Growth and Characterization of Lead-free (K,Na)NbO3-based Piezoelectric Single Crystals

Lead-free piezoelectric materials have received increasing attention in the last decade, driven by environmental issues and health concerns. Of considerable interest is the (K,Na)NbO3 (KNN)-based system, which possesses a relatively high Curie temperature and good piezoelectric properties. Abundant publications on KNN-based polycrystalline ceramics increased the interest in studying their single-crystalline form, based on two major concerns. The first concern refers to the negative role of grain interactions on the electromechanical response. The second concern deals with domain engineering. The relationship between external electric field direction, crystallographic orientation, and spontaneous polarization vectors for a specific structure can be more readily established in single crystals and thus offers a pathway for an in-depth understanding of fundamental mechanism and potential applications. The exciting enhancement of both piezoelectric and ferroelectric response in lead-based single crystals also encourages the further exploration of KNN-based piezoelectric crystals, as they possess the same perovskite structure. The main goal of this thesis is to find possible approaches for improved electromechanical properties in KNN-based piezoelectric single crystals. In Chapter 2, the current development of KNN-based single crystals as piezoelectrics is reviewed, following a short introduction of fundamental knowledge on piezoelectrics and ferroelectrics. Both submerged-seed solution growth and top-seeded solution growth techniques were employed to produce single crystals, as described detailed in Chapter 3. Emphasis is subsequently placed on issues of the crystal growth process, effective methods to enhance electrical properties, and crystallographic orientation-dependent electrical properties in Li-, Ta-, and/or Sb-substituted KNN single crystals. The main conclusions from the crystal growth aspect are presented in Chapter 4 and can be summarized as follows: (i) For individual elements, segregation coefficients highly rely on the initial concentration in the liquid solution. The systematic discussion in this work contributes to future composition design in KNN-based crystals. (ii) A competition between elements occupied on the same lattice site was found. (iii) The very low Li segregation coefficient in the KNN matrix is importantly responsible for the occurrence of a secondary phase with the tetragonal tungsten bronze structure. (iv) The observed optically-cloudy regions in as-grown KNN-based single crystals decrease the electrical response and can be reduced by thermal treatment with slow cooling. In the second part of the thesis we used three approaches to enhance the piezoelectric and ferroelectric behavior of KNN-based single crystals, which is shown in Chapter 5. Chemical substitution with Ta or Sb ions indicates that enhanced electromechanical response is achieved when the orthorhombic-tetragonal phase transition temperature is in the proximity of room temperature, as previously reported for polycrystalline ceramics. Thermal treatment in pure O2 atmosphere resulted in a twofold increase of the piezoelectric coefficient and ferroelectric parameters (maximum and remanent polarization) of a (K,Na,Li)(Ta,Nb,Sb)O3 single crystal. The up-to-date highest room-temperature piezoelectric coefficient in annealed KNN-based single crystals of 732 pC/N was obtained, which is attributed to the lower defect concentration after the thermal treatment. The third approach, doping with a small amount of transition metal Mn ions in (K,Na,Li)(Ta,Nb)O3 single crystals, is also presented. Orientation dependence of electromechanical properties in Chapter 6 indicates that high maximum polarization, remanent polarization, coercive field, maximum strain, and negative strain were observed when the electric field was applied along one of the spontaneous polarization vectors in both tetragonal and orthorhombic phases. This is related to the effect of polarization rotation under different electric field directions.