Journal Article

The role of phase impurities and lattice defects on the electron dynamics and photochemistry of CuFeO2 solar photocathodes

Clement, Mathew C., Baker, L. Robert, Kim, Minkyu, Kim, Dongjoon, Fugate, Elizabeth A., Biswas, Somnath, Asthagiri, Aravind

2019

Overview

CuFeO 2 is a promising photocathode for H 2 evolution and CO 2 reduction reactions. To better understand the complex defect chemistry and role of impurity phases in this material and their effect on the photochemical performance, we employ visible light transient absorption spectroscopy and density functional theory (DFT) calculations to investigate the electron dynamics in electrochemically deposited Cu-Fe oxide thin films. Kinetic analysis of carrier lifetime shows a fast, sub-ps contribution to relaxation followed by persistence of a long-lived state to time delays greater than 2 ns. Increasing amplitude of the long-lived state is shown to correlate with the rate of fast initial relaxation, and this is explained in terms of a competition between charge carrier trapping and charge separation. Charge separation in CuFeO 2 occurs via hole thermalization from O 2p to Cu 3d valence band states leading to segregation of electrons and holes across layers in the CuFeO 2 lattice. Correlation between transient absorption measurements and DFT calculations suggest that Cu vacancies enhance photochemical performance by facilitating charge separation kinetics. In contrast, O interstitials are predicted to switch the relative positions of O 2p and Cu 3d valence band states, which would inhibit charge separation by inter-band hole thermalization. Finally, we find no evidence for electron injection from CuFeO 2 to CuO suggesting that charge separation at this heterostructure interface does not play a role in the carrier lifetime or photochemical performance of the catalysts studied here.

• Publisher: Tsinghua University Press
• Subject: Absorption spectroscopy / Atmospheric chemistry / Atomic/Molecular Structure and Spectra / Biomedicine / Biotechnology / Carbon dioxide / Carrier lifetime / Catalysts / Chemical reduction / Chemistry / Chemistry and Materials Science / Condensed Matter Physics / Correlation analysis / Crystal defects / Current carriers / Defects / Density functional theory / Efficiency / Electrons / Heterostructures / Hydrogen evolution / Impurities / Interstitials / Kinetics / Lattice vacancies / Lifetime / Light / Materials Science / Mathematical analysis / Nanotechnology / Organic chemistry / Photocathodes / Photochemicals / Photochemistry / Reaction kinetics / Research Article / Semiconductors / Separation / Thermalization (energy absorption) / Thin films / Timing / Valence band