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Review
. 2021 Sep 9;8(1):26.
doi: 10.1186/s40580-021-00275-6.

Approaches to modelling the shape of nanocrystals

Affiliations
Review

Approaches to modelling the shape of nanocrystals

Christina Boukouvala et al. Nano Converg. .

Abstract

Unlike in the bulk, at the nanoscale shape dictates properties. The imperative to understand and predict nanocrystal shape led to the development, over several decades, of a large number of mathematical models and, later, their software implementations. In this review, the various mathematical approaches used to model crystal shapes are first overviewed, from the century-old Wulff construction to the year-old (2020) approach to describe supported twinned nanocrystals, together with a discussion and disambiguation of the terminology. Then, the multitude of published software implementations of these Wulff-based shape models are described in detail, describing their technical aspects, advantages and limitations. Finally, a discussion of the scientific applications of shape models to either predict shape or use shape to deduce thermodynamic and/or kinetic parameters is offered, followed by a conclusion. This review provides a guide for scientists looking to model crystal shape in a field where ever-increasingly complex crystal shapes and compositions are required to fulfil the exciting promises of nanotechnology.

Keywords: Nanoparticle shape; Shape modelling; Shape modelling tools; Winterbottom construction; Wulff construction.

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Conflict of interest statement

The authors declare that they have no competing interests.

Figures

Fig. 1
Fig. 1
Yearly number of publications featuring the words “Wulff construction” (purple) or all of the words “nanoparticle”, “shape” and “thermodynamic” (orange) in their title or abstract. Data obtained from https://app.dimensions.ai/discover/publication
Fig. 2
Fig. 2
Single crystal and modified (twinned) Wulff constructions. Gamma and v-plots viewed along < 110 > for the (a) thermodynamic, (b) kinetic, (d) thermodynamic modified and (e) kinetic modified with re-entrant enhancement Wulff constructions. γ and v correspond to surface energy and growth velocity, respectively, and the twin energy/twin growth velocity is considered to be negligible. Examples of TEM images of (c) a single crystal AgI octahedron, reprinted from [25] with permission from Elsevier, and (f) a twinned Ag right bipyramid, adapted with permission from [26]. Copyright (2021) American Chemical Society
Fig. 3
Fig. 3
Nanocrystal shapes in the single crystal thermodynamic/kinetic, thermodynamic modified and kinetic modified Wulff constructions for FCC and HCP crystal structures. The FCC structures are twinned along the (111) plane, while the twinning plane varies for HCP as described in ref. [31] Facets are colour coded according to legend and shapes were created in Crystal Creator [32]
Fig. 4
Fig. 4
Winterbottom and related constructions for supported crystals. Gamma and v-plots viewed along < 110 > for the (a) thermodynamic, (b) kinetic, (d) thermodynamic modified and (e) kinetic modified with re-entrant enhancement Winterbottom constructions λ and v correspond to surface energy and growth velocity, respectively, and γeff and veff correspond to the effective interface energy and effective growth velocity, respectively. The twin energy/growth velocity is considered to be negligible. TEM images of (c) a single Pt crystal grown on a SrTiO3 nanocube, adapted with permission from [46], and (f) a five-fold Au Marks decahedron grown on a faceted LnScO3 nanoparticle, adapted with permission from [19]. Copyright (2021) American Chemical Society
Fig. 5
Fig. 5
Schematic of the steps required to generate an atomistic Wulff construction, here shown for a Au octahedron. The Wulff shape was rendered in Crystal Creator [32], the atomistic representation was obtained from NanoCrystal [57] and the atomistic illustrations were created in CrystalMaker [58]
Fig. 6
Fig. 6
Diagram of the terminology of the various shape constructions based on the considered surface property (energy for thermodynamic, growth velocity for kinetic), crystal structure (single or twinned crystal) and the growth environment (supported or unsupported)
Fig. 7
Fig. 7
Flow chart illustrating the forward and inverse Wulff construction modelling

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