Study of metal-insulator transition in rare-earth oxides and nickel.

Author(s)

Marcia Tsuyama Escote

• Document type: Doctoral Thesis
• Press: São Paulo.
• Institution: Universidade de São Paulo (USP). Instituto de Física (IF/SBI)
• Defense date: 2002-02-06

Examining board members

Renato de Figueiredo Jardim; Adalberto Fazzio; Reginaldo Muccillo; Elson Longo da Silva; Jose Arana Varela

• Advisor: Renato de Figueiredo Jardim

Abstract

This work reports a systematic study on the synthesis and general physical properties of polycrystalline samples of Nd IND. 1-X R IND. X NiO IND. 3; R = Sm, Eu, 0 < OU = X < OU = 1. These compounds exhibit a metal-insulator MI phase transition in a broad range of temperature 200 < OU = T IND. MI < OU = 400 K. The samples were prepared through sol-gel precursors and sintered at extreme conditions: high temperatures 1000 GRAUSC and under oxygen pressures up to 80 bar. These samples were characterized by several techniques including X-ray powder diffraction XRD, neutron diffraction as a function of temperature NRD, electrical resistivity ro(T), thermal conductivity capa(T), Seebeck coefficient S(T), differential scanning calorimetry DSC, and magnetic susceptibility qui(T). The results of XRD revealed that all samples are single phase and crystallize in an orthorhombic structure, space group Pbnm. The NRD data, combined with the Rietveld analysis, indicated small changes in the lattice parameters a, b, and c and in the volume V of the unit cell T DA ORDEM DE T IND. MI. Such a small change in these parameters is accompained by either a little decrease of the superexchange angle teta and a small expansion of the Ni-O bond-length. The ro(T) data exhibit interesting features such as: (1) a metallic-like behavior of ro(T) at high temperatures; (2) a huge increase of the magnitude of ro(T) at T DA ORDEM DE T IND. MI; and (3) a thermal hysteresis occurring just below T DA ORDEM DE T IND. MI in a temperature interval as large as 100K. Such a thermal hysteresis is characteristic of a first order MI transition and was found to vanish with increasing substitution of x. This strongly suggests that increasing x modify the character of this transition to second order. Thermal properties were carried out and confirmed the change of this MI transition with increasing x. In addition, an analysis of the capa(T) data indicate that phonons are the major thermal carriers in these nickelates. Also, the Seebeck coefficient S(T) data revealed features of a conventional metal at higher temperatures with electrons as carriers. An accurate analysis of the S(T) data based on simple band structure arguments indicate a density of states at the Fermi level of 10 POT. 23 (eVcm POT. 3) POT. -1 and energy gaps in the insulating regime close to 20 meV. The character of the first order transition in lightly substituted samples at T DA ORDEM DE T IND. MI was also inferred from the DSC data. The S(T) data confirmed the occurrence of the metal-insulator transition and the already observed change from first to second order character with increasing x. The magnetic susceptibility ípsilon(T) data have been precisely corrected by a systematic subtraction of the R POT.3+-ion contribution of the measured qui(T). Linear adjusts of the corrected curves above 150K where found to fit the Curie-Weiss law with effective magnetic moment of mü IND. EFF ~ 1.76 mü IND. B, which is close to the free-ion value of mü IND. EFF ~ 1.76 mü IND. B (Ni POT. 3+). These results indicate that the Ni POT. 3+ array displays an antiferromagnetic ordering below a well-defined temperature T IND. N, which is close to T IND.MI for Nd IND. 1-X R IND. X NiO IND. 3 and lightly substituted samples. However, the evolution of the susceptibility of the Ni POT. 3+ array displays features which are fingerprints of unconventional antiferromagnetic state. These features, observed mostly below T IND. N, include a field independent irreversibility of qui(T) and a systematic increase of qui(T) with decreasing temperature, resembling that of a paramagnet. An analysis of the electronic contribution to ípsilon(T) resulted in a density of states at the Fermi level close to the one estimated from the S(T) data. These results are discussed within the context of recent experimental results and theories employed to explain the origin of the metal-insulator transition in these nickelates. (AU)