Carrier Localization on the Nanometer-Scale limits Transport in Metal Oxide Photoabsorbers

Markus Schleuning; Moritz Kölbach; Ibbi Ahmet; Raphael Präg; Ronen Gottesman; René Gunder; Mengyuan Zhang; Dan Ralf Wargulski; Daniel Abou-Ras; Daniel A. Grave; Fatwa F. Abdi; Roel van de Krol; Klaus Schwarzburg; Rainer Eichberger; Dennis Friedrich; Hannes Hempel

doi:10.1002/adfm.202300065

Carrier Localization on the Nanometer-Scale limits Transport in Metal Oxide Photoabsorbers

Markus Schleuning, Moritz Kölbach, Ibbi Ahmet, Raphael Präg, Ronen Gottesman, René Gunder, Mengyuan Zhang, Dan Ralf Wargulski, Daniel Abou-Ras, Daniel A. Grave, Fatwa F. Abdi, Roel van de Krol, Klaus Schwarzburg, Rainer Eichberger, Dennis Friedrich, Hannes Hempel

Research output: Contribution to journal › Article › peer-review

Abstract

Metal oxides are considered as stable and low-cost photoelectrode candidates for hydrogen production by photoelectrochemical solar water splitting. However, their power conversion efficiencies usually suffer from poor transport of photogenerated charge carriers, which has been attributed previously to a variety of effects occurring on different time and length scales. In search for common understanding and for a better photo-conducting metal oxide photoabsorber, CuFeO₂, α-SnWO₄, BaSnO₃, FeVO₄, CuBi₂O₄, α-Fe₂O₃, and BiVO₄ are compared. Their kinetics of thermalization, trapping, localization, and recombination are monitored continuously 100 fs–100 µs and mobilities are determined for different probing lengths by combined time-resolved terahertz and microwave spectroscopy. As common issue, we find small mobilities < 3 cm²V^-1s^-1. Partial carrier localization further slows carrier diffusion beyond localization lengths of 1–6 nm and explains the extraordinarily long conductivity tails, which should not be taken as a sign of long diffusion lengths. For CuFeO₂, the localization is attributed to electrostatic barriers that enclose the crystallographic domains. The most promising novel material is BaSnO₃, which exhibits the highest mobility after reducing carrier localization by annealing in H₂. Such overcoming of carrier localization should be an objective of future efforts to enhance charge transport in metal oxides.

Original language	English
Article number	2300065
Journal	Advanced Functional Materials
Volume	33
Issue number	25
DOIs	https://doi.org/10.1002/adfm.202300065
State	Published - 19 Jun 2023
Externally published	Yes

Bibliographical note

Funding Information:
M.K., M.S., and H.H. initiated and outlined the study. M.S. performed and analyzed the TRMC, oc-TRMC, st-TRMC, and OPTP measurements. M.S. and H.H. wrote the manuscript. M.S. and H.H. designed the figures. H.H. derived Equation 3. H.H. and D.F. supervised the project. K.S. performed the COMSOL simulations of the TRMC cavity. R.G. (HZB) measured and analyzed the XRD pattern. D.A.R. and D.R.W. measured and analyzed the EBSD. R.v.d.K., supervised the contributions from his group. R.v.d.K. and D.F. secured funding for the project. M.K. prepared the BiVO4 (PLD) and α-SnWO4. R.P. prepared CuFeO2. I.A. prepared the BiVO4 (spray) and BaSnO3. R.G. (HUJI) prepared CuBi2O4. A.R., and D.G. prepared the α-Fe2O3:Sn. M.Z. prepared the FeVO4.All authors discussed the results and revised the manuscript. The authors acknowledge the financial support for this work from the Helmholtz International Research School “Hybrid Integrated Systems for Conversion of Solar Energy” (HI-SCORE), an initiative co-funded by the Initiative and Networking Fund of the Helmholtz Association (HIRS-0008). M.K. acknowledges funding from the German Bundesministerium für Bildung and Forschung (BMBF), project “H2Demo” (no. 03SF0619K). We acknowledge Avner Rothschild for providing lab facilities at the Technion. Open access funding enabled and organized by Projekt DEAL.

