Nominally pure nanocrystalline KTaO 3 was thoroughly investigated by micro-Raman and magnetic resonance spectroscopic techniques. In all samples the defect driven ferroelectricity and magnetism are registered. Both ordering states are suggested to appear due to the iron atoms and oxygen vacancies. The concentration of defects was estimated to be 0.04 and 0.06-0.1 mole %, respectively. Note that undoped single crystals of KTaO 3 are nonmagnetic and have never exhibited ferromagnetic properties. The results enable us to refer a nanosized KTa(Fe)O 3 to the class of multiferroics and assume that it could perform the magnetoelectric effect at T<29 K. It was also established that the critical concentration of impurity defects necessary to provoke the appearance of the new phase states in the material strongly correlates with the size of the particle; as the size of the particle decreases, the critical concentration decreases as well.

The coupled system of the microwave cylindrical TE 011 cavity and the TE 01␦ dielectric modes has been analyzed in order to determine the maximum achievable resonator efficiency parameter of a dielectric inserted into a cavity, and whether this value can exceed that of a dedicated TE 01␦ mode dielectric resonator. The frequency, Q value, and resonator efficiency parameter ⌳ for each mode of the coupled system were calculated as the size of the dielectric was varied. Other output parameters include the relative field magnitudes and phases. Two modes are found: one with fields in the dielectric parallel to the fields in the cavity center and the other with antiparallel fields. Results closely match those from a computer program that solves Maxwell's equations by finite element methods. Depending on the relative natural resonance frequencies of the cavity and dielectric, one mode has a higher Q value and correspondingly lower ⌳ than the other. The mode with the higher Q value is preferentially excited by a coupling iris or loop in or near the cavity wall. However, depending on the frequency separation between modes, either can be excited in this way. A relatively narrow optimum is found for the size of the insert that produces maximum signal for both modes simultaneously. It occurs when the self-resonance frequencies of the two resonators are nearly equal. The maximum signal is almost the same as that of the dedicated TE 01␦ mode dielectric resonator alone, ⌳ Х 40 G / W 1/2 at X-band for a KTaO 3 crystal. The cavity is analogous to the second stage of a two-stage coupler. In general, there is no electron paramagnetic resonance ͑EPR͒ signal benefit by use of a second stage. However, there is a benefit of convenience. A properly designed sample-mounted resonator inserted into a cavity can give EPR signals as large as what one would expect from the dielectric resonator alone.

By changing the size and the shape of ferroelectric nanoparticles, one can govern their polar properties including their improvements in comparison with the bulk prototypes. At that the shift of the ferroelectric transition temperature can reach as much as hundreds of Kelvins. Phenomenological description of these effects was proposed in the framework of Landau-Ginsburg-Devonshire (LGD) theory using the conceptions of surface tension and surface bond contraction. However, this description contains a series of poorly defined parameters, which physical nature is ambiguous. It is appeared that the size and shape dependences of the phase transition temperature along with all polar properties are defined by the nature of the size effect.Existing LGD-type models do not take into account that defects concentration strongly increases near the particle surface. In order to develop an adequate phenomenological description of size effects in ferroelectric nanoparticles, one should consider Vegard strains (local lattice deformations) originated from defects accumulation the near surface.In the paper we propose a theoretical model that takes into account Vegard strains and perform a detailed quantitative comparison of the theoretical results with experimental ones for quasi-spherical nanoparticles, which reveal the essential (about 100 K) increase of the transition temperature in spherical nanoparticles in comparison with bulk crystals. The average radius of nanoparticles was about 25 nm, they consist of KTa 1х Nb х O 3 solid solution, where KTaO 3 is a quantum paraelectric, while KNbO 3 is a ferroelectric. From the comparison between the theory and experiment we unambiguously established the leading contribution of Vegard strains into the extrinsic size effect in ferroelectric nanoparticles. We determined the dependence of * Corresponding author 1: anna.n.morozovska@gmail.com † Corresponding author 2: isgolovina@ukr.net 1 Vegard strains on the content of Nb and reconstructed the Curie temperature dependence on the content of Nb using this dependence. Appeared that the dependence of the Curie temperature on the Nb content becomes non-monotonic one for the small (< 20 nm) elongated KTa 1-х Nb х O 3 nanoparticles. We established that the accumulation of intrinsic and extrinsic defects near the surface can play the key role in the physical origin of extrinsic size effect in ferroelecric nanoparticles and govern its main features.

The paper reports on thorough Raman-scattering study of newly synthesized nanoscale powders of potassium niobate (KNbO3) aimed at evaluating the possible modification of the phase transition temperatures versus the corresponding bulk values. We register a significant expansion of the temperature ranges of all phase transitions, which is attributed to a wide distribution of particle sizes. An average temperature of each phase transition shifts to the high-temperature region differently, namely by 10°, 25°, and 40°, as compared with corresponding transition temperature in bulk crystals of KNbO3 and amounts 0, 248, and 475 °C, respectively. In the range from 100 to 110 °C, we also find the features, which could be associated with an additional rearrangement of the structure.

Newly synthesized undoped and iron-doped nanoscale powders of KNbO3 are investigated using magnetic resonance and static magnetization methods in order to determine how the crystal size and doping affect the structure of magnetic defects and material properties. Although the bulk crystals of KNbO3 are nonmagnetic, the undoped KNbO3 powder with average particle size of 80 nm exhibits magnetic properties. The ferromagnetic resonance signal and the magnetization curve registered on the powder are thoroughly analyzed. It is concluded that the appearance of the defect driven ferromagnetism in the undoped powder is due to the nano-size of the particles. This effect disappears in the iron-doped KNbO3 powder with particle sizes above 300 nm. In case of low doping (&lt;1 mol. % Fe), a new electron paramagnetic resonance signal with geff = 4.21 is found out in the KNbO3:Fe powder. Such a signal has not been observed in the bulk crystals of KNbO3:Fe. We suppose that this signal corresponds to individual paramagnetic Fe3+ ions having rhombic symmetry.