In situ imaging of temperature-dependent fast and reversible nanoscale domain switching in a single-crystal perovskite

Open Access

In situ imaging of temperature-dependent fast and reversible nanoscale domain switching in a single-crystal perovskite

Lucas A. B. Marçal, Dmitry Dzhigaev, Zhaojun Zhang, Ella Sanders, Amnon Rothman, Edoardo Zatterin, Ewen Bellec, Tobias U. Schülli, Anders Mikkelsen, Ernesto Joselevich, and Jesper Wallentin

Phys. Rev. Materials 6, 054408 – Published 18 May 2022

Abstract

Metal halide perovskites exhibit a rich crystal structure, with multiple phases as well as ferroelastic domains, which is crucial for the optical and electrical properties. The average crystal phase-transition temperatures can be shifted by size, strain, or defects, but it is not clear whether such differences can also appear locally within a single crystal. The experimental study of domain dynamics within nanocrystals is challenging and requires a method capable of probing crystal lattice variations with both high spatial and temporal resolution. Here, we show that in situ full-field diffraction x-ray microscopy can be used to image domains in a single crystal ${CsPbBr}_{3}$ nanoplatelet as the temperature traverses the orthorhombic to tetragonal phase transition, at 150 nm spatial resolution and 6 s time resolution. The images reveal sudden domain pattern changes faster than the temporal resolution. Surprisingly, we observe substantial local variations during heating, with domain changes occurring at different temperatures within the single crystal. The nanoplatelet exhibits a high-temperature domain pattern completely different from the low-temperature one, but both patterns are reproducible, and we reversibly switch between them in multiple cycles. These results demonstrate that single ${CsPbBr}_{3}$ crystals can exhibit substantial local variation of their basic crystal properties.

Received 2 January 2022
Revised 23 April 2022
Accepted 26 April 2022

DOI:https://doi.org/10.1103/PhysRevMaterials.6.054408

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI. Funded by Bibsam.

Published by the American Physical Society

Physics Subject Headings (PhySH)

Domain walls Ferroelasticity Temperature Transition temperature

Condensed Matter, Materials & Applied Physics

Authors & Affiliations

Lucas A. B. Marçal ^1,2,*, Dmitry Dzhigaev ¹, Zhaojun Zhang ¹, Ella Sanders³, Amnon Rothman³, Edoardo Zatterin⁴, Ewen Bellec⁴, Tobias U. Schülli⁴, Anders Mikkelsen¹, Ernesto Joselevich ³, and Jesper Wallentin ¹

¹Synchrotron Radiation Research and NanoLund, Lund University, Box 118, Lund 22100, Sweden
²MAX IV Laboratory, Lund University, Lund 22100, Sweden
³Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot 76100, Israel
⁴European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9, France

^*lucas.marcal@sljus.lu.se

Article Text

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Issue

Vol. 6, Iss. 5 — May 2022

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Images

Figure 1
(a) Schematic representation of the FFDXM experimental setup. The nanoplatelet was rotated to the Bragg angle θ, and the x-ray detector was positioned at 2θ. The bright areas are domains with both lattice tilts aligned by the rotation motor as well as lattice spacing within the 2θ condition selected by the lenses. The lenses create a 65 times magnified image of the bright parts of the nanoplatelet on the detector. Inset shows a SEM image of the nanoplatelet, acquired after the experiment. The right part of the structure bends 4 ° relative to its left part, tilting the crystal out of the lenses’ acceptance range. (b) Projections at a specific θ of the nanoplatelet acquired at temperatures ranging from 20 °C to 70 °C during temperature increase. (c) Images near 75.7 °C, evidencing a sudden change in the domain orientation pattern in the central part. (d) Images near 83.3 °C, showing another sudden change in the left part of the nanoplatelet. Note the marginal differences between the last frame in (c) and the first two frames in (d), despite the large temperature change. Subsequent frames in (c),(d) were acquired with a time difference on the order of 6 s. Movies showing the changes represented in (c),(d) can be found in the Supplemental Material [43].
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Figure 2
(a) Projections of the nanoplatelet acquired during first cooldown. (b) Projections near 73.7 °C, acquired during second heating cycle, showing a sudden and localized change in the domain pattern. Frames were acquired with a time difference on the order of 6 s.
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Figure 3
(a) Maps of the integrated intensity (left panels), lattice tilt (middle panels), and peak width measured as FWHM (right panels), of the nanoplatelet at selected temperatures along the heating cycles. The maps are stacked from top to bottom following the chronological order. Note that the range of the color scale is adapted for each map, for better visualization of local features. (b) Schematic graph of the full temperature cycle. Numbers from 1 to 11 indicate where rocking curves were acquired and correspond to the maps plotted in (a). Fast single-frame measurements as in Figs. 1 and 2 were performed during the changes in temperature, between the rocking curves. (c),(d) Diffracted intensity as a function of the incident angle θ plotted for the rocking curves at 20 °C and 80 °C, respectively. Curves are stacked from top to bottom in chronological order and numbers correspond to the maps in (a). The θ values were retrieved from the nominal motor position and do not correspond to the exact sample rotation with respect to the x-ray beam. (e) Plot showing the θ peak position for each map at both 20 °C and 80 °C, as marked in (c),(d) by the black dashed lines.
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Figure 4
Sketch showing the top and cross-sectional view of the nanoplatelet at 20 °C (blue) and 80 °C (red). Different color tones represent domains along the structure. White lines indicate the orientation of orthorhombic or tetragonal (001) planes, evidencing the tilts along θ and α in multiple domains at both temperatures. Black lines indicate tetragonal (110) planes at 80 °, which are invisible since their 2θ is out of the acceptance range of the imaging lenses.
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