Funding Information:
M.K., M.S., and H.H. initiated and outlined the study. M.S. performed and analyzed the TRMC, oc‐TRMC, st‐TRMC, and OPTP measurements. M.S. and H.H. wrote the manuscript. M.S. and H.H. designed the figures. H.H. derived Equation 3 . H.H. and D.F. supervised the project. K.S. performed the COMSOL simulations of the TRMC cavity. R.G. (HZB) measured and analyzed the XRD pattern. D.A.R. and D.R.W. measured and analyzed the EBSD. R.v.d.K., supervised the contributions from his group. R.v.d.K. and D.F. secured funding for the project. M.K. prepared the BiVO (PLD) and α‐SnWO. R.P. prepared CuFeO. I.A. prepared the BiVO (spray) and BaSnO. R.G. (HUJI) prepared CuBiO A.R., and D.G. prepared the α‐FeO:Sn. M.Z. prepared the FeVO.All authors discussed the results and revised the manuscript. The authors acknowledge the financial support for this work from the Helmholtz International Research School “Hybrid Integrated Systems for Conversion of Solar Energy” (HI‐SCORE), an initiative co‐funded by the Initiative and Networking Fund of the Helmholtz Association (HIRS‐0008). M.K. acknowledges funding from the German Bundesministerium für Bildung and Forschung (BMBF), project “H2Demo” (no. 03SF0619K). We acknowledge Avner Rothschild for providing lab facilities at the Technion. 4 4 2 4 3 2 4. 2 3 4

Publisher Copyright:
© 2023 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH.

Keywords

carrier localization
metal oxides
mobilities
photoconductivity
water splitting

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/adfm.202300065

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Schleuning, M., Kölbach, M., Ahmet, I., Präg, R., Gottesman, R., Gunder, R., Zhang, M., Wargulski, D. R., Abou-Ras, D., Grave, D. A., Abdi, F. F., van de Krol, R., Schwarzburg, K., Eichberger, R., Friedrich, D., & Hempel, H. (2023). Carrier Localization on the Nanometer-Scale limits Transport in Metal Oxide Photoabsorbers. Advanced Functional Materials, 33(25), Article 2300065. https://doi.org/10.1002/adfm.202300065

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abstract = "Metal oxides are considered as stable and low-cost photoelectrode candidates for hydrogen production by photoelectrochemical solar water splitting. However, their power conversion efficiencies usually suffer from poor transport of photogenerated charge carriers, which has been attributed previously to a variety of effects occurring on different time and length scales. In search for common understanding and for a better photo-conducting metal oxide photoabsorber, CuFeO2, α-SnWO4, BaSnO3, FeVO4, CuBi2O4, α-Fe2O3, and BiVO4 are compared. Their kinetics of thermalization, trapping, localization, and recombination are monitored continuously 100 fs–100 µs and mobilities are determined for different probing lengths by combined time-resolved terahertz and microwave spectroscopy. As common issue, we find small mobilities < 3 cm2V-1s-1. Partial carrier localization further slows carrier diffusion beyond localization lengths of 1–6 nm and explains the extraordinarily long conductivity tails, which should not be taken as a sign of long diffusion lengths. For CuFeO2, the localization is attributed to electrostatic barriers that enclose the crystallographic domains. The most promising novel material is BaSnO3, which exhibits the highest mobility after reducing carrier localization by annealing in H2. Such overcoming of carrier localization should be an objective of future efforts to enhance charge transport in metal oxides.",

