Tuning Intermediate Bands of Protective Coatings to Reach the Bulk-Recombination Limit of Stable Water-Oxidation GaP Photoanodes

Shen, Xin; Zhao, Tianshuo; Su, Haoqing; Yang, Meiqi; Chen, Jiaye; Liu, Yulin; Yanagi, Rito; Solanki, Devan; Hu, Shu

doi:10.1002/aenm.202201314

Title: Tuning Intermediate Bands of Protective Coatings to Reach the Bulk-Recombination Limit of Stable Water-Oxidation GaP Photoanodes

Journal Article · Fri Jun 17 00:00:00 EDT 2022 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202201314· OSTI ID:1976251

^[1]; Zhao, Tianshuo ^[1]; Su, Haoqing ^[1]; Yang, Meiqi ^[1]; Chen, Jiaye ^[1]; Liu, Yulin ^[1]; Yanagi, Rito ^[1]; Solanki, Devan ^[1];

^[1]

Yale University, New Haven, CT (United States); Energy Sciences Institute, West Haven, CT (United States)

Abstract Stable photoelectrochemical solar fuel production requires protective coatings to achieve effective charge separation, transport, and injection at the semiconductor–liquid interfaces, implying that the coating should energetically align its intermediate band (IB) with both the photoabsorber's band edge and co‐catalyst's potentials. Yet approaches to adjust coating IB positions to accommodate various semiconductor light absorbers for constructing efficient and stable photoelectrodes have not been developed. Herein, three types of transition metal (M = Mn ²⁺ , Mn ³⁺ , and Cr ³⁺ ions) alloyed TiO ₂ coatings are discovered using atomic layer deposition (ALD). The IB energetics of these coatings are characterized by X‐ray photoelectron spectroscopy and are found to be tunable inside the TiO ₂ bandgap, through varying ALD growth conditions. By applying these coatings to n‐type GaP and integrating with IrO _x co‐catalysts, the water‐oxidation J – E performance is comparable to an uncoated corroding GaP photoanode. It reaches the bulk recombination limit of the GaP and achieves ≈28% absorbed photon to current efficiency under 475‐nm light excitation (6.48 mW cm ⁻² ) and 100‐h stable water oxidation. The outstanding performance and stability are attributed to the efficient charge separation and hole transport, as allowed by the energy alignment of the coating IB and the GaP valence band edge.

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Research Organization:: Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); Naval Research Office (NRO); USDOE

Grant/Contract Number:: SC0021953; N00014-19-1-2132; DE‐SC0021953

OSTI ID:: 1976251

Alternate ID(s):: OSTI ID: 1873002

Journal Information:: Advanced Energy Materials, Vol. 12, Issue 29; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Tuning Intermediate Bands of Protective Coatings to Reach the Bulk-Recombination Limit of Stable Water-Oxidation GaP Photoanodes

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