Investigation of the metal-insulator transition in NdNiO3 films by site-selective X-ray absorption spectroscopy

In this work, multifunctional oxide NdNiO3 (NNO) thin films grown on a SrTiO3 (STO) substrate using pulsed-laser deposition are studied. Temperature dependent resistivity measurements revealed that NNO/STO samples exhibit a sharp thickness dependent metal-insulator transition (MIT) over a range of 150-200 K. It is known that the electronic properties of correlated oxides are extremely complex and sensitive to changes in orbital occupancy. To evaluate the changes in the electronic and/or crystallographic structure responsible for the MIT, a site-selective (O, Ni and Nd) X-ray absorption near edge structure (XANES) analysis is performed above and below the transition temperature. Analysis of XANES spectra suggests that: (i) in NNO films nominally trivalent Ni ions exhibit multiple valency (bond disproportionation), (ii) intermetallic hybridization plays an important role, (iii) the presence of strong O 2p-O 2p hole correlation at low temperature results in the opening of the p-p gap and (iv) the valency of Nd ions matches well with that of Nd3+. For NNO films exhibiting a sharp MIT, Ni 3d electron localization and concurrent existence of Ni 3d(8) and Ni 3d(8)(L) under bar (2) states are responsible for the observed transition. At temperatures below the MIT the O 2p-O 2p hole correlation is strong enough to split the O 2p band stabilizing insulating phase. Temperature and thickness dependent differences observed in the site-selective XANES data are discussed in terms of possible mechanisms for the MIT (negative charge-transfer type).