TY - JOUR

T1 - Origin of the absorption edge fine structure in Pb-based organic–inorganic 1D perovskites

AU - Kuznetsov, Vyacheslav N.

AU - Chizhov, Yuri V.

AU - Glazkova, Nadezhda I.

AU - Mikhaylov, Ruslan V.

AU - Ryabchuk, Vladimir K.

AU - Emeline, Alexei V.

AU - Serpone, Nick

PY - 2025/6/2

Y1 - 2025/6/2

N2 - Herein, using UV-vis variable temperature diffuse reflectance (DR) spectroscopy, significant findings were revealed upon the examination of the absorption spectra of three one-dimensional (1D) perovskites (pyridinium lead bromide (PyPbBr3), piperidinium lead bromide (PipPbBr3), and piperidinium lead iodide (PipPbI3)) in the temperature range of 100–300 K. Results were analyzed and combined with our previously reported data on pyridinium lead iodide (PyPbI3). A distinct fine structure at the edge of the absorption/DR spectra was observed for all four compounds at cryogenic temperatures. The analysis of the temperature-stimulated evolution of the absorption edge fine structure enabled the identification of the apparent fundamental transition in each spectrum. Two low-energy absorption bands, shifted by 0.05–0.085 eV (ab1) and 0.20–0.27 eV (ab2) at 100 K relative to the apparent bandgap, were also identified. The absorption bands were relatively narrow (fwhm ≤ 0.21 eV) and temperature-independent, making them unobservable at ambient temperatures due to overlap with the red-shifted intrinsic absorption edge. The absorption bands showed similarities in properties of all the compounds. They were tentatively assigned to electronic transitions within Pb2+ ions in the [PbBr6] and [PbI6] units, given that Pb was the single common compositional element in the investigated 1D perovskites.

AB - Herein, using UV-vis variable temperature diffuse reflectance (DR) spectroscopy, significant findings were revealed upon the examination of the absorption spectra of three one-dimensional (1D) perovskites (pyridinium lead bromide (PyPbBr3), piperidinium lead bromide (PipPbBr3), and piperidinium lead iodide (PipPbI3)) in the temperature range of 100–300 K. Results were analyzed and combined with our previously reported data on pyridinium lead iodide (PyPbI3). A distinct fine structure at the edge of the absorption/DR spectra was observed for all four compounds at cryogenic temperatures. The analysis of the temperature-stimulated evolution of the absorption edge fine structure enabled the identification of the apparent fundamental transition in each spectrum. Two low-energy absorption bands, shifted by 0.05–0.085 eV (ab1) and 0.20–0.27 eV (ab2) at 100 K relative to the apparent bandgap, were also identified. The absorption bands were relatively narrow (fwhm ≤ 0.21 eV) and temperature-independent, making them unobservable at ambient temperatures due to overlap with the red-shifted intrinsic absorption edge. The absorption bands showed similarities in properties of all the compounds. They were tentatively assigned to electronic transitions within Pb2+ ions in the [PbBr6] and [PbI6] units, given that Pb was the single common compositional element in the investigated 1D perovskites.

UR - https://www.mendeley.com/catalogue/2caec4f6-810d-3444-87c9-6a64bcffb438/

U2 - 10.1039/d5cp00135h

DO - 10.1039/d5cp00135h

M3 - Article

VL - 27

SP - 13534

EP - 13542

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 25

ER -