Anchored Ligands Facilitate Efficient B-Site doping in metal halide perovskites

Zhenyu Yang, Mingyang Wei, Oleksandr Voznyy, Petar Todorovic, Mengxia Liu, Rafael Quintero-Bermudez, Peining Chen, James Z. Fan, Andrew H. Proppe, Li Na Quan, Grant Walters, Hairen Tan, Je Wei Chang, U. Ser Jeng, Shana O. Kelley, Edward H. Sargent*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

51 Scopus citations

Abstract

Metal halide perovskites exhibit outstanding optoelectronic properties: Superior charge carrier mobilities, low densities of deep trap states, high photoluminescence quantum yield, and wide color tunability. The introduction of dopant ions provides pathways to manipulate the electronic and chemical features of perovskites. In metal halide perovskites ABX3, where A is a monovalent cation (e.g., methylammonium (MA+), Cs+), B is the divalent metal ion(s) (e.g., Pb2+, Sn2+), and X is the halide group (e.g., Cl-, Br-, or I-), the isovalent exchange of A- A nd X-site ions has been widely accomplished; in contrast, strategies to exchange B-site cations are underexamined. The activation energies for vacancymediated diffusion of B-site cations are much higher than those for A- A nd X-sites, leading to slow doping processes and low doping ratios. Herein we demonstrate a new method that exchanges B-site cations in perovskites. We design a series of metal carboxylate solutions that anchor on the perovskite surface, allowing fast and efficient doping of B-sites with both homovalent and heterovalent cations (e.g., Sn2+, Zn2+, Bi3+) at room temperature. The doping process in the reduced-dimensional perovskites is complete within 1 min, whereas a similar reaction only leads to the surface attachment of dopant ions in threedimensional structures. We offer a model based on ammonium extraction and surface ion-pair substitution.

Original languageEnglish (US)
Pages (from-to)8296-8305
Number of pages10
JournalJournal of the American Chemical Society
Volume141
Issue number20
DOIs
StatePublished - 2020

ASJC Scopus subject areas

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

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