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Phase analysis of PZT 52/48 thin lms by synchrotron XRD

Y. LIU, C. XU Kyushu National Industrial Research Institute, Saga 841, Japan E-mail: yun@kniri.go.jp H. LIU, H. TORAYA Ceramics Research Laboratory, Nagoya Institute of Technology, Tajimi 507-0071, Japan T. WATANABE Kyushu National Industrial Research Institute, Saga 841, Japan

The phase analysis of ferroelectric PZT 52/48 thin lms was carried out by ab initio structure analysis with the aid of the synchrotron X-ray diffraction (SXRD) technique. The pseudocubic phase of the PZT thin lm from conventional X-ray diffraction (XRD) was rened to both rhombohedral (R3m) and tetragonal (P4mm) phases. The composition of the two phases signicantly depends on the preparation condition of the thin lm. The post-treatment in oxygen favored the coexistence of the two phases. This means that the preparation process of the PZT thin lm near the morphotropic phase boundary (MPB) must be carefully controlled to obtain the desired piezoelectric properties. Besides, it was also found that distortion of the thin lm from cubic symmetry is lower than the corresponding bulk material in the PZT materials. The lead zirconate titanate, Pb(Zrx Ti1x )O3 (PZT), near the morphotropic phase boundary (MPB) exhibits an excellent piezoelectric property due to a high electromechanical coupling factor resulting from the coexistence of the rhombohedral and tetragonal phases. Most research has focused on the PZT chemical composition near the MPB for various sensors and actuators. In fact, it is very difcult to exactly control the chemical or phase composition of the PZT materials in the vicinity of the MPB. Most PZT materials have a spatial compositional uctuation caused by the process, etc. Sugiyama and coworkers had investigated the broad phase composition of the PZT ceramics (x was from 0.12 to 0.87) using an X-ray photoelectron spectroscopic technique [1]. Fernandes and coworkers studied the inuence of the chemical compositional uctuation on the phase composition of the PZT ceramic powders in the range of the Zr/Ti ratio from 51/49 to 55/45 [2] by high resolution XRD. However, the PZT thin lm presented a more complex situation than the PZT ceramic bulk and powders due to the strong surface and interface effects as well as the variable process. Particularly, in the sputtering process, the chemical composition of the thin lm usually quite differed from the target composition. Furthermore, only a pseudocubic phase in the PZT thin lm near MPB could be observed by the conventional X-ray diffraction technique; therefore, the more rened analysis technique is expected to be used for the analysis of the phase composition, and then
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achieve the desired property by controlling the process. In this letter, the synchrotron X-ray diffraction (SXRD) technique was used to collect the XRD data and determine the rened crystalline phases of the PZT lms. The PZT thin lms were prepared on glass substrates with the LaNiO3 lm using the RF sputtering technique [3]. The perovskite-like LaNiO3 thin lm was then used as a bottom electrode and a buffer layer to improve the structure mismatch between the PZT lm and the amorphous glass substrate. Preparation of the LaNiO3 thin lm has been described in a previous paper [4] using the aqueous method. The target for the sputtering was a hot pressure ceramic with a composition of 0.4 at% Nb-doped Pb1.15 (Zr0.52 Ti0.48 )O3 near the MPB. Samples A, B, and C were obtained by sputtering at the different substrate temperatures of 660 C, 670 C and 670 C, respectively, in an argon atmosphere for 3 h. After sputtering, samples A and B were treated at 650 C in situ in a vacuum growth chamber for 2 h, and sample C was processed in an oxygen atmosphere. All samples were conrmed to have the pure pseudocubic perovskite phase and the preferred orientation along the (100) direction based on the conventional X-ray diffraction technique. The synchrotron X-ray diffraction (SXRD) data were collected using the X-ray diffraction with a step interval of 0.005 , which was located at the Photon Factory in Tsukuba, Japan [5]. The X-ray wavelength was A detailed treatment data was done by the 1.200 A. TREOR90 program [6] for pattern indexing and the WPPF [7] for whole pattern tting. The space groups were analyzed by the direct-methods package SIRPOW92 [8] and these structural parameters were rened by the Rietveld method [9]. Some typical data of the PZT lms from SXRD are listed in Table I. The sputtering temperature had only a slight inuence on the d -values of the PZT lms over 650 C [3], where the d -value increased with increasing sputtering temperature (samples A and B). Furthermore, the d -value of the PZT lm post-treated in situ in a vacuum (sample B) is larger than that in the oxygen atmosphere (sample C) for the same sputtering temperature (670 C). From the FWHM of the PZT lms, the growth of grains had not been clearly determined, which was reasonable due to only a 10 C difference in
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T A B L E I Typical SXRD data of PZT thin lms Sample No. d (101)/(110) d (111) d (211) FWHM of (101)/(110) FWHM of (111) FWHM of (211) A 2.874285 2.346074 1.659171 0.087495 0.113886 0.196598 B 2.884395 2.352927 1.664517 0.077763 0.121397 0.182499 C 2.876372 2.348821 1.660756 0.080786 0.133955 0.190318

