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Lead-free ferroelectric ceramics for multilayer ceramic capacitors

Abstract : MLCC consumption is today increasing due to their high efficiency, reliability and frequency characteristics. MLCCs that can work from 300 to 350°C are required both for miniaturization, resulting in greater volume heat dissipation and for new applications. Moreover, environmental requirements are also increasing, the REACH and RoHS regulations prohibiting the use of lead in Europe. It is imperative to create new lead-free materials that are able to meet those requirements.However, the compatibility with the production methods, price, and market are important industrial limitations that need to be considered.Three families of lead-free materials were examined: BaTiO3-based, K0.5Na0.5NbO3-based and Na0.5Bi0.5TiO3-based materials. NBT-BT at the morphotropic phase boundary (6% BT) was chosen as the base dielectric material.Several synthesis methods and parameters were studied to determine the best synthesis conditions. Solid-state synthesis and traditional sintering were chosen for the bulk samples and tape casting was chosen for the layer samples preparation. Sintering was done under ZrO2 powder to prevent the evaporation of volatile species.All samples had secondary Ba-containing phases (Ba2TiO4 and Ba2Ti9O20) formed because of the evaporation of Na during sintering. A skin-effect was observed due to a phase coexistence (tetragonal, rhombohedral, and cubic) due to the local concentration of Ba in the NBT lattice.The effects of the synthesis parameters and the stoichiometry of the reactants on dielectric properties, insulation resistance, and phase separation were analysed.The Na0.44Bi0.48Ba0.06TiO3 nominal stoichiometry was the most suitable for the MLCCs due to its high insulation resistance, low dielectric losses, and stability of permittivity in temperature.The phase separation was initially beneficial, due to the resulting elimination of oxygen vacancies. Above a critical volume fraction (2.5 to 3.0%) and a critical mean surface area (0.9 to 3.0 m2), the trend was reversed due to the conductive nature of the secondary phases.To achieve the critical volume fraction and surface area of the secondary phases, a dispersing agent was used during ball-milling in YSZ jar, with MEK and ethanol as solvents, and without drying the reactants prior to weighing. Finally, a strain relaxation was done at 400°C for 3 hours.Three models explained the frequency dispersion of the dielectric properties: the Maxwell-Wagner model, the Nyquist plot and the modified Curie-Weiss law.Incompatibilities between the dielectric properties of NBT-BT reported in the literature were then analysed, showing the importance of maintaining strict synthesis and measurement methods. The three main factors affected the dielectric properties, creating these incompatibilities in the bulk samples. There were the stoichiometry, the metallization method, and the fixing of the electrical leads using silver paste.An increase of the high-temperature dielectric losses after each thermal cycle reaching more than 300°C was observed, indicating a thermal degradation of the material.Finally, the sintered ceramic monolayers showed a low density (62%), limiting the temperature range corresponding to Exxelia’s specifications. However, after pressing the layers together before sintering, the sintered multilayer sample showed a high density (89%). Dielectric property measurement should be carried out for these synthesized multilayers.
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Vitoria Mussi Toschi. Lead-free ferroelectric ceramics for multilayer ceramic capacitors. Micro and nanotechnologies/Microelectronics. Université Paris Saclay (COmUE), 2019. English. ⟨NNT : 2019SACLC089⟩. ⟨tel-02495353v2⟩

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