Electronic Excitations of Hematite Heteroepitaxial Films Measured by Resonant Inelastic X-Ray Scattering at the Fe L-edge

TL;DR

This study used resonant inelastic X-ray scattering to analyze electronic excitations in hematite thin films, revealing temperature effects and dopant influences on ligand field excitations, with implications for photoanode efficiency.

Contribution

It provides the first detailed RIXS analysis of doped hematite films, showing temperature-dependent electronic excitations and their relation to electronic structure and photoelectrochemical performance.

Findings

Ligand field excitations are mostly non-dispersive across momentum transfers.

Temperature significantly affects the RIXS spectral features.

Dopant type influences free charge carrier effects in the spectra.

Abstract

Resonant Inelastic X-Ray Scattering (RIXS) spectra of hematite were measured at the Fe L3-edge for heteroepitaxial thin films which were undoped and doped with 1% Ti, Sn or Zn, in the energy loss range in excess of 1 eV to study electronic transitions. The spectra were measured for several momentum transfers (q), conducted at both low temperature (T=14K) and room temperature. While we can not rule out dispersive features possibly owing to propagating excitations, the coarse envelopes of the general spectra did not appreciably change shape with q, implying that the bulk of the observed L-edge RIXS intensity originates from (mostly) non-dispersive ligand field (LF) excitations. Summing the RIXS spectra over q and comparing the results at T=14 K to those at T=300 K, revealed pronounced temperature effects, including an intensity change and energy shift of the 1.4 eV peak, a broadband intensity increase of the 3-4 eV range, and higher energy features. The q-summed spectra and their temperature dependences are virtually identical for nearly all of the samples with different dopants, save for the temperature dependence of the Ti-doped sample's spectrum, which we attribute to being affected by a large number of free charge carriers. Comparing with magnetization measurements for different temperatures and dopings likewise did not show a clear correlation between the RIXS spectra and the magnetic ordering states. To clarify the excited states, we performed spin multiplet calculations which were in excellent agreement with the RIXS spectra over a wide energy range and provide detailed electronic descriptions of the excited states. The implications of these findings to the photoconversion efficiency of hematite photoanodes is discussed.