Elucidating the Structure and Photophysics of Layered Perovskites through Cation Fluorination

Eelco K. Tekelenburg, Simon Kahmann, Machteld E. Kamminga, Graeme R. Blake, Maria A. Loi*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review


Optoelectronic devices based on layered perovskites containing fluorinated cations display a well-documented improved stability and enhanced performance over non-fluorinated cations. The effect of fluorination on the crystal structure and photophysics, however, has received limited attention up until now. Here, 3-fluorophenethylammonium lead iodide ((3-FPEA)(2)PbI4) single crystals are investigated and their properties to the non-fluorinated ((PEA)(2)PbI4) variant are compared. The bulkier 3-FPEA cation increases the distortion of the inorganic layers, resulting in a blue-shifted absorbance and photoluminescence. Temperature-dependent photoluminescence spectroscopy reveals an intricate exciton substructure in both cases. The fluorinated variant shows hot-exciton resonances separated by 12 to 15 meV, values that are much smaller than the 40 to 46 meV found for (PEA)(2)PbI4. In addition, high-resolution spectra show that the emission at lower energies consists of a substructure, previously thought to be a single line. With the analysis on the resolved photoluminescence, a vibronic progression is excluded as the origin of the emission at lower energies. Instead, part of the excitonic substructure is proposed to originate from bound excitons. This work furthers the understanding of the photophysics of layered perovskites that has been heavily debated lately.

Original languageEnglish
Article number2001647
Number of pages7
JournalAdvanced optical materials
Publication statusE-pub ahead of print - 10-Feb-2021


  • crystal substructure
  • fluorinated cations
  • layered perovskites
  • luminescence spectroscopy
  • photophysics
  • Ruddlesden&#8211
  • Popper phase
  • single crystals

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