

Department of Electrical Engineering, Nan Jeon Institute of Technology, 178 Chau-Chin Road, Yen-Shui , Tainan City 73746, Taiwan, R.O.C

Department of Electronics Engineering, Far-East University, 49 Jhonghua Road, Sinshih ,Tainan City, Taiwan, R.O.C
3

Department of Computer Science & Information Engineering, Asia University, 500, Lioufeng Rd., Wufeng, Taichung 41354, Taiwan, R.O.C *E-mail: chenbh@mail.njtc.edu.tw

The sol-gel method was used to prepare the high purity lead zirconate titanate Pb(Zr,Ti)O3 (PZT) piezoelectric ceramic powders. To determine the optimum fabrication process, the influence of calcined conditions and sintering conditions on the characteristics of PZT bulk was studied. After calcined at 900oC for 4hr, and then sintered at 1100oC for 2hr, the density of the bulk ceramics nearly equal to 8g/cm3. The polycrystalline PZT thin film was prepared by using spin coating method. The PZT thin films with lower gel concentration of 0.2M were used, and deposited on Al/Si3N4/Si(100) substrate. After drying at 150oC, pre-baking at 350oC and sintering at 600oC~700oC, the amorphous PZT thin films have been changed to perovskite-type crystal structure. The influence of gel solutions concentration and heating conditions on the morphology of PZT thin films were discussed. The cracking problem was alleviated by employing lower gel concentration of 0.2 M with a drying at 150oC for 5 min and a pre-baking at 350oC for 10 min, and then sintering at 700oC for 30 min with a heating rate 50oC/min. The values of the remanent polarization (Pr) and coercive field (Ec) are 11.39c/cm2 and 84.52 kV/cm, respectively. Keywords: Lead zirconate titanate, sol-gel method, spin coating method, piezoelectric thin film

1.

Introduction

Lead zirconate titanate (PZT) piezoceramic system functions discovered by Jaffe et al. [1] and the basic components are the ferroelectric lead titanate (PbTiO3), anti-ferroelectric lead zirconate (PbZrO3) phase, with tetragonal and orthorhombic crystal structures, respectively. PbTiO3 and PbZrO3 are soluble mutually in all proportions. Morphotropic phase boundary (MPB) compositions (Zr/Ti~0.53/0.47), i.e., the rhombohedral and tetragonal phase coexisted was well known to have superior dielectric, elastic and piezoelectric properties including a high electromechanical coupling factor, large spontaneous polarization, high dielectric constant, low dielectric loss and low internal stress, etc,[2]. Ceramic processing has been made to control the amount, uniformity and distribution of dopants by modifying their ceramic characteristics. Modifications of the PZT materials and the effects of dopants had been researched extensively to improve its piezoelectric properties for various applications in gas sensor[3], MEMS devices[4-6], ferroelectric random access memory (FRAM)[7], infrared detectors, actuators, 978-1-4244-9821-5/10/$26.00 2010 IEEE
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piezoelectric resonators, transducers, energy harvesting, etc[8-10]. Therefore, PZT piezoelectric materials have become one of the most promising candidates for device applications. PZT powders could be fabricated by such methods as sol-gel, solid-state reaction, co-precipitation and hydrothermal solution. Budd et al. developed the sol-gel method to fabricate PbTiO3, PbZrO3, PZT and PLZT thin films[11]. Also, the sol-gel method is currently under investigation for the fabrication of nanoscale ceramic materials. Recently, we developed a safer solgel method that utilizes non-hazardous propyl alcohol as a solvent. Thus, the main purpose of this investigation is to evaluate the lower temperature preparation of PbZr0.53Ti0.47O3 (PZT) bulk ceramic under various firing conditions including calcining and sintering to finally determine the high-performance composition of the PZT ceramic suitable for piezoelectric devices. Using a simple method to obtain fine and uniform PZT powders and scaling down the processing temperature by 100oC~200oC relative to the solid-state reaction method enable suitable processing conditions to be obtained.

Besides, in the present paper, the PZT thin films coated on Pt/Ti substrate had been reported in many literatures [12-14]. Checking the Al against the Pt, Al is cheaper than Pt and can be directly deposited on Si3N4/Si substrate to simplify the preparation of PZT films comparing with Pt/Ti/SiO2/Si, so it could reduce production step and costs in manufacturing. Therefore, the Al/Si3N4/Si (100) substrate was used and the PZT ferroelectrics thin films were prepared by sol-gel method and spin coating technique. 2. Experimental Setup

