Out-of-equilibrium processes in crystallization of organic-inorganic perovskites during spin coating

Shambhavi Pratap; Finn Babbe; Nicola S Barchi; Zhenghao Yuan; Tina Luong; Zach Haber; Tze-Bin Song; Jonathan L Slack; Camelia V Stan; Nobumichi Tamura; Carolin M Sutter-Fella; Peter Müller-Buschbaum

doi:10.1038/s41467-021-25898-5

Out-of-equilibrium processes in crystallization of organic-inorganic perovskites during spin coating

Nat Commun. 2021 Sep 24;12(1):5624. doi: 10.1038/s41467-021-25898-5.

Authors

Shambhavi Pratap^{1

2}, Finn Babbe³, Nicola S Barchi^{4

5}, Zhenghao Yuan^{4

6}, Tina Luong⁴, Zach Haber⁴, Tze-Bin Song⁴, Jonathan L Slack², Camelia V Stan^{2

7}, Nobumichi Tamura², Carolin M Sutter-Fella^{8

9}, Peter Müller-Buschbaum^{10

11}

Affiliations

¹ Physik-Department, Lehrstuhl für Funktionelle Materialien, Technische Universität München, Garching, Germany.
² Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, USA.
³ Chemical Sciences Division, Joint Center for Artificial Photosynthesis, Lawrence Berkeley National Laboratory, Berkeley, USA.
⁴ Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, USA.
⁵ Laboratoire des Matériaux Semiconducteurs, École Polytechnique Fédérale de Lausanne, Lausanne, Switzerland.
⁶ Department of Chemistry, The Pennsylvania State University, University Park, PA, USA.
⁷ NIF & Photon Science, Lawrence Livermore National Laboratory, Livermore, USA.
⁸ Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, USA. csutterfella@lbl.gov.
⁹ Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, USA. csutterfella@lbl.gov.
¹⁰ Physik-Department, Lehrstuhl für Funktionelle Materialien, Technische Universität München, Garching, Germany. muellerb@ph.tum.de.
¹¹ Heinz Maier-Leibnitz-Zentrum, Technische Universität München, Garching, Germany. muellerb@ph.tum.de.

Abstract

Complex phenomena are prevalent during the formation of materials, which affect their processing-structure-function relationships. Thin films of methylammonium lead iodide (CH₃NH₃PbI₃, MAPI) are processed by spin coating, antisolvent drop, and annealing of colloidal precursors. The structure and properties of transient and stable phases formed during the process are reported, and the mechanistic insights of the underlying transitions are revealed by combining in situ data from grazing-incidence wide-angle X-ray scattering and photoluminescence spectroscopy. Here, we report the detailed insights on the embryonic stages of organic-inorganic perovskite formation. The physicochemical evolution during the conversion proceeds in four steps: i) An instant nucleation of polydisperse MAPI nanocrystals on antisolvent drop, ii) the instantaneous partial conversion of metastable nanocrystals into orthorhombic solvent-complex by cluster coalescence, iii) the thermal decomposition (dissolution) of the stable solvent-complex into plumboiodide fragments upon evaporation of solvent from the complex and iv) the formation (recrystallization) of cubic MAPI crystals in thin film.

Abstract

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