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Band Gap Adjustment in Perovskite-type Eu1−xCaxTiO3 via Ammonolysis

Widenmeyer, Marc ; Kohler, Tobias ; Samolis, Margarita ; Denko, Alexandra T. De ; Xiao, Xingxing ; Xie, Wenjie ; Osterloh, Frank E. ; Weidenkaff, Anke (2020)
Band Gap Adjustment in Perovskite-type Eu1−xCaxTiO3 via Ammonolysis.
In: Zeitschrift für Physikalische Chemie, 234 (5)
doi: 10.1515/zpch-2019-1429
Artikel, Bibliographie

Kurzbeschreibung (Abstract)

Perovskite-type oxynitrides AB(O,N)3 are potential candidates for photoelectrode materials in solar water splitting. A drawback of these materials is their low sintering tendency resulting in low electrical conductivities. Typically, they are prepared by ammonia treatment of insulating, wide band gap oxides. In this study, we propose an approach starting from small band gap oxides Eu1−xCaxTiO3− δ and then widen the band gaps in a controlled way by ammonolysis and partial Ca2+ substitution. Both together induced a distortion of the octahedral network and dilution of the Eu4f and N2p levels in the valence band. The effect is the stronger the more Ca2+ is present. Within the series of samples, Eu0.4Ca0.6Ti(O,N)3 had the most suitable optical band gap (EG ≈ 2.2 eV) for water oxidation. However, its higher Eu content compared to Eu0.1Ca0.9Ti(O,N)3 slowed down the charge carrier dynamics due to enhanced trapping and recombination as expressed by large accumulation (τ on) and decay (τ off) times of the photovoltage of up to 109 s and 486 s, respectively. In contrast, the highly Ca2+-substituted samples (x ≥ 0.7) were more prone to formation of TiN and oxygen vacancies also leading to Ti3+ donor levels below the conduction band. Therefore, a precise control of the ammonolysis temperature is essential, since even small amounts of TiN can suppress the photovoltage generation by fast recombination processes. Water oxidation tests on Eu0.4Ca0.6Ti(O,N)3 revealed a formation of 7.5 μmol O2 from 50 mg powder together with significant photocorrosion of the bare material. Combining crystal structure, chemical composition, and optical and electronical band gap data, a first simplified model of the electronical band structure of Eu1−xCaxTi(O,N)3 could be proposed.

Typ des Eintrags: Artikel
Erschienen: 2020
Autor(en): Widenmeyer, Marc ; Kohler, Tobias ; Samolis, Margarita ; Denko, Alexandra T. De ; Xiao, Xingxing ; Xie, Wenjie ; Osterloh, Frank E. ; Weidenkaff, Anke
Art des Eintrags: Bibliographie
Titel: Band Gap Adjustment in Perovskite-type Eu1−xCaxTiO3 via Ammonolysis
Sprache: Englisch
Publikationsjahr: Februar 2020
Verlag: De Gruyter
Titel der Zeitschrift, Zeitung oder Schriftenreihe: Zeitschrift für Physikalische Chemie
Jahrgang/Volume einer Zeitschrift: 234
(Heft-)Nummer: 5
DOI: 10.1515/zpch-2019-1429
URL / URN: https://doi.org/10.1515/zpch-2019-1429
Kurzbeschreibung (Abstract):

Perovskite-type oxynitrides AB(O,N)3 are potential candidates for photoelectrode materials in solar water splitting. A drawback of these materials is their low sintering tendency resulting in low electrical conductivities. Typically, they are prepared by ammonia treatment of insulating, wide band gap oxides. In this study, we propose an approach starting from small band gap oxides Eu1−xCaxTiO3− δ and then widen the band gaps in a controlled way by ammonolysis and partial Ca2+ substitution. Both together induced a distortion of the octahedral network and dilution of the Eu4f and N2p levels in the valence band. The effect is the stronger the more Ca2+ is present. Within the series of samples, Eu0.4Ca0.6Ti(O,N)3 had the most suitable optical band gap (EG ≈ 2.2 eV) for water oxidation. However, its higher Eu content compared to Eu0.1Ca0.9Ti(O,N)3 slowed down the charge carrier dynamics due to enhanced trapping and recombination as expressed by large accumulation (τ on) and decay (τ off) times of the photovoltage of up to 109 s and 486 s, respectively. In contrast, the highly Ca2+-substituted samples (x ≥ 0.7) were more prone to formation of TiN and oxygen vacancies also leading to Ti3+ donor levels below the conduction band. Therefore, a precise control of the ammonolysis temperature is essential, since even small amounts of TiN can suppress the photovoltage generation by fast recombination processes. Water oxidation tests on Eu0.4Ca0.6Ti(O,N)3 revealed a formation of 7.5 μmol O2 from 50 mg powder together with significant photocorrosion of the bare material. Combining crystal structure, chemical composition, and optical and electronical band gap data, a first simplified model of the electronical band structure of Eu1−xCaxTi(O,N)3 could be proposed.

Freie Schlagworte: Electronic band structure, europium, oxynitride, perovskite, surface photovoltage spectroscopy, titanium
Fachbereich(e)/-gebiet(e): 11 Fachbereich Material- und Geowissenschaften
11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft
11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft > Werkstofftechnik und Ressourcenmanagement
Hinterlegungsdatum: 20 Mai 2020 07:11
Letzte Änderung: 22 Mai 2020 08:06
PPN:
Projekte: This research study was supported by the Deutsche Forschungsgemeinschaft through the DFG Priority Program SPP 1613 (Funder Id: http://dx.doi.org/10.13039/501100001659, Grant WE 2803/7-1)., Support for surface photovoltage spectroscopy measurements was provided by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DOE-SC0015329.
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