Thick-Layer Lead Iodide Perovskites with Bifunctional Organic Spacers Allylammonium and Iodopropylammonium Exhibiting Trap-State Emission

Eugenia S. Vasileiadou, Xinyi Jiang, Mikaël Kepenekian, Jacky Even, Michael C. De Siena, Vladislav V. Klepov, Daniel Friedrich, Ioannis Spanopoulos, Qing Tu, Imra S. Tajuddin, Emily A. Weiss, Mercouri G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

The nature of the organic cation in two-dimensional (2D) hybrid lead iodide perovskites tailors the structural and technological features of the resultant material. Herein, we present three new homologous series of (100) lead iodide perovskites with the organic cations allylammonium (AA) containing an unsaturated Câ C group and iodopropylammonium (IdPA) containing iodine on the organic chain: (AA)2MAn-1PbnI3n+1(n = 3-4), [(AA)x(IdPA)1-x]2MAn-1PbnI3n+1(n = 1-4), and (IdPA)2MAn-1PbnI3n+1(n = 1-4), as well as their perovskite-related substructures. We report the in situ transformation of AA organic layers into IdPA and the incorporation of these cations simultaneously into the 2D perovskite structure. Single-crystal X-ray diffraction shows that (AA)2MA2Pb3I10crystallizes in the space group P21/c with a unique inorganic layer offset (0, <1/2), comprising the first example of n = 3 halide perovskite with a monoammonium cation that deviates from the Ruddlesden-Popper (RP) halide structure type. (IdPA)2MA2Pb3I10and the alloyed [(AA)x(IdPA)1-x]2MA2Pb3I10crystallize in the RP structure, both in space group P21/c. The adjacent I···I interlayer distance in (AA)2MA2Pb3I10is ∼5.6 Å, drawing the [Pb3I10]4-layers closer together among all reported n = 3 RP lead iodides. (AA)2MA2Pb3I10presents band-edge absorption and photoluminescence (PL) emission at around 2.0 eV that is slightly red-shifted in comparison to (IdPA)2MA2Pb3I10. The band structure calculations suggest that both (AA)2MA2Pb3I10and (IdPA)2MA2Pb3I10have in-plane effective masses around 0.04m0and 0.08m0, respectively. IdPA cations have a greater dielectric contribution than AA. The excited-state dynamics investigated by transient absorption (TA) spectroscopy reveal a long-lived (∼100 ps) trap state ensemble with broad-band emission; our evidence suggests that these states appear due to lattice distortions induced by the incorporation of IdPA cations.

Original languageEnglish (US)
Pages (from-to)6390-6409
Number of pages20
JournalJournal of the American Chemical Society
Volume144
Issue number14
DOIs
StatePublished - Apr 13 2022

Funding

This work was supported by the Office of Naval Research, under grant N00014-17-1-2231 (synthesis, structural characterization of materials, M.G.K.). E.S.V. acknowledges the Dr. John N. Nicholson fellowship through Northwestern University. This work was supported by the Northwestern Materials Research Science and Engineering Center (NU-MRSEC, DMR-1720139) (measurement of optical properties). This work made use of the NUANCE Center and IMSERC facilities of Northwestern University, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633). Q.T. acknowledges support through the startup funds from the Texas A&M Engineering Experiment Station (TEES) and the Texas A&M Triads for Transformation (T3) grant. E.S.V. thanks Dr. Ido Hadar, Dr. Abishek Iyer, Dr. Jennifer Rote, and Prof. Regan Thomson for productive discussion.

ASJC Scopus subject areas

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

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