Applied Science and Convergence Technology 2018; 27(6): 126-129
Published online November 30, 2018
Copyright © The Korean Vacuum Society.
Yeon Jung Kim
Center for Innovative Engineering Education, Dankook University, Gyeonggi-do 16890, Korea
Correspondence to:*Corresponding author: E-mail: firstname.lastname@example.org
Structural properties for the substitution of Ta5+ ions in the BaTiO3 crystal lattice were observed by SEM/EDS. The formation of perovskite phase and the change of (111), (200) and (002) planes of BaTiO3 solid solution containing a small amount of Ta5+ were studied. As a result, the relationship between the dielectric properties and the polycrystalline structure of Ta5+-doped BaTiO3 was confirmed. It was found that the maximum dielectric constant of the Ta5+-doped BaTiO3 solid solution was more than about 8000, and the transition temperature shifted slightly toward the lower temperature as compared with the pure BaTiO3. The dielectric constants of all the samples measured in the temperature region above the transition temperature showed some diffusivity and satisfied the modified Curie-Weiss law.
Keywords: Ta5+-doped BaTiO3, Dielectric properties, Modified Curie-Weiss law
Nowadays electric and electronic materials are required to be environmentally friendly. Since BaTiO3 (BT) crystals are ferroelectric materials that are widely used in capacitors, IR sensors, and PTCR fields, the discovery of ferroelectricity in BT crystals is historically very important . The dielectric maximum of BT can move toward room temperature due to composition substitution, and the BT dielectric is sensitive to temperature, electric field strength and frequency, especially around Curie temperature .
Powder processing and sintering conditions have a strong influence on the mechanism of doping, the generation of defects, the resulting crystalline structure and finally the properties of the BT. The purpose of this paper is to investigate the effect of donor dopant (Ta5+) on the microstructure and dielectric properties of BT, and to develop a lead-free environmentally friendly ceramic capacitor composition in the electronics industry.
Ta5+-doped BT solid solutions were prepared using raw materials of BaO, TiO2 and Ta2O5 oxides. BT powder was added with 0.5 and 1.0 mole % Ta2O5. Finally, compact Ta5+-doped BT solid solutions was synthesized by firing at 1260~1340 °C for 4 hours. The Ta5+ ion has a different valence from the valence of Ba2+ and Ti4+, so that if the Ta5+ is substituted with BT, charge imbalance occurs like a 2BaO+Ta2O5→2BaBa+2TaTi+6Oo+O2(g)/2+2e’. As a result, the titanium atomic valence decreases from Ti4+ to Ti3+, and consequently has the structure of Ba2+(Ti1-2x4++4Tax5++5Tix3+)O3 [3,4]. The formation of the perovskite phase was confirmed by the diffraction pattern obtained by XRD using Cu
Pure BT crystals exhibit two phases: tetragonal and cubic. Figure 1 shows the X-ray diffraction peaks of (110), (111), (200) and (002) planes of Ta5+-doped BT solid solutions. The formation of a perovskite phase without any impurities in the X-ray diffraction pattern was confirmed. In other words, the results of this experiment could not detect the evidence of BaO, TiO2 and Ta2O5 precursors by XRD. There was no evidence of coexistence in the XRD diffraction peak, but the diffraction results of the XRD peak show characteristics of phases different from those of pure BT by adding Ta5+. The XRD measurement results of the small chart inserted in Fig. 1 show two BT phases. Analysis of 002 (tetragonal), 200 (tetragonal) and 200 (cubic) observed at 44.5~45.5° confirmed tetragonal and cubic phases.
Figure 2 shows SEM/EDS images of BT doped with 0.5 and 1.0 mole % of Ta5+ composed of spherical particles with a visually rounded grain size distribution in the SEM image. Often EDS is commonly used to discover the abundance of certain elements present in a material. In this experiment, Ta5+-doped BT crystals caused charge imbalance due to different oxidation states. In the EDS spectra, it was found that the Ta5+ ion is related to a part of the sample having a long and needle shaped particle. In addition, the EDS spectra were associated with non-homogeneous particles in the region with a large amount of Ta5+ ions. The corresponding EDS spectrum indicates that the regions rich in Ta5+ ions were associated with non-homogeneous grains. Thus, the dielectric constant was slightly reduced due to the non-uniform distribution of Ta5+ and segregation. In the EDS image, the influence on the microstructure uniformity was negligible because there was almost no region rich in Ta5+.
