Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe2O3/NiO heterojunction

Biswas, Somnath; Husek, Jakub; Londo, Stephen; Fugate, Elizabeth A.; Baker, L. Robert

doi:10.1039/c8cp04502j

Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe₂O₃/NiO heterojunction

Journal Article · Wed Sep 05 00:00:00 UTC 2018 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c8cp04502j· OSTI ID:1594155

^[1]; ^[2]; Londo, Stephen ^[2]; Fugate, Elizabeth A. ^[2]; ^[2]

The Ohio State Univ., Columbus, OH (United States); The Ohio State University, Department of chemistry and biochemistry
The Ohio State Univ., Columbus, OH (United States)

NiO is widely utilized as a hole transport layer in solar energy devices where light absorption in a photoactive layer is followed by charge separation and hole injection into a NiO collection layer. Due to the complex electronic structure of the hybridized valence band in NiO, the chemical nature of the hole acceptor state has remained an open question, despite the fact that hole localization in this material significantly influences device efficiency. To comment on this, we present results of ultrafast charge carrier dynamics in a NiO based model heterojunction (Fe₂O₃/NiO) using extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy. Element specific XUV-RA spectroscopy demonstrates the formation of transient Ni³⁺ within 10 ps following selective photoexcitation of the underlying Fe₂O₃ substrate. This indicates that hole transfer in this system occurs to NiO valence band states composed of significant Ni 3d character. Additionally, we show that this hole injection process proceeds via a two-step sequential mechanism where fast, field-driven exciton dissociation occurs in Fe₂O₃ in 680 ± 60 fs, followed by subsequent hole injection to NiO in 9.2 ± 2.9 ps. Furthermore, these results reveal the chemical nature of the hole acceptor state in widely used NiO hole transport layers and provides a direct observation of exciton dissociation and interfacial hole transfer in this model system.

View Accepted Manuscript (DOE)

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0014051

OSTI ID:: 1594155

Alternate ID(s):: OSTI ID: 1469409

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 38 Vol. 20; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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