Double-hole codoped huge-gap semiconductor ZrO2 for visible-light photocatalysis

Area of Science:

• Materials Science
• Physical Chemistry
• Semiconductor Physics

Background:

• Photoelectrochemical (PEC) performance relies on semiconductor band structure engineering.
• Anionic doping is a strategy to modify semiconductor properties.
• Zirconium dioxide (ZrO2) is a wide-band-gap semiconductor with potential for photocatalysis.

Purpose of the Study:

• To investigate the effects of anionic monodoping and codoping on ZrO2's electronic structure and photocatalytic activity.
• To explore double-hole doping strategies for enhancing solar water splitting.
• To identify promising codoped ZrO2 materials for visible light photocatalysis.

Main Methods:

• Density functional theory (DFT) calculations were extensively performed.
• Anionic monodoping (N, C, P) and codoping (N+N, C+S, N+P) effects were studied.
• Electronic structures, band gaps, and band edge positions were analyzed.

Main Results:

• Anionic monodoping introduced unoccupied impurity states, potentially hindering photocatalysis.
• Double-hole doping with (N+N), (C+S), and (N+P) pairs narrowed the band gap.
• Codoping created delocalized intermediate bands, suppressing electron-hole recombination and improving visible light absorption.

Conclusions:

• Double-hole doping via anionic codoping pairs is an effective strategy for tuning wide-band-gap semiconductor properties.
• Codoped ZrO2 systems exhibit favorable band edge positions for water splitting.
• Engineered ZrO2 with double-hole doping shows significant potential as efficient photocatalysts for visible light water splitting.