This study examines the volatilization of alkali elements on the surfaces of ceramic targets and in the deposited films during the deposition of potassium sodium niobate (KNN) thin films using a ceramic target with the nominal composition K0.55Na0.55NbO3 via a RF magnetron sputtering process. Under a 100 W RF power condition, significant volatilization of alkali elements occurred on the surface of the ceramic target, resulting in the inevitable formation of a Nb-rich secondary phase in the thin films. However, perovskite-phase KNN thin films with excellent reproducibility and without secondary phases were obtained under 50 W RF power and a substrate temperature of 600 °C. When the RF power was reduced to 20 W or the substrate temperature was lowered to 500 °C under 50 W RF power, no crystalline thin films could be obtained. Additionally, when the substrate temperature was raised to 700 °C under 50 W RF power, the niobium-rich secondary phase appeared in the thin films due to the volatilization of alkali elements. The conditions of 50 W RF power and a substrate temperature of 600 °C were found to be optimal for depositing perovskite-phase KNN thin films. However, complete suppression of potassium volatilization from the thin films was not achievable. Consequently, the resulting films had a sodium-rich composition compared to K0.5Na0.5NbO3 and exhibited lower dielectric constants along with relaxor ferroelectric characteristics. This study highlights the importance of monitoring the compositional changes in ceramic targets during the RF sputtering process to ensure high reproducibility in KNN thin film fabrication.

In this study, we investigated the microstructure and piezoelectric properties of 0.96(K0.456Na0.536)Nb0.95Sb0.05-0.04 Bi0.5(Na0.82K0.18)0.5ZrO3 (KNNS-BNKZ) ceramics based on one-step and two-step sintering processes. One-step sintering led to significant abnormal grain (AG) growth at temperatures above 1,085 °C. With increasing sintering temperature, piezoelectric and dielectric properties were enhanced, resulting in a high d33 = 506 pC/N for one-step specimen sintered at 1,100 °C (one-step 1,100 °C specimen). However, for one-step 1,115 °C specimen, a slight decrease in d33 was observed, emphasizing the importance of a high tetragonal (T) phase fraction for superior piezoelectric properties. Achieving a relative density above 84 % for samples sintered by the one-step sintering process was challenging. Conversely, two-step sintering significantly improved the relative density of KNNS-BNKZ ceramics up to 96 %, attributed to the control of AG nucleation in the first step and grain growth rate control in the second step. The quantity of AG nucleation was affected by the duration of the first step, determining the final microstructure. Despite having a lower T phase fraction than that of the one-step 1,100 °C specimen, the two-step specimen exhibited higher piezoelectric coefficients (d33 = 574 pC/N and kp = 0.5) than those of the one-step 1,100 °C specimen due to its higher relative density. Performance evaluation of magnetoelectric composite devices composed of one-step and twostep specimens showed that despite having a higher g33, the magnetoelectric composite with the one-step 1,100 °C specimen exhibited the lowest magnetoelectric voltage coefficient, due to its lowest kp. This study highlights the essential role of phase fraction and relative density in enhancing the performance of piezoelectric materials and devices, showcasing the effectiveness of the two-step sintering process for controlling the microstructure of ceramic materials containing volatile elements.

The volatilization of alkali ions in (K,Na)NbO3 (KNN) ceramics was inhibited by doping them with alkaline earth metal ions. In addition, the grain growth behavior changed significantly as the sintering duration (ts) increased. At 1,100 °C, the volatilization of alkali ions in KNN ceramics was more suppressed when doped with alkaline earth metal ions with smaller ionic size. A Ca2+-doped KNN specimen with the least alkali ion volatilization exhibited a microstructure in which grain growth was completely suppressed, even under long-term sintering for ts = 30 h. The grain growth in Sr2+-doped and Ba2+-doped KNN specimens was suppressed until ts = 10 h. However, at ts = 30 h, a heterogeneous microstructure with abnormal grains and small-sized matrix grains was observed. The size and number of abnormal grains and size distribution of matrix grains were considerably different between the Sr2+-doped and Ba2+-doped specimens. This microstructural diversity in KNN ceramics could be explained in terms of the crystal growth driving force required for two-dimensional nucleation, which was directly related to the number of vacancies in the material.