High Permittivity Ceramics for Dielectrically Loaded Applications

A temperature-stable, ultra-high permittivity dielectric ceramic, based on CTLNT, has been successfully fabricated at significantly reduced sintering temperatures with no deterioration of microwave properties, through the addition of a Bi_4B_2O_9 (BBO) sintering aid. This work has been an extension of previous findings where it was shown that 0.2CaTiO_3-0.8(Li_0.5Nd_0.5)TiO_3 (CTLNT) with 4wt% BBO as a liquid-phase sintering aid gives rise to exceptional microwave (MW) dielectric properties, (relative permittivity, ε_r = 127, quality factor, Qf_0 = 2700 GHz, and temperature coefficient of the resonant frequency, τ_f = +4 ppm/°C) at reduced sintering temperatures (1200°C). Prior to this, it has been exceptionally difficult to produce a large ε_r dielectric material, with both a low sintering temperature and near-zero temperature stability, without dramatic deterioration of the dielectric properties of the material. This contribution set out to investigate and understand the sintering mechanism between the CTLNT + xwt% BBO system, to aid in the development of designer sintering aids in the development of other microwave dielectric ceramic materials and devices. CTLNT + 1, 3, 4 and 5wt% BBO compositions were fabricated and a variety of analysis techniques were used, such as density, XRD, SEM, TEM, EDS and MW characterisation. Density increased with increasing BBO concentration and sintering temperature, and the MW results reflected the changes in density. The 1wt% BBO composition showed the greatest variation between the sintering temperatures, and 4wt% composition demonstrated optimum MW results of: ε_r=125, Qf_0=2518 GHz and τ_f=4 ppm/°C, at a sintering temperature of 1200°C. The variation of τ_f with changes in BBO concentration was non-linear, which suggested a chemical reaction was taking place. XRD results revealed no secondary phases, regardless of BBO concentration. SEM results showed increased crystal grain size as BBO concentration and sintering temperatures increased, as well as increased contrast variation on the polished surface and darker-contrast amorphous phase in the fracture surface. The contrast variation in the polished surfaces were also indicative of a chemical reaction. Using a combination of XRD, TEM and SEM it was demonstrated that highly polarisable Bi3+ ions entered the CTLNT perovskite lattice and locally increasing ε_r. The accompanying ex-solution of TiO2 precipitates, observed and analysed under SEM and TEM, as the BBO concentration increased implied the formation of Ti vacancies (V_Ti^'''') in the perovskite matrix to compensate for the extra positive charge of the Bi3+. The ex-solution of Ti indicates Bi3+ ions substitute onto the A-site of the perovskite crystal system for lower valence ionic elements, after the following generic defect equation: 4(A)_A^x+(Ti)_Ti^x⇒4(Bi)_A^∙+V_Ti^'''' The residual phase was found to be a boron-rich liquid-phase, which acted as the sintering aid, with a large negative τ_f which compensates for the positive τ_f of the CTLNT. The CTLST + xwt% BBO system (S = Sm) was then investigated to determine if a similar mechanism would occur. CTLST + 1, 2, 3 and 4wt% BBO compositions were fabricated and underwent the same analysis techniques. Density increased with increasing BBO concentration up to 1250°C, after which density fell for all samples; the 4wt% BBO composition exhibited the largest density, at 1250°C. The MW results reflected this trend, which saw a general increase in ε_r as BBO concentration and sintering temperature increased, which fell universally at 1300°C. 〖Qf〗_0 would generally increase with increased BBO concentration, across all sintering temperatures, while a dip was observed at 1250°C, and the 4wt% BBO composition demonstrated optimum properties of: ε_r = 105.7, Qf_0 = 3295 GHz and τ_f = -4 ppm/°C, sintered at 1200°C. Contrary to the CTLNT system, the variation of τ_f with BBO content and sintering temperature was linear. SEM reflected density changes, where crystal grain increased with increasing BBO concentration, up to 1250°C. At 1300°C, samples suffered from dissolution into the liquid-phase, increasing pore sizes, decreasing density and, thus, impacting on the MW properties of the samples. Similar to the CTLNT system, contrast variation was observed, in addition to darker B-rich liquid phase in the fracture surface. EDS from both SEM and TEM revealed that Bi was present within the CTLST matrix, however no TiO2 precipitates were observed. Large Zr contamination within CTLST is the likely cause of the difference in defect chemistry, as excess of Zr substitution onto the perovskite B-site compensates for Bi substitution onto the A-site, negating the need for TiO_2 precipitates to ex-solve. Multi-layer ceramic capacitors (MLCCs) of the CTLNT + 4wt% BBO composition were fabricated to determine whether the temperature stabilities of the material in conjunction with a large ε_r would allow the material to be a suitable candidate as a Class 1 C0G/NP0 MLCC device. Fabrication of the devices followed the conventional method, but required modification due to delamination. These modifications included: longer firing times to allow for binders and plasticisers to burn-out fully; calcined alumina powder base to fire and sinter samples upon, to avoid sticking issues; and solvent wetting of individual layers to adequately fuse layers together pre-firing and sintering. Successful MLCC devices had case sizes of EIA ‘2928’ and IEC ‘7472’. SEM and EDS revealed no mixing or exchange of materials between the dielectric and the platinum internal electrode, and generally good adhesion between both materials. Electrical tests revealed that, despite the temperature stability observed at 1-3 GHz in the MW study, that the MLCC devices would be classed as EIA “M8J” and IEC “P1000”, however maximum available test frequency of 1 MHZ is much lower than the average operating frequencies of class 1 devices, which lie between 100 MHz – 30 GHz