Multi-Electron Transfer at H-Terminated p-Si Electrolyte Interfaces: Large Photovoltages under Inversion Conditions

Keller, Niklas D.; Vecchi, Pierpaolo; Grills, David C.; Polyansky, Dmitry E.; Bein, Gabriella P.; Dempsey, Jillian L.; Cahoon, James F.; Parsons, Gregory N.; Sampaio, Renato N.; Meyer, Gerald J.

doi:10.1021/jacs.3c01990

Title: Multi-Electron Transfer at H-Terminated p-Si Electrolyte Interfaces: Large Photovoltages under Inversion Conditions

Journal Article · 10 May 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c01990 · OSTI ID:1984780

^[1]; Vecchi, Pierpaolo ^[2];

^[3];

^[1];

^[1]

Univ. of North Carolina, Charlotte, NC (United States)
Univ. of North Carolina, Charlotte, NC (United States); Univ. of Bologna (Italy)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

Here, photovoltages for hydrogen terminated p-Si(111) in an acetonitrile electrolyte were quantified with methyl viologen [1,1'-(CH₃)₂-4,4'-bipyridinium](PF₆)₂, abbreviated MV²⁺, and [Ru(bpy)₃](PF₆)₂, where bpy is 2,2'-bipyridine, that respectively undergo two and three one-electron transfer reductions. The reduction potentials, E°, of the two MV²⁺ reductions occurred at energies within the forbidden bandgap, while the three [Ru(bpy)₃]²⁺ reductions occurred within the continuum of conduction band states. Bandgap illumination resulted in reduction that were more positive than that measured with a degenerately doped n⁺-Si demonstrative of a photovoltage, Vph, that increased in the order: MV^2+/+ (260 mV) < MV^+/0 (400 mV) < Ru^2+/+ (530 mV) ~ Ru^+/0 (540 mV) ~ Ru^0/– (550 mV). Pulsed 532 nm excitation generated electron-hole pairs whose dynamics were nearly constant under depletion conditions and increased markedly as the potential was raised or lowered. A long wavelength absorption feature assigned to conduction band electrons provided additional evidence for the presence of an inversion layer. Collectively, the data reveal that the most optimal photovoltage, as well at the longest electron-hole pair lifetime and the highest surface electron concentration, occur when E° lies energetically within the unfilled conduction band states where an inversion layer is present. The bell-shaped dependence for electron-hole pair recombination with the surface potential was predicted by the time-honored SRH model providing a clear indication that this interface provides access to all four bias conditions, i.e., accumulation, flat band, depletion, and inversion. The implications of these findings for photocatalysis applications and solar energy conversion are discussed.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); University of North Carolina, Chapel Hill, NC (United States). Center for Hybrid Approaches in Solar Energy to Liquid Fuels (CHASE)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Alexander von Humboldt Foundation

Grant/Contract Number:: SC0012704; SC0021173

OSTI ID:: 1984780

Report Number(s):: BNL-224504-2023-JAAM

Journal Information:: Journal of the American Chemical Society, Vol. 145, Issue 20; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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