Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe2O3/NiO heterojunction. Issue 38 (11th September 2018)

• Record Type: Journal Article
• Authors: Biswas, Somnath; Husek, Jakub; Londo, Stephen; Fugate, Elizabeth A.; Baker, L. Robert
• Is Part Of: Physical chemistry chemical physics. Volume 20:Issue 38(2018)
• Page Start: 24545
• Page End: 24552
• Publication Date: 2018-09-11
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c8cp04502j
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Ultrafast XUV reflection–absorption identifies interfacial charge transfer mechanism and the hole acceptor state in a Fe2 O3 /NiO model heterojunction Abstract : 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 (Fe2 O3 /NiO) using extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy. Element specific XUV-RA spectroscopy demonstrates the formation of transient Ni 3+ within 10 ps following selective photoexcitation of the underlying Fe2 O3 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 Fe2 O3 in 680 ± 60 fs, followed by subsequent hole injection to NiO in 9.2 ± 2.9 ps. 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.