Size effects in radiospectroscopy spectra of ferroelectric nanopowders

TL;DR

This study investigates size-dependent phase transitions in ferroelectric nanopowders using radiospectroscopy, revealing a critical particle size of 40 nm where ferroelectric properties vanish, supported by theoretical and experimental analysis.

Contribution

It provides a combined theoretical and experimental analysis of size effects on ferroelectric phase transitions in nanopowders, identifying a critical size of 40 nm.

Findings

Critical size for ferroelectric transition is 40 nm.

Spectral transformation from tetragonal to cubic symmetry observed.

Surface region of about 3 nm influences ESR spectral features.

Abstract

The theoretical and experimental investigation of ferroelectric nanopowders is performed. The manifestation in radiospectroscopy spectra of size driven ferroelectric-paraelectric phase transition at some critical particle average size was the main goal of the consideration. In theoretical part the size effect for the materials with ferroelectric tetragonal phase and cubic paraelectric phase was considered allowing for the spontaneous polarization inhomogeneity inside a particle and distribution of particle sizes. In ESR the transformation of the spectra from tetragonal symmetry to cubic symmetry with decreasing of nanoparticle sizes was calculated. Measurements of Fe3+ ESR spectra in nanopowder of BaTiO3 were carried out at room temperature. The decrease of intensity of tetragonal symmetry ESR lines of Fe3+ and appearance of cubic symmetry line with asymmetry of the shoulders was observed with the average sizes decrease with complete disappearance of tetragonal spectrum at average size less or equal 40 nm. The comparison of the theory with experiment was carried out. The value of critical size Rc = 40 nm was extracted from ESR data. The asymmetry and broadening of right hand side shoulder of ESR cubic symmetry line was shown to be related to contribution of paramagnetic centers in the vicinity of the particles surface. The deconvolution of the cubic line allowed to show, that this region size is about 3 nm.