Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening

Xiaotong Li, Yongping Fu, Laurent Pedesseau, Peijun Guo, Shelby Cuthriell, Ido Hadar, Jacky Even, Claudine Katan, Constantinos C. Stoumpos, Richard D. Schaller, Elad Harel, Mercouri G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

115 Scopus citations

Abstract

Organic-inorganic hybrid halide perovskites are promising semiconductors with tailorable optical and electronic properties. The choice of A-site cation to support a three-dimensional (3D) perovskite structure AMX3 (where M is a metal and X is a halide) is limited by the geometric Goldschmidt tolerance factor. However, this geometric constraint can be relaxed in two-dimensional (2D) perovskites, providing us an opportunity to understand how various A-site cations modulate the structural properties and thereby the optoelectronic properties. Here, we report the synthesis and structures of single-crystal (BA)2(A)Pb2I7 where BA = butylammonium and A = methylammonium (MA), formamidinium (FA), dimethylammonium (DMA), or guanidinium (GA), with a series of A-site cations varying in size. Single-crystal X-ray diffraction reveals that the MA, FA, and GA structures crystallize in the same Cmcm space group, while the DMA imposes the Ccmb space group. We observe that as the A-site cation becomes larger, the Pb-I bond continuously elongates, expanding the volume of the perovskite cage, equivalent to exerting "negative pressure"on the perovskite structures. Optical studies and DFT calculations show that the Pb-I bond length elongation reduces the overlap of the Pb s-and I p-orbitals and increases the optical bandgap, while Pb-I-Pb tilting angles play a secondary role. Raman spectra show lattice softening with increasing size of the A-site cation. These structural changes with enlarged A cations result in significant decreases in photoluminescence intensity and lifetime, consistent with a more pronounced nonradiative decay. Transient absorption microscopy results suggest that the PL drop may derive from a higher concentration of traps or phonon-assisted nonradiative recombination. The results highlight that extending the range of Goldschmidt tolerance factors for 2D perovskites is achievable, enabling further tuning of the structure-property relationships in 2D perovskites.

Original languageEnglish (US)
Pages (from-to)11486-11496
Number of pages11
JournalJournal of the American Chemical Society
Volume142
Issue number26
DOIs
StatePublished - Jul 1 2020

Funding

At Northwestern University this work is mainly supported by the Department of Energy, Office of Science, Basic Energy Sciences, under Grant No. SC0012541 (synthesis, structure, and physical property characterization). Transient absorption microscopy measurement was provided in part by the Enabling Quantum Leap program, an NSF EAGER grant under award number DMR-1838507. DFT calculations were performed at Institut FOTON, and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2019-A0060906724 made by GENCI. J.E. acknowledges the financial support from the Institut Universitaire de France. Raman measurements were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation, Earth Sciences (EAR - 1634415). The Raman system acquisition was supported by the NSF MRI proposal (EAR-1531583). This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This work made use of the SPID (confocal microscopy) facilities of Northwestern University\u2019s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF ECCS1542205), the Materials Research Science and Engineering Centers (NSF DMR-1720139), the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN.

ASJC Scopus subject areas

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

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