The sol-gel method was used to synthesize PbZr0.53Ti0.47O3 stock solutions and gel powders. Propyl alcohol (1-Pro) as solvent, lead acetate, Pb(CH3CO2)2 3H2O(AcPb), zirconium n-propoxide, Zr(C3H7O)4(n-Zr), and titanium isopropoxide, Ti[(CH3)2CHO]4(i-Ti) as raw precursors, and acetic acid (CH3COOH)(OAc) as chelating agent and catalyst have been used. The final solutions must be stable under ambient conditions and have a composition close to PbZr0.53Ti0.47O3. To prepare the 0.5 M PZT gel solutions, lead acetate was added to propyl alcohol in the proportion of 1 g to 0.1 ml, lead acetate, zirconium n-propoxide and titanium isopropoxide in a desired nominal molar ratio of 53:47. An excess of 5 wt% PbO with respect to the nominal composition was adopted in order to compensate for preferential PbO evaporation during high temperature firing, then appropriate quantities of PZT solutions can be homogenized by stirring. Essentially, the lead acetate was dissolved in propyl alcohol, and then the solution was heated to 110oC and refluxed for 2 h to remove the water of crystallization. The dehydrated solution was cooled to 90oC before the required quantities of zirconium npropoxide, titanium isopropoxide and acetic acid were added sequentially. After that, the solution was heated to 110oC again. Zirconium n-propoxide must be added first because it reacts with acetic acid to form solutions that will not hydrolyze[15]. After refluxing and vigorously stirring for 1 h, the titanium isopropoxide was added in the same manner as zirconium npropoxide, the processing lasting for 2 h. Light-yellow and clear PZT stock solutions were obtained by aircooling. Subsequently, PZT gels were heated to 110oC~120oC for 15~25 min, and when they solidified and were cooled in air, resulting in fine PZT gel powders. The dried PZT gel powders were capsulated in

an Al2O3 crucible to prevent the loss of Pb, and this was put into a high temperature furnace and calcined at 400oC~900oC for 1 h to 4 h. All the calcined powders were ground and compacted into disk samples having 12 mm in diameter and 1 mm in thickness. These were then sintered at 1000oC~1300oC for 2 h to obtain gelderived PZT piezoceramics. 0.5 M concentration of PZT gel solutions were be diluted by the addition of distilled water. Diluted 0.2~ 0.3 M PZT gel solutions were deposited on Al/Si3N4/Si (100) substrate by spin coating; dried at 150oC in a hot plate and then pre-baked at 350oC in a furnace, and these processes repeatedly for several times until the film thickness nearly equal to 3~5m. After the last cycle, the films were sintered in the same furnace at 600oC~700oC, and a fast heating rate (50oC/min~150oC/min) was used to rising the temperature from 350oC to desired sintering temperature to get PZT ferroelectric thin films. The crystal phase structure including bulk and ferroelectric thin films PZT materials was examined using a Rigaku X-ray diffractionmeter (XRD) with CuK radiation (= 1.5418), scanned from 20o to 60o at a scanning speed of 4o/min, operating voltage 30 kV, current 20 mA, to identify whether the pyrochlore phase disappear or not. In addition to, surface morphology including grain size variations, crack, et al., was analyzed by high resolution scanning electron microscopy (SEM). The relative density of PZT ceramics was measured by an Archimedess method. The samples were polished, cleaned and coated with a 10 mm diameter silver electrode to get a better ohmic contact for electric properties measurement. The samples were poled under high electric field 3.0 kV/mm at elevated temperature 90oC for 30 min in the silicone oil bath. Polarization-electric field (P-E) characteristics were evaluated at a frequency of 1 KHz using a SawyerTower bridge equipped with an Agilent Technologies 54622A oscilloscope, where the film deposited on the Al/Si3N4/Si substrate covered with the mesa served as the sample. The mesa layer is served as the lower electrode, and coated with a 2 mm diameter upper silver electrode to obtain good ohmic contact. 3. Results and Discussion

Table 1 demonstrated the results of ICP/MS, it found that if the reflux time of Pb:Zr:Ti = 2:1:2 (sample No.S5), the Zr/Ti ratio of the gel solutions were greater

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than 1 and close to PbZr0.53Ti0.47O3, the PZT gel solutions were clear and light yellow without precipitates. If the reflux time of Pb:Zr:Ti deviated from the ratio 2:1:2 (sample No.S1 to S4), the Zr/Ti ratio of the gel solutions were less than 1, and precipitates occurred though the PZT gel solutions were clear and light yellow. The results indicated that PZT gel solutions had improper reflux time ratio, the reaction between Zr and Ti was not complete, so PZT composition was off the MPB and precipitates happened. Namely, the reflux time of lead acetate, zirconium npropoxide and titanium isopropoxide played an extremely important role.
Sample S1 S2 S3 S4 S5 Table 1 The reflux time and Zr/Ti ratio. Pb:Zr:Ti Color Precipitate Reflux time (hr) 0.5:0.5:0.5 1:1:1 1:1:2 2:1:1 2:1:2 Light yellow Light yellow Light yellow Light yellow Light yellow Yes Yes Yes Yes No Zr/Ti 35/65 <1 44/56 <1 48/52 <1 45/55 <1 52/48 >1

known that the crystalline phase of PZT film depends on the fabrication processes.

