EFFECTS OF SINTERING CONDITIONS ON THE DIELECTRIC PROPERTIES OF CaCu3Ti4O12 (CCTO) CERAMICS

Sanjesh Babu#, A.Govindan Deptt of Physics, M.M.H College, Ghaziabad (C.C.S University Meerut, U.P. India)

ABSTRACT:

The effects of sintering conditions on the dielectric properties of CaCu3Ti4O12 were studied in this paper. In this study CaCu3Ti4O12 was prepared by the conventional solid state ceramic process. The relative dielectric constants (r) up to ~ 3000 at 1 KHz were gradually increased with increasing the sintered density of samples in the case that no exaggerated grain growth occurred. An abrupt increase in r values were, however, accompanied by the formation of abnormally grown large grains and thus with increasing the population of abnormally grown grains, which could be achieved by a prolonged sintering at 1060 0C, the r values were remarkably increased from several thousands to ~ 105.

INTRODUCTION: Subramanian et al. first reported high dielectric constant of 12,000 at 1 kHz for CCTO polycrystalline ceramics, which remained almost constant between room temperature and 600 K. A very high r of ~ 80,000 below 20 kHz was subsequently reported by Homes et al. for CCTO single crystals at 250 K. These extremely high r values and their relatively low variation in a wide temperature region without any ferroelectric or relaxor-type phase transition made CCTO very attractive for capacitor applications in the electronic devices. Thus, many groups studied the dielectric properties of CCTO materials including single crystal, polycrystalline ceramics and also thin films. While there are numerous reports on polycrystalline CCTO ceramics, the reported r values show a very wide distribution from 103 to 105 at 1 kHz with various sintering process and conditions, and the reason for this disagreement has not been fully clarified, which motivated the present study. In this paper, an attempt is made to study the effects of the sintering period up to 24 h at two different sintering temperatures of 980 and 1060 0C on the dielectric properties of CCTO samples to uncover the important factors affecting the r values of sintered CCTO ceramics. EXPERIMENTAL PROCEDURE: Polycrystalline CCTO samples were synthesized by the conventional solid - state reaction. Precursors were CaCO3 , CuO , and TiO2 powder. Starting materials were weighed and ball-milled in ethyl alcohol using a polyethylene bottle and ZrO2 balls for 24 h. The milled powder were dried, ground, sieved, and then calcined at 950C for 24 h in air. Calcined powder were ball-milled again for 24 h, and uniaxially pressed into disk-shaped pellets of 15 mm in diameter and then isostatically pressed under the pressure of 100 MPa using a cold isostatic press. The pellets were sintered at 980 and 1060C, respectively in air and the holding time
2

during sintering was varied from 30 min to 24 h. Phases of samples were analyzed by X-ray powder diffraction (XRD). The lattice parameter of the calcined powder was calculated on the basis of XRD data which included silicon peaks as the internal standard. Relative sintered density of the samples was measured using the Archimedes method in the distilled water. Microstructures of sintered samples were observed by scanning electron microscopy (SEM). Ag electrodes were pasted on the top and bottom surfaces of the samples by the screen printing and then fired at 600C for 30 min for the measurements of the dielectric properties. Relative dielectric constant, r and dielectric loss, tan of the samples were measured by an impedance/gain-phase analyzer as a function of frequency at room temperature. RESULTS AND DISCUSSION: The variation of the relative dielectric constant, r and dielectric loss, tan as a function of frequency at room temperature for the samples sintered at 980 and 1060C in air, respectively with various sintering periods are shown in fig(1). From this figure, it is clear that, while the r values are increased with increasing the holding time, the increasing behavior of r in samples sintered at 1060C is quite different from that in samples sintered at 980C. At 980C, with increasing the holding time, the r values in fig. 1(a) exhibit an abrupt increase from 30 min to 2 h and then a gradual increase up to 24 h (r ~3,100 at 1 kHz). However, at 1060C, the r values in fig. 1(b) are almost unaltered from 30 min to 6 h (r ~3,500 at 1 kHz), abruptly increased after 9 h (r ~43,000 at 1 kHz), and then gradually increased up to 24 h (r ~90,000 at 1 kHz). Regardless of the sintering conditions, with increasing frequency, dielectric properties were almost unaffected in relatively low frequency region (100 Hz ~ 1 MHz), and then they were abruptly degraded at higher frequency, of which behaviour is in good agreement with previous reports. With increasing frequency from 1 kHz to 15 MHz, the r value of the sample sintered at

980C for 24 h was decreased from 3,100 to 130, and similarly the r of the sample sintered at 1060C for 24 h was rapidly decreased from 90,000 to 350. The r values of all samples sintered at different holding times remained almost unaltered in relatively low-frequency region and drastically degraded with increasing frequency. To identify the origin of the above variation in dielectric properties with sintering conditions in fig.1, we measured the sintered densities of all samples. The results are shown in fig (2).

