Electronic Structure and Performance Bottlenecks of CuFeO 2 Photocathodes

Chang Ming Jiang, Sebastian E. Reyes-Lillo, Yufeng Liang, Yi Sheng Liu, Guiji Liu, Francesca M. Toma, David Prendergast, Ian D. Sharp, Jason K. Cooper

Resultado de la investigación: Article

3 Citas (Scopus)

Resumen

The path to realizing low-cost, stable, and earth-abundant photoelectrodes can be enabled through a detailed understanding of the optoelectronic properties of these materials by combining theory and experimental techniques. Of the limited set of oxide photocathode materials currently available, CuFeO 2 has emerged as a promising candidate warranting detailed attention. In this work, highly compact thin films of rhombohedral (3R) CuFeO 2 were prepared via reactive co-sputtering. Despite its 1.43 eV indirect band gap, a cathodic photocurrent of 0.85 mA/cm 2 was obtained at 0.4 V versus reversible hydrogen electrode in the presence of a sacrificial electron acceptor. This unexpected performance was related to inefficient bulk charge separation because of the ultrafast (<1 ps) self-trapping of photogenerated free carriers. The electronic structure of 3R-CuFeO 2 was elucidated through a combination of optical and X-ray spectroscopic techniques and further complemented by first-principles computational methods including a many-body approach for computing the O K-edge X-ray absorption spectrum. Through resonant inelastic X-ray scattering spectroscopy, the visible absorption edges of CuFeO 2 were found to correspond to Cu ↠Fe metal-to-metal charge transfer, which exhibits a high propensity toward self-trapping. Findings of the present work enable us to understand the performance bottlenecks of CuFeO 2 photocathodes and suggest feasible strategies for improving material limitations.

Idioma originalEnglish
Páginas (desde-hasta)2524-2534
Número de páginas11
PublicaciónChemistry of Materials
Volumen31
N.º7
DOI
EstadoPublished - 9 abr 2019

Huella dactilar

Photocathodes
Electronic structure
Metals
Inelastic scattering
X ray absorption
Computational methods
X ray scattering
Photocurrents
Optoelectronic devices
Oxides
Sputtering
Charge transfer
Absorption spectra
Hydrogen
Energy gap
Earth (planet)
Spectroscopy
X rays
Thin films
Electrodes

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Citar esto

Jiang, C. M., Reyes-Lillo, S. E., Liang, Y., Liu, Y. S., Liu, G., Toma, F. M., ... Cooper, J. K. (2019). Electronic Structure and Performance Bottlenecks of CuFeO 2 Photocathodes. Chemistry of Materials, 31(7), 2524-2534. https://doi.org/10.1021/acs.chemmater.9b00009
Jiang, Chang Ming ; Reyes-Lillo, Sebastian E. ; Liang, Yufeng ; Liu, Yi Sheng ; Liu, Guiji ; Toma, Francesca M. ; Prendergast, David ; Sharp, Ian D. ; Cooper, Jason K. / Electronic Structure and Performance Bottlenecks of CuFeO 2 Photocathodes. En: Chemistry of Materials. 2019 ; Vol. 31, N.º 7. pp. 2524-2534.
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Jiang, CM, Reyes-Lillo, SE, Liang, Y, Liu, YS, Liu, G, Toma, FM, Prendergast, D, Sharp, ID & Cooper, JK 2019, 'Electronic Structure and Performance Bottlenecks of CuFeO 2 Photocathodes', Chemistry of Materials, vol. 31, n.º 7, pp. 2524-2534. https://doi.org/10.1021/acs.chemmater.9b00009

Electronic Structure and Performance Bottlenecks of CuFeO 2 Photocathodes. / Jiang, Chang Ming; Reyes-Lillo, Sebastian E.; Liang, Yufeng; Liu, Yi Sheng; Liu, Guiji; Toma, Francesca M.; Prendergast, David; Sharp, Ian D.; Cooper, Jason K.

En: Chemistry of Materials, Vol. 31, N.º 7, 09.04.2019, p. 2524-2534.

Resultado de la investigación: Article

TY - JOUR

T1 - Electronic Structure and Performance Bottlenecks of CuFeO 2 Photocathodes

AU - Jiang, Chang Ming

AU - Reyes-Lillo, Sebastian E.

AU - Liang, Yufeng

AU - Liu, Yi Sheng

AU - Liu, Guiji

AU - Toma, Francesca M.

AU - Prendergast, David

AU - Sharp, Ian D.

AU - Cooper, Jason K.

PY - 2019/4/9

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N2 - The path to realizing low-cost, stable, and earth-abundant photoelectrodes can be enabled through a detailed understanding of the optoelectronic properties of these materials by combining theory and experimental techniques. Of the limited set of oxide photocathode materials currently available, CuFeO 2 has emerged as a promising candidate warranting detailed attention. In this work, highly compact thin films of rhombohedral (3R) CuFeO 2 were prepared via reactive co-sputtering. Despite its 1.43 eV indirect band gap, a cathodic photocurrent of 0.85 mA/cm 2 was obtained at 0.4 V versus reversible hydrogen electrode in the presence of a sacrificial electron acceptor. This unexpected performance was related to inefficient bulk charge separation because of the ultrafast (<1 ps) self-trapping of photogenerated free carriers. The electronic structure of 3R-CuFeO 2 was elucidated through a combination of optical and X-ray spectroscopic techniques and further complemented by first-principles computational methods including a many-body approach for computing the O K-edge X-ray absorption spectrum. Through resonant inelastic X-ray scattering spectroscopy, the visible absorption edges of CuFeO 2 were found to correspond to Cu ↠Fe metal-to-metal charge transfer, which exhibits a high propensity toward self-trapping. Findings of the present work enable us to understand the performance bottlenecks of CuFeO 2 photocathodes and suggest feasible strategies for improving material limitations.

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U2 - 10.1021/acs.chemmater.9b00009

DO - 10.1021/acs.chemmater.9b00009

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JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

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