Evidence for near-surface NiOOH species in solution-processed NiO x selective interlayer materials: Impact on energetics and the performance of polymer bulk heterojunction photovoltaics

Erin L. Ratcliff, Jens Meyer, K. Xerxes Steirer, Andres Garcia, Joseph J. Berry, David S. Ginley, Dana C. Olson, Antoine Kahn, Neal R. Armstrong

Research output: Contribution to journalArticle

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Abstract

The characterization and implementation of solution-processed, wide bandgap nickel oxide (NiOx) hole-selective interlayer materials used in bulk-heterojunction (BHJ) organic photovoltaics (OPVs) are discussed. The surface electrical properties and charge selectivity of these thin films are strongly dependent upon the surface chemistry, band edge energies, and midgap state concentrations, as dictated by the ambient conditions and film pretreatments. Surface states were correlated with standards for nickel oxide, hydroxide, and oxyhydroxide components, as determined using monochromatic X-ray photoelectron spectroscopy. Ultraviolet and inverse photoemission spectroscopy measurements show changes in the surface chemistries directly impact the valence band energies. O2-plasma treatment of the as-deposited NiO x films was found to introduce the dipolar surface species nickel oxyhydroxide (NiOOH), rather than the p-dopant Ni2O3, resulting in an increase of the electrical band gap energy for the near-surface region from 3.1 to 3.6 eV via a vacuum level shift. Electron blocking properties of the as-deposited and O2-plasma treated NiOx films are compared using both electron-only and BHJ devices. O2-plasma-treated NiOx interlayers produce electron-only devices with lower leakage current and increased turn on voltages. The differences in behavior of the different pretreated interlayers appears to arise from differences in local density of states that comprise the valence band of the NiOx interlayers and changes to the band gap energy, which influence their hole-selectivity. The presence of NiOOH states in these NiOx films and the resultant chemical reactions at the oxide/organic interfaces in OPVs is predicted to play a significant role in controlling OPV device efficiency and lifetime.

Original languageEnglish (US)
Pages (from-to)4988-5000
Number of pages13
JournalChemistry of Materials
Volume23
Issue number22
DOIs
StatePublished - Nov 22 2011

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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