Figure 3 shows a SEM micrograph of the fracture surfaces of the Ta5+-doped BT solid solution. In the case of the solid solution, it is a common phenomenon that during the sintering, the crystal grains of the specimen composed of the powder increase with the decrease of the amount of pores. The grain size of the sintered Ta5+-doped BT was about 3.5~4.5 μm and formed into relatively dense grains.
Figure 4 shows the frequency dependence of the dielectric constant of Ta5+-doped BT. Dielectric constants were measured in the frequency range of 10 Hz to 106 Hz. As shown in the 0.5 mole % Ta5+-doped BT, the dielectric constant decreased markedly to ~103 Hz, but it slowly decreased in the high frequency range. On the other hand, the dielectric constant of 1.0 mole % Ta5+-doped BT abruptly decreased to ~102 Hz and gradually decreased in the high frequency region. Thus, a significant change in the dielectric constant is due to the higher energy required for the orientation of the dipoles as the frequency increases. These results were similar to those reported by other researchers. As shown in the small chart in Fig. 4, the frequency dependence of the dielectric loss is similar to the frequency dependence of the dielectric constant. The addition of Ta5+ to pure BT increased the dielectric constant at the phase transition temperature, but the dielectric constant at room temperature did not find a relatively large change. These results show that BT with added BT has more crystal defects in crystal structure and Ta5+ ion exchanges Ti4+ ions at B site (higher coordination number) of ABO3. Therefore, it is considered that adding Ta5+ optimally to pure BT reduces the local disorder around the Ba2+ atom and also has some effect on the local structure of Ti4 +. At 1 kHz frequency, the maximum dielectric constants of BT doped with 0.5 mole % Ta and 1.0 mole % Ta were measured to be 7161 at 105 °C and 9940 at 118 °C, respectively. However, the dielectric loss at room temperature for both compositions was relatively large as shown in Fig. 4. The dielectric constants of BT doped with 0.5 mole % Ta5+ and 1.0 mole % Ta5+ at room temperature were measured to be 3490 and 2513, respectively. In Ta5+-doped BT, chemically heterogeneous systems can be formed. The Ta5+ ions lead to the formation of core-shell structure, with BT core and Ti4+ modified BT shell. Ta5+ ions also segregating at grain boundaries, act as grain growth inhibitors. Since the Ta5+-doped BT samples exhibit a different dielectric behavior it is for expected that the Curie constant would be very sensitive to the type and concentration of additive. Therefore, the dielectric constant of Ta5+-doped BT solid solution can vary greatly because it is governed by two different microstructural regions. It was judged that non-ferroelectric behavior was observed in a part of the sample due to the composition fluctuation. In all investigated samples dielectric constant after initially large value at low frequency attains a constant value at f ≥ 10 kHz. Pure BT undergoes a sharp phase transition from ferroelectric to paraelectric phase at Curie temperature. However, in this experiment, the phase transition of Ta5+-doped BT was slightly different from that of pure BT.
The modified Curie-Weiss law was used to investigate the diffusional phase transition properties of the BT solid solution with the addition of Ta5+. It is clear that the degree of diffuse phase transition change will change as the addition of Ta5+ increases, which can be analyzed by diffuseness parameter in
In this paper, the microstructure and dielectric properties of BT solid solution doped with Ta5+ were analyzed. According to the results, the grain size increased slightly from 3.5 μm to 4.5 μm when the addition amount was increased from 0.5 mole % Ta5+ to 1.0 mole % Ta5+. In addition, the fine-grain and high density of BT ceramic result in its excellent dielectric properties. The dielectric behavior of Ta5+-doped BT is in agreement with the presence of the tetragonal structure observed by XRD. The dielectric constant of 0.5 mole % Ta5+-doped BT reaches to 3490 at room temperature. These results show that the additives such as Ta5+ did not cause a significant change in the local structure around the Ti4+ atom, and that the local structure is similar to the pseudo-cubic crystal in comparison with other references. The crystal structure of Ta5+-doped BaTiO3 is considered to show some tetragonality. The BT added with Ta5+ showed a characteristic of a relatively uniform microstructure having a homogeneous additive distribution in the formation of the crystal structure. Therefore, BT with Ta5+ was analyzed for a large change in dielectric constant, which is a function of temperature. The phase transition temperature of all samples analyzed by the experimental results is lower than that of pure BT solid solution. The dielectric behavior in the transition temperature range above the Curie temperature in both compositions with Ta5+ was well satisfied with the modified Curie-Weiss law.