Elucidating the Structure and Photophysics of Layered Perovskites through Cation Fluorination. Issue 18 (10th February 2021)

• Record Type: Journal Article
• Authors: Tekelenburg, Eelco K.; Kahmann, Simon; Kamminga, Machteld E.; Blake, Graeme R.; Loi, Maria A.
• Is Part Of: Advanced optical materials. Volume 9:Issue 18(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-02-10
• Subjects: crystal substructure -- fluorinated cations -- layered perovskites -- luminescence spectroscopy -- photophysics -- Ruddlesden–Popper phase -- single crystals; Optical materials -- Periodicals; Photonics -- Periodicals; 620.11295
• DOI: 10.1002/adom.202001647
• Languages: English
• ISSNs: 2195-1071

Abstract

Abstract: 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. Abstract : The optical properties of 3‐fluorophenethylammonium lead iodide and phenethylammonium lead iodide single crystals are compared. Noticeably, in both materials but most clearly in the fluorinated one, the high‐resolution photoluminescence spectra show a sub‐structure which originates from excitons bound to defects.