Ligand-Induced Surface Charge Density Modulation Generates Local Type-II Band Alignment in Reduced-Dimensional Perovskites

Rafael Quintero-Bermudez, Andrew H. Proppe, Arup Mahata, Petar Todorović, Shana O. Kelley, Filippo De Angelis*, Edward H. Sargent

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

61 Scopus citations


Two-dimensional (2D) and quasi-2D perovskite materials have enabled advances in device performance and stability relevant to a number of optoelectronic applications. However, the alignment among the bands of these variably quantum confined materials remains a controversial topic: there exist multiple experimental reports supporting type-I, and also others supporting type-II, band alignment among the reduced-dimensional grains. Here we report a combined computational and experimental study showing that variable ligand concentration on grain surfaces modulates the surface charge density among neighboring quantum wells. Density functional theory calculations and ultraviolet photoelectron spectroscopy reveal that the effective work function of a given quantum well can be varied by modulating the density of ligands at the interface. These induce type-II interfaces in otherwise type-I aligned materials. By treating 2D perovskite films, we find that the effective work function can indeed be shifted down by up to 1 eV. We corroborate the model via a suite of pump-probe transient absorption experiments: these manifest charge transfer consistent with a modulation in band alignment of at least 200 meV among neighboring grains. The findings shed light on perovskite 2D band alignment and explain contrasting behavior of quasi-2D materials in light-emitting diodes (LEDs) and photovoltaics (PV) in the literature, where materials can exhibit either type-I or type-II interfaces depending on the ligand concentration at neighboring surfaces.

Original languageEnglish (US)
Pages (from-to)13459-13467
Number of pages9
JournalJournal of the American Chemical Society
Issue number34
StatePublished - Aug 28 2019

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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