Fig 1(a)

Fig 1(b)

Fig (1) Relative dielectric constant (r) and dielectric loss(tan) of CCTO samples sintered at (a) 9800C and (b) 10600C, respectively with various sintering periods.

Fig(2). Relative sintered densities of CCTO samples sintered at 980 and 10600C as a function of the sintering period.

The theoretical density of CCTO is 5.05g/cm3. As shown in fig (2), the relative sintered densities of samples were increased with increasing the holding time, reached above 98% after 12 h, and then remained constant up to 24 h. For the samples sintered at 980C, this behaviour seems to be very similar to that of r in fig.1(a) since the behaviour of a gradual increase with increasing the holding time is observed in both cases. In addition, samples sintered at 980C for 6 ~ 24 h and those sintered at 1060C for up to 6 h representing similar relative densities (96~98%) exhibit similar r values of several thousand. These facts suggest that the increase in r
6

may be attributed to the increase in the sintered density. However an abrupt increase in r for the samples sintered at 1060C for 9~24 h in fig1(b) is unexplainable simply with the sintered density. To further verify the origin for the variation in dielectric properties of CCTO samples in fig(1), we observed the structure of samples. Unlike the samples sintered at 980C, which showed no apparent visual change up to 24 h, an interesting visual change could be observed for those sintered at 1060C. Although not presented, large grains visible with bare eyes were started to appear after 6 h, their population was abruptly increased after 9 h, and almost fully covered after 12 h. Detailed microstructures are represented in fig(3). For the samples sintered at 980C for 12 and 24 h, only a slight increase in average grain size is observable with increasing the holding time. On the other hand, the sample sintered at 1060C for 12 h is composed of abnormally grown large grains and a small portion of the fine-grained matrix, and the small portion of the fine-grained matrix is almost unobservable after 24 h. Thus, it is obvious that the abrupt increase in r values from several thousands of the samples sintered for 6 h to ~105 of the sample sintered for 24 h in fig. 1(b) are closely related to increase in the population of abnormally grown grains. The r value of ~ 90,000 at 1 kHz for the sample sintered for 24 h is similar to that of the CCTO single crystal.

Fig (3). SEM morphologies of the chemically etched surfaces of CCTO samples sintered at 9800C for (a) 12 h and (b) 24h and CCTO samples sintered at 10600C for (c) 12 h and (d) 24h. CONCLUSION: In this article, an attempt has been made to study the effects of sintering conditions on the dielectric properties of CCTO polycrystalline ceramics prepared by the conventional solid-state ceramic process. The important factors affecting the relative dielectric constants of CCTO polycrystalline samples in relatively low frequency region (< 1 MHz) could be classified like the following. First, r values up to several thousands (~ 3,000 at 1 kHz) were dependent on the sintered density, in which case no exaggerated grain growth was observed. Next, an abrupt increase in r values were accompanied by the formation of abnormally grown large grains. With

increasing the population of abnormally grown grains, which could be achieved by a prolonged sintering at higher sintering temperature like 1060C, r values were increased from several thousands to ~105, which is very close to the value of the CCTO single crystal. The above results indicate that the r values are strongly affected by the microstructures, especially the existence of abnormally grown large grains with a high sintered density. ACKNOWLEDGEMENT: The author is sincerely grateful for the guidance provided by Dr. Anil Govindan, Associate Professor of Physics, MMH College, Ghaziabad (U.P.). REFERENCES: 1. A. P. Ramirez, M. A. Subramanian, M. Gardel, G. Blumberg, D. Li, T. Vogt, S. M. Shapiro, Solid State Commun. 115, 217 (2000). 2. B. A. Bender, M.-J. Pan, Mater. Sci. and Eng. B 117, 339 (2005) 3. C. C. Homes, T. Vogt, S. M. Shapiro, S. Wakimoto, A. P. Ramirez, Science 293, 673 (2001) 4. C. C. Homes, T. Vogt, S.M. Shapiro, S. Wakimoto, A. P. Ramirez, Phys. Rev. B 67, 092106(2003) 5. D. C. Sinclair, T. B. Adams, F. D. Morrison, A. R. West, Appl. Phys. Lett. 80, 2153 (2002) 6. G. Zang, J. Zhang, P. Zheng, J. Wang, C. Wang, J. Phys. D: Appl.Phys. 38, 1824 (2005) 7 L. Fang, M. Shen, Thin Solid Films 440, 60 (2003)

8. M. A. Subramanian, D. Li, N. Duan, B. A. Reisner,A. W. Sleight, J. Solid State Chem.151,323(2000) 9. P. Lunkenheimer, R. Fichtl, S. G. Ebbinghaus, A. Loidl, Phys. Rev. B 70, 172102 (2004) 10. T. B. Adams, D. C. Sinclair, A. R. West, Adv. Mater. 14, 1321 (2002) 11. V. Brize, G. Gruener, J. Wolfman, K. Fatyeyeva, M. Tabellout, M. Gervais, F. Gervais, Mater.Sci. and Eng. B 129, 135 (2006).