Issue 45, 2023

Crystalline restacking of 2D-materials from their nanosheets suspensions

Abstract

We report here the highly ordered restacking of the layered phosphatoantimonic dielectric materials H3(1−x)M3xSb3P2O14, (where M = Li, Na, K, Rb, Cs and 0 ≤ x ≤ 1), from their nanosheets dispersed in colloidal suspension, induced by a simple pH change using alkaline bases. H3Sb3P2O14 aqueous suspensions are some of the rare examples of colloidal suspensions based on 2D materials exhibiting a lamellar liquid crystalline phase. Because the lamellar period can reach several hundred nanometers, the suspensions show vivid structural colors and because these colors are sensitive to various chemicals, the suspensions can be used as sensors. The structures of the lamellar liquid crystalline phase and the restacked phase have been studied by X-ray scattering (small and wide angle), which has followed the dependence of the lamellar/restacked phase equilibrium on the cation exchange rate, x. The X-ray diffraction pattern of the restacked phase is almost identical to that of the M3Sb3P2O14 crystalline phase, showing that the restacking is highly accurate and avoids the turbostratic disorder of the nanosheets classically observed in nanosheet stacking of other 2D materials. Strikingly, the restacking process exhibits features highly reminiscent of a first-order phase transition, with the existence of a phase coexistence region where both ∼1 nm (interlayer spacing of the restacked phase) and ∼120 nm lamellar periods can be observed simultaneously. Furthermore, this first-order phase transition is well described theoretically by incorporating a Lennard-Jones-type lamellar interaction potential into an entropy-based statistical physics model of the lamellar phase of nanosheets. Our work shows that the precise cation exchange produced at room temperature by a classical neutralization reaction using alkaline bases leads to a crystal-like restacking of the exfoliated free Sb3P2O143− nanosheets from suspension, avoiding the turbostratic disorder typical of van der Waals 2D materials, which is detrimental to the controlled deposition of nanosheets into complex integrated electronic, spintronic, photonic or quantum structures.

Graphical abstract: Crystalline restacking of 2D-materials from their nanosheets suspensions

Supplementary files

Article information

Article type
Paper
Submitted
27 Sep 2023
Accepted
16 Okt 2023
First published
06 Nov 2023
This article is Open Access
Creative Commons BY-NC license

Nanoscale, 2023,15, 18359-18367

Crystalline restacking of 2D-materials from their nanosheets suspensions

L. Cherni, K. El Rifaii, H. H. Wensink, S. M. Chevrier, C. Goldmann, L. J. Michot, P. Davidson and J. P. Gabriel, Nanoscale, 2023, 15, 18359 DOI: 10.1039/D3NR04885C

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