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author = "Markus Schleuning and Moritz K{\"o}lbach and Ibbi Ahmet and Raphael Pr{\"a}g and Ronen Gottesman and Ren{\'e} Gunder and Mengyuan Zhang and Wargulski, {Dan Ralf} and Daniel Abou-Ras and Grave, {Daniel A.} and Abdi, {Fatwa F.} and {van de Krol}, Roel and Klaus Schwarzburg and Rainer Eichberger and Dennis Friedrich and Hannes Hempel",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH.",

year = "2023",

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Schleuning, M, Kölbach, M, Ahmet, I, Präg, R, Gottesman, R, Gunder, R, Zhang, M, Wargulski, DR, Abou-Ras, D, Grave, DA, Abdi, FF, van de Krol, R, Schwarzburg, K, Eichberger, R, Friedrich, D & Hempel, H 2023, 'Carrier Localization on the Nanometer-Scale limits Transport in Metal Oxide Photoabsorbers', Advanced Functional Materials, vol. 33, no. 25, 2300065. https://doi.org/10.1002/adfm.202300065

TY - JOUR

T1 - Carrier Localization on the Nanometer-Scale limits Transport in Metal Oxide Photoabsorbers

AU - Schleuning, Markus

AU - Kölbach, Moritz

AU - Ahmet, Ibbi

AU - Präg, Raphael

AU - Gottesman, Ronen

AU - Gunder, René

AU - Zhang, Mengyuan

AU - Wargulski, Dan Ralf

AU - Abou-Ras, Daniel

AU - Grave, Daniel A.

AU - Abdi, Fatwa F.

AU - van de Krol, Roel

AU - Schwarzburg, Klaus

AU - Eichberger, Rainer

AU - Friedrich, Dennis

AU - Hempel, Hannes

PY - 2023/6/19

Y1 - 2023/6/19

N2 - Metal oxides are considered as stable and low-cost photoelectrode candidates for hydrogen production by photoelectrochemical solar water splitting. However, their power conversion efficiencies usually suffer from poor transport of photogenerated charge carriers, which has been attributed previously to a variety of effects occurring on different time and length scales. In search for common understanding and for a better photo-conducting metal oxide photoabsorber, CuFeO2, α-SnWO4, BaSnO3, FeVO4, CuBi2O4, α-Fe2O3, and BiVO4 are compared. Their kinetics of thermalization, trapping, localization, and recombination are monitored continuously 100 fs–100 µs and mobilities are determined for different probing lengths by combined time-resolved terahertz and microwave spectroscopy. As common issue, we find small mobilities < 3 cm2V-1s-1. Partial carrier localization further slows carrier diffusion beyond localization lengths of 1–6 nm and explains the extraordinarily long conductivity tails, which should not be taken as a sign of long diffusion lengths. For CuFeO2, the localization is attributed to electrostatic barriers that enclose the crystallographic domains. The most promising novel material is BaSnO3, which exhibits the highest mobility after reducing carrier localization by annealing in H2. Such overcoming of carrier localization should be an objective of future efforts to enhance charge transport in metal oxides.

AB - Metal oxides are considered as stable and low-cost photoelectrode candidates for hydrogen production by photoelectrochemical solar water splitting. However, their power conversion efficiencies usually suffer from poor transport of photogenerated charge carriers, which has been attributed previously to a variety of effects occurring on different time and length scales. In search for common understanding and for a better photo-conducting metal oxide photoabsorber, CuFeO2, α-SnWO4, BaSnO3, FeVO4, CuBi2O4, α-Fe2O3, and BiVO4 are compared. Their kinetics of thermalization, trapping, localization, and recombination are monitored continuously 100 fs–100 µs and mobilities are determined for different probing lengths by combined time-resolved terahertz and microwave spectroscopy. As common issue, we find small mobilities < 3 cm2V-1s-1. Partial carrier localization further slows carrier diffusion beyond localization lengths of 1–6 nm and explains the extraordinarily long conductivity tails, which should not be taken as a sign of long diffusion lengths. For CuFeO2, the localization is attributed to electrostatic barriers that enclose the crystallographic domains. The most promising novel material is BaSnO3, which exhibits the highest mobility after reducing carrier localization by annealing in H2. Such overcoming of carrier localization should be an objective of future efforts to enhance charge transport in metal oxides.

KW - carrier localization

KW - metal oxides

KW - mobilities

KW - photoconductivity

KW - water splitting

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ER -

Carrier Localization on the Nanometer-Scale limits Transport in Metal Oxide Photoabsorbers

Abstract

Bibliographical note

Keywords

UN SDGs

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