Advanced chemical state studies of oxide films by lab-based HAXPES combining soft and hard X-ray sources

TL;DR

This paper demonstrates how lab-based combined soft and hard X-ray photoelectron spectroscopy (HAXPES) can non-destructively analyze the chemical and electronic structure of buried oxide interfaces at different depths, previously only possible at synchrotrons.

Contribution

It introduces the use of commercial lab-based HAXPES systems with both soft and hard X-ray sources for routine chemical state analysis of functional oxides.

Findings

Able to probe local chemical states at various depths in oxide films

Validated technique on Al2O3, SiO2, TiO2 films

Discussed calibration procedures for kinetic energy scale

Abstract

The greater information depth provided in Hard X-ray Photoelectron Spectroscopy (HAXPES) enables non-destructive analyses of the chemistry and electronic structure of buried interfaces. Moreover, for industrially relevant elements like Al, Si and Ti, the combined access to the Al 1s, Si 1s or Ti 1s photoelectron line and its associated Al KLL, Si KLL or Ti KLL Auger transition, as required for local chemical state analysis on the basis of the Auger parameter, is only possible with hard X-rays. Until now, such photoemission studies were only possible at synchrotron facilities. Recently however, the first commercial XPS/HAXPES systems, equipped with both soft and hard X-ray sources, have entered the market, providing unique opportunities for monitoring the local chemical state of all constituent ions in functional oxides at different probing depths, in a routine laboratory environment. Bulk-sensitive shallow core-levels can be excited using either the hard or soft X-ray source, whereas more surface-sensitive deep core-level photoelectron lines and associated Auger transitions can be measured using the hard X-ray source. As demonstrated for thin Al2O3, SiO2 and TiO2 films, the local chemical state of the constituting ions in the oxide may even be probed at near constant probing depth by careful selection of sets of photoelectron and Auger lines, as excited with the combined soft and hard X-ray sources. We highlight the potential of lab-based HAXPES for the research on functional oxides and also discuss relevant technical details regarding the calibration of the kinetic binding energy scale.