T A B L E I I Effect of the preferred orientation on microstructures No preferred orientation Sample No. A B C Rp% 12.35 12.56 11.56 Rwp% 16.50 18.41 16.99 Preferred orientation Rp% 11.35 12.29 11.24 Rwp% 15.07 17.48 16.07

sputtering temperature. The large FWHM at high angles generally reected the high defect state density and some incomplete cells in the thin lms. For comparison, sample B had a relatively completed cell structure. On the assumption of only a single phase, the effect of the preferred orientation on the microstructures is also discussed in Table II. The symbols of Rp and Rwp in Table II are the prole R -factor in the pattern decomposition process and the weight R -factor of the Rietveld method, respectively, which should be expected to have a smaller value for a correct model. All of the Rp and Rwp with no orientation were larger than ones in the preferred orientation. This implied that these lms have the preferred orientation to some extent, in agreement with the conventional XRD patterns where the samples showed a tendency for the preferred orientation. Table III shows the lattice parameters and phase compositions of the PZT lms analyzed by the WPPF prole tting and Rietveld method. It is apparent that the pseudocubic PZT thin lm was composed of both rhombohedral and tetragonal phases, corresponding to the R3m and P4mm space groups, respectively. Their cell parameters, a and c, are also listed in Table III. In R3m, the primitive cell is a rhombohedral structure with an a ; therefore, in rhombohedral symmeedge of 3/2 try, R = c/a/ 3/2. In the P4mm tetragonal symmetry, R = c/a. The R -values in the PZT thin lms were in the range from 0.99995 to 1.00292. Obviously, all of the

R -values in the thin lms were smaller than 1.02725, the R value in the bulk PZT52/48 ceramics. This illustrates that the distortion of the thin lms from the cubic symmetry is much smaller than the one for the corresponding bulk materials. This was the reason why we frequently found only a pseudocubic structure in the PZT thin lms with their compositions in the vicinity of the MPB. Table III also shows that the post-treatment atmosphere signicantly inuences the phase composition of the PZT thin lm according to the Rp and Rwp values. The R3m phase was dominant in the PZT thin lms treated in vacuum, which were the 98.98 mol% and 99.40 mol% in samples A and B, respectively. The PZT thin lm post-treated in the oxygen atmosphere showed the coexistence of the two phases with the R3m/P4mm ratio of 41.90/58.10. Besides, the dielectric properties of the PZT thin lms were also investigated using a NF 2330A LCZ meter (NF Electronic Instrument Co., Japan). The appearance of the P4mm phase apparently increased the dielectric constant of the PZT thin lms. The dielectric constant in sample C reached 1407. This illustrated that the post-treatment in the oxygen atmosphere is favored for the formation of the coexisting two phases, thus achieving the high dielectric constant and high piezoelectric property. An increase in the dielectric constant of the thin lm was attributed to the appearance of the P4m phase. As a function of the P4m phase content, , the tting curve of the dielectric constant K was satised with = e( K 225)/1011 as shown in Fig. 1. Obviously, a little P4m phase could lead to obviously increase in the dielectric constant, but the highest dielectric constant appeared at relatively higher P4m phase content. This suggests that the introduction of a little P4m phase into the R3m phase can effectively increase the dielectric activity as well as the piezoelectric activity. In summary, the pseudocubic phase in the PZT thin lms was successfully rened to the rhombohedral phase with the R3m space group and the tetragonal phase with the P4mm space group by SXRD. This phase composition is greatly dependent on the preparation process. A little P4m phase can effectively improve the dielectric activity of the PZT thin lm. Besides, the analysis also indicates that the distortion of the PZT thin lm from cubic symmetry is smaller than the corresponding bulk material, therefore, only a

T A B L E I I I Cell parameters and phase compositions of PZT thin lms by a WPPF prole tting and Rietveld method as well as its dielectric constant A Space group Cell parameters C/a R Rp% Rwp% Weight % Molar % Dielectric constant (1 Khz, 50 mV) a c R3m 5.74681 7.04486 1.22587 1.00092 8.31 11.20 99.95 98.98 1024 P4mm 4.06284 4.06384 1.00025 1.00025 9.32 12.30 2.65 1.02 R3m 5.76040 7.05470 1.22469 0.99995 8.67 12.26 98.79 99.40 951 B P4mm 4.06490 4.07697 1.00292 1.00292 10.52 15.12 1.21 0.60 R3m 5.75040 7.05464 1.22681 1.00168 7.42 9.84 26.22 41.90 1407 C P4mm 4.06540 4.07201 1.00162 1.00162 7.43 9.89 73.73 58.10

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References
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Figure 1 Effect of the phase composition on dielectric constant in the PZT thin lm.

pseudocubic phase of the thin lm could be observed by the conventional XRD technique. This study is of great worth for researches on the preparation and property of the PZT thin lm.

Received 4 October and accepted 26 December 2000

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