Figure 1. X-ray diffraction patterns for PZT powders calcined at 900oC as a function of calcining time, and then sintered at 1100oC for 2hr.

No.S5 gel solutions were made into gel powders. In Fig. 1, with a calcining temperature higher than 850oC, PZT phase transformation was completed and the pyrochlore phase disappeared. From X-ray diffraction analysis, it was demonstrated that the formation of the pyrochlore phase appeared to be necessary before crystallization to the perovskite structure occurred. The densities of all the fired PZT ceramics samples were measured by the Archimedes method. It was evident that at a calcining temperature of 900oC for 30 min, followed by sintering at 1100oC for 2 h, the samples practical density was close to the theoretical value of 8g/cm3. It was deduced that calcining at an appropriate sintering temperature and time makes the bulk ceramic powder reaction complete; the pyrochlore phase was transformed into the perovskite phase, with good fluidity and density, and thus density was increased. Fig. 2 shows the X-ray diffraction (XRD) patterns of the 0.2 M PZT films deposited on Al/Si3N4/Si (100) substrate as a function of sintering temperature and heating rate. From the results, it found under constant sintering time and heating rate, the pyrochlore phase will exist at lower sintering temperature, but it has been vanished at higher sintering temperature. It is well

Figure 2. XRD patterns of PZT thin films sintered at various temperature for 30 min at 50oC/min.

Fig. 3 shows the XRD pattern of 3 layers 0.2 M PZT films with different processes. In Fig. 3(a) PZT thin film was dried at 150oC, pre-baked at 350oC, and then sintered at 700oC for 30min with a heating rate 50oC/min; these processes were repeated for 3 times. In Fig. 3(b) PZT thin film was dried at 150oC and then prebaked at 350oC, these processes were repeated for 3 times, and then the whole sintering at 700oC for 30 min with heating rate 50oC/min. The processes of Fig. 3(c) were the same as that of Fig. 3(b) but the heating rate was slower, only 5oC/min. The volume fraction of pyrochlore is 4.03 %, 0 % and 4.40 % for Fig. 3(a), (b) and (c), respectively. A sequence of drying, pre-baking and sintering, as the above condition will make Pb disappear but pyrochlore phase still exists during higher temperature, unless prompt heat treatment at faster ramping rate. Fig. 4 shows the surface morphology of 3 layers PZT films with different gel solution concentration after sintering at 700oC for 30 min at 50oC/min. Films prepared with 0.2 M show a less crack surface morphology [Fig. 4.1(a)], but pores existed in the matrix as that reported by Huffman et al [16], who attributed to

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an excess amount of PbO. Films prepared with 0.3 M shows a higher number of cracks due to excess of desired PZT materials on substrate surface [Fig. 4.2(b)]. Therefore, the better concentration of gel solution was 0.2 M; pointed to the fact that higher concentration leads to the appearance of cracks in the films the same as reported in [17].

Figure 5. P-E hysteresis curve of PZT thin film deposited at 0.2 M gel concentration with a drying at 150oC for 5 min and a pre-baking at 350oC for 10 min, and then sintering at 700oC for 30 min with a heating rate 50oC/min.

4.

Conclusion

Figure 3. XRD patterns of 0.2 M PZT films with sintering at 700oC for 30 min (a) drying, pre-baking and sintering with heating rate 50oC/min repeatedly. (b) drying and pre-baking repeatedly, then sintering with heating rate 50oC/min. (c)drying and pre-baking repeatedly, then sintering with heating rate 5oC/min.

Figure 4. SEM micrographs of PZT film surface obtained with different molar concentration and sintered at 700oC for 30 min with 50oC/min (a) 0.2 M (b) 0.3 M.

Polarization-electric field (P-E) characteristics were evaluated at a frequency of 1 KHz using a SawyerTower bridge equipped with an Agilent Technologies 54622A oscilloscope, where the film deposited on the Al/Si3N4/Si substrate covered with the mesa served as the sample. The mesa layer is served as the lower electrode, and coated with a 2 mm diameter upper silver electrode to obtain good ohmic contact. For the PZT thin film by employing lower gel concentration of 0.2 M with a drying at 150oC for 5 min and a pre-baking at 350oC for 10 min, and then sintering at 700oC for 30 min with a heating rate 50oC/min, a P-E hysteresis loop was obtained as shown in Fig. 5.9, which revealed ferroelectricity. The values of the remanent polarization (Pr) and coercive field (Ec) are 11.39 c/cm2 and 84.52 kV/cm, respectively. The polarization is not saturated enough at high electric field, and Pr is not larger. One possible reason for the poor ferroelectric properties is the porous nature of the film as reported [18].

