Influence of oxygen vacancy on the electronic structure of HfO$_2$ film

TL;DR

This study explores how oxygen vacancies affect the electronic structure of HfO₂ thin films, revealing band-tail states and occupation of Hf 5d states without inducing ferromagnetism, challenging previous claims.

Contribution

It provides new insights into the electronic states caused by oxygen vacancies in HfO₂ and clarifies the absence of ferromagnetism in such defective films.

Findings

Band-tail states beneath Hf 5d band observed

Occupation of Hf 5d states confirmed

No long-range ferromagnetic order detected

Abstract

We investigated the unoccupied part of the electronic structure of the oxygen-deficient hafnium oxide (HfO$_{\sim1.8}$) using soft x-ray absorption spectroscopy at O $K$ and Hf $N_3$ edges. Band-tail states beneath the unoccupied Hf 5$d$ band are observed in the O $K$-edge spectra; combined with ultraviolet photoemission spectrum, this indicates the non-negligible occupation of Hf 5$d$ state. However, Hf $N_3$-edge magnetic circular dichroism spectrum reveals the absence of a long-range ferromagnetic spin order in the oxide. Thus the small amount of $d$ electron gained by the vacancy formation does not show inter-site correlation, contrary to a recent report [M. Venkatesan {\it et al.}, Nature {\bf 430}, 630 (2004)].