X-ray photoelectron study and first principle calculations of the electronic structure of PbFe1/2Nb1/2O3 single crystal in the ferroelectric and paraelectric phases

The present study is the first in which the theoretical prediction of the changes in the density of states of single crystal of PbFe1/2Nb1/2O3 (PFN) multiferroic depending on a temperature at the ferroelectric - paraelectric transition is experimentally confirmed by the X-ray photoelectron spectroscopy. The valence band XPS spectra of PFN single-crystal at three temperatures T1 = 297 K (monoclinic phase), T2 = 368 K (tetragonal) and T3 = 403 K (cubic) were obtained by X-ray photoelectron study using ESCALAB 250. It is found out that the experimental valence band XPS spectra of PFN single-crystals in ferroelectric and paraelectric phases consist of two main peaks with a difference in relative intensity and energy position of the second peak. The density of states of PFN was calculated for tetragonal ferroelectric (368 K) and cubic paraelectric (403 K) phases. The first main peak corresponds to strongly hybridized Fe3d, Nb3d and O2p states while the second peak is mainly composed of Pb6s states. According to the experimental data, the position of the second main peak of the total density of states of PFN in the ferroelectric monoclinic phase is shifted toward the first peak relatively to its position in the paraelectric phase by 0.28 eV and for the tetragonal phase by 0.15 eV, the latter value coincides well with the calculated value equal to 0.17 eV.