Band Gap Modulation of SrTiO3 upon CO2 Adsorption

TL;DR

This study uses ab initio calculations to show how CO2 adsorption on SrTiO3 surfaces modulates the band gap, revealing potential for chemical sensing based on surface termination and coverage effects.

Contribution

It demonstrates the distinct effects of CO2 adsorption on different SrTiO3 surface terminations and their impact on band gap modulation for sensing applications.

Findings

CO2 adsorption opens the band gap of SrTiO3.

Surface termination influences how CO2 affects electronic states.

Band gap modulation depends on CO2 coverage.

Abstract

CO2 chemisorption on SrTiO3(001) surfaces is studied using ab initio calculations in order to establish new chemical sensing mechanisms. We find that CO2 adsorption opens the material band gap, however, while the adsorption on the TiO2-terminated surface neutralizes surface states at the valence band (VB) maximum, CO2 on the SrO-terminated surfaces suppresses the conduction band (CB) minimum. For the TiO2-terminated surface, the effect is explained by the passivation of dangling bonds, whereas for the SrO-terminated surface, the suppression is caused by the surface relaxation. Modulation of the VB states implies a more direct change in charge distribution, and thus the induced change in band gap is more prominent at the TiO2 termination. Further, we show that both CO2 adsorption energy and surface band gap are strongly dependent on CO2 coverage, suggesting that the observed effect can be utilized for sensing application in a wide range of CO2 concentrations.