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Communication Dans Un Congrès Année : 2022

Synergic experimental and theoretical study of the ss-NMR response of halide perovskites: mixed and layered halide perovskites as test bed

Jens Dittmer
Nicolas Mercier
Eric Furet
Claudine Katan

Résumé

Halide perovskites and related nanostructures show complex structural interplay between well-defined long-range structural order, associated to their corner-shared MX6 organization, and short-range dynamic disorder, due to the soft nature of the lattice, libration motion and conformational freedom of the organic component. The structural characterization of these materials reveals therefore challenging, as it calls for an appropriate description of both short-range and long-range structural features, then requiring a smart combination of different structural investigation techniques. In this frame, solid state Nuclear Magnetic Resonance (ss-NMR) emerges as unique technique to complement long-range description routinely addressed via X-ray diffraction, to probe the material structure at different scales[1]. We perform ss-NMR characterization of halide perovskites adopting synergic experimental and theoretical tools. The ss-NMR of 3D methylammonium lead halide perovskites is investigated, first, via periodic Density Functional Theory (DFT) simulations, with good match between the theoretical results for 1H and 13C nuclei and the experimental literature data. Theoretical/experimental agreement is comparably less accurate for 207Pb nuclei, due to lack of Spin-Orbit-Coupling (SOC) in our computational set-up, but still provides correct trends with respect to the PbX6 octahedra halide composition, hence making the NMR signature of 207Pb the ideal marker for characterizing halide segregation down to the atomic scale.[2] Further investigations involve a recently synthesized <110> terminated, m=3 halide perovskite. Again, ssNMR of 207Pb nicely distinguishes between the lead atoms in the inner and outer layers.[3] Further efforts in the directions of incorporation of SOC in the computational set-up and better framing of thermal narrowing is needed but the present results highlight the potential of joint theoretical/experimental NMR simulations in the field of halide perovskites for energy conversion applications. [1] Dahlman C. J., Kubicki D. J., Reddy G. N. M., Interfaces in metal halide perovskites probed by solid-state NMR spectroscopy, J. Mater. Chem. A, 2021,9, 19206 [2] Quarti C., Furet E., Katan C., DFT simulations as valuable tool to support NMR characterization of halide perovskites: the case of pure and mixed halide perovskites, Helv. Chim. Acta 2021, 104, e2000231. [3] M. Ben Haj Salah, N. Mercier, M. Allain, A. Leblanc, J. Dittmer, C. Botta, C. Quarti, C. Katan, Synthesis and characterization of (FA)3(HEA)2Pb3I11: a rare example of <1 1 0>-oriented multilayered halide perovskite, accepted in Chemistry of Materials.
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Dates et versions

hal-03758522 , version 1 (23-08-2022)

Identifiants

  • HAL Id : hal-03758522 , version 1

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Claudio Quarti, Jens Dittmer, Nicolas Mercier, Eric Furet, Claudine Katan. Synergic experimental and theoretical study of the ss-NMR response of halide perovskites: mixed and layered halide perovskites as test bed. 23rd International Conference on Photochemical Conversion and Storage of Solar Energy, Aug 2022, Lausanne, Switzerland. ⟨hal-03758522⟩
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