The fabrication of ferroelectric PbZr0.53Ti0.47O3 (PZT) ceramic with powders derived from the sol-gel method was affected by many key factors including gel composition, reflux time ratio, control of annealing conditions, and particularly with an excess of Pb to compensate for the loss during high-temperature heat treatment. A PZT precursor was obtained by chelating the respective metal alkoxides with acetic acid. This precursor formed a gel through sol-gel process, the better reflux time ratio of Pb:Zr:Ti = 2:1:2, with this reflux time ratio the PZT solutions were transparent and no precipitates, and the composition was similar to PbZr0.53Ti0.47O3. After drying and firing, PZT ceramic was obtained. The PZT ceramics, by calcining at 900oC for 4 h, then sintered at 1100oC for 2 h, PZT phase transformation was completed and the pyrochlore phase disappeared. The perovskite phase transformed from pyrochlore phase fired at high temperature by consuming the pyrochlore grains in the pyrochlore matrix, so the formation of a pyrochlore phase appeared to be a necessary step before crystallization to perovskite structure. On the basis of production step and costs in manufacturing, PZT gel solutions were directly deposited on Al/Si3N4/Si substrate instead of Pt/Ti/SiO2/Si to simplify the preparation of PZT films. Under controlled parameters, including gel concentration, substrate-film adhesion, heat treatment conditions, and crack-free PZT films could be obtained. Moreover, the differences of thermal expansion coefficients between PZT films and substrate also influenced the crack behavior. In the survey, the cracking problem was alleviated by employing lower gel concentration of 0.2 M with a drying at 150oC for 5 min and a pre-baking at 350oC for 10 min, and then sintering at 700oC for 30 min with a heating rate 50oC/min. Unfortunately, cracks were still existed. Therefore, processing conditions was utilized to ameliorate crack phenomenon. It found that crack in

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PZT films were extremely improved under glycerin adding and sintering immediately in the prescribed temperature 700oC for 30 minutes. Further, the fabrication and performance of a energy harvesting device on crack-free PZT piezoelectric thin films would be further investigated. Acknowledgments This paper was performed with the support Nan-Jeon Institute of Technology(NJIT). References 1. 2. 3. 4. 5. 6. 7. B. Jaffe, W. R. Cook and H. Jaffe, Piezoelectric Ceramics, p.50. Academic Press, New York, 1971. P. Curie and J. Curie, Bull. Soc. Min. de. France. 3, 90, 1880. V. V. Prisedsky, Ferroelectrics 41, 97, 1982. G. Arlt and P. Sasko, J.Appl.Phys. 51, 4956, 1980. G. King and E. K. Goo, J. Am. Ceram. Soc. 73, 1534, 1990. H. Y. Hu, M. H. Chan, Z. H. Wen and M. P. Harmer, J. Am. Ceram. Soc. 69, 594, 1986. E. Goo, R. K. Mishra and G. Tomas, J. Appl. Phys. 52, 2940 , 1981.

8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18.

J. R. Maldonado and A. H. Meitzler, Ferroelectrics 3, 169, 1972. N. Uchida and T. Ikeda, Jpn. J. Appl. Phys. 4, 867, 1965. D. Berlincourt and H. A. Krueger, J. Appl. Phys. 30, 1804, 1959. K. D. Budd, S. K. Dey and D. A. Payne: Ceram. Proc. 36, 107, 1985. L. Wu, Ph. D. Thesis, NCKU, Tainan, Taiwan, R.O.C, 1982. S. B. Majumder, B. Roy, R. S. Katiyar and S. B. Krupanidhi, J. Appl. Phys. 90, 2975, 2001. A. S. Bhalla and K. M. Nair, Ceramics Intl. 25, 1992. G. Yi, Z. Wu and M. Sayer, J. Appl. Phys. 64, 2717, 1988. M. Huffman, J. P. Goral, M. M. Al-Jassium, A. R. Mason and K. M. Jones, Thin Solid Films 193/194, 1071, 1990. A. Z. Simoes, M. A. Zaghete, M. Cilense, J. A. Varela and B. D. Stojanovic, J. Euro. Ceram. Soc. 21, 1151, 2001. H. Kozuka and S. Takenaka, J. Am. Ceram. Soc. 85, 2701, 2002.

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