Sensitivity of Nitrogen K-Edge X-ray Absorption to Halide Substitution and Thermal Fluctuations in Methylammonium Lead-Halide Perovskites.

Sterling, Cody M; Kamal, Chinnathambi; Man, Gabriel J; Nayak, Pabitra K; Simonov, Konstantin A; Svanström, Sebastian; García-Fernández, Alberto; Huthwelker, Thomas; Cappel, Ute B; Butorin, Sergei M; Rensmo, Håkan; Odelius, Michael

Sterling, Cody M; Kamal, Chinnathambi; Man, Gabriel J; Nayak, Pabitra K; Simonov, Konstantin A; Svanström, Sebastian; García-Fernández, Alberto; Huthwelker, Thomas; Cappel, Ute B; Butorin, Sergei M; Rensmo, Håkan; Odelius, Michael.

Afiliación

Sterling CM; Department of Physics, Stockholm University, AlbaNova University Center, SE-106 91 Stockholm, Sweden.
Kamal C; Department of Physics, Stockholm University, AlbaNova University Center, SE-106 91 Stockholm, Sweden.
Man GJ; Theory and Simulations Laboratory, HRDS, Raja Ramanna Centre for Advanced Technology, 452013 Indore, India.
Nayak PK; Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala, Sweden.
Simonov KA; TIFR Centre for Interdisciplinary Sciences, Tata Institute of Fundamental Research, 36/P, Gopanpally Village, Serilingampally Mandal, 500046 Hyderabad, India.
Svanström S; Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala, Sweden.
García-Fernández A; Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala, Sweden.
Huthwelker T; Division of Applied Physical Chemistry, Department of Chemistry, KTH Royal Institute of Technology, SE-100 44 Stockholm, Sweden.
Cappel UB; Swiss Light Source, Paul Scherrer Institut, WLGA/212, Forschungsstrasse 111, 5232 Villigen, Switzerland.
Butorin SM; Division of Applied Physical Chemistry, Department of Chemistry, KTH Royal Institute of Technology, SE-100 44 Stockholm, Sweden.
Rensmo H; Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala, Sweden.
Odelius M; Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala, Sweden.

J Phys Chem C Nanomater Interfaces ; 125(15): 8360-8368, 2021 Apr 22.

Article en En | MEDLINE | ID: mdl-34084262

RESUMEN

The performance of hybrid perovskite materials in solar cells crucially depends on their electronic properties, and it is important to investigate contributions to the total electronic structure from specific components in the material. In a combined theoretical and experimental study of CH3NH3PbI3-methylammonium lead triiodide (MAPI)-and its bromide cousin CH3NH3PbBr3 (MAPB), we analyze nitrogen K-edge (N 1s-to-2p*) X-ray absorption (XA) spectra measured in MAPI and MAPB single crystals. This permits comparison of spectral features to the local character of unoccupied molecular orbitals on the CH3NH3 + (MA+) counterions and allows us to investigate how thermal fluctuations, hydrogen bonding, and halide-ion substitution influence the XA spectra as a measure of the local electronic structure. In agreement with the experiment, the simulated spectra for MAPI and MAPB show close similarity, except that the MAPB spectral features are blue-shifted by +0.31 eV. The shift is shown to arise from the intrinsic difference in the electronic structure of the two halide atoms rather than from structural differences between the materials. In addition, from the spectral sampling analysis of molecular dynamics simulations, clear correlations between geometric descriptors (N-C, N-H, and H···I/Br distances) and spectral features are identified and used to explain the spectral shapes.

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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Tipo de estudio: Diagnostic_studies Idioma: En Revista: J Phys Chem C Nanomater Interfaces Año: 2021 Tipo del documento: Article País de afiliación: Suecia Pais de publicación: Estados Unidos

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