Creation of two-dimensional layered Zintl phase by dimensional manipulation of crystal structure

Abstract

The discovery of new families, beyond graphene, of two-dimensional (2D) layered materials has always attracted great attention. However, it has been challenging to artificially develop layered materials with honeycomb atomic lattice structure composed of multicomponents such as hexagonal boron nitride. Here, through the dimensional manipulation of a crystal structure from sp3-hybridized 3D-ZnSb, we create an unprecedented layered structure of Zintl phase, which is constructed by the staking of sp2-hybridized honeycomb ZnSb layers. Using structural analysis combined with theoretical calculation, it is found that the 2D-ZnSb has a stable and robust layered structure. The bidimensional polymorphism is a previously unobserved phenomenon at ambient pressure in Zintl families and can be a common feature of transition metal pnictides. This dimensional manipulation of a crystal structure thus provides a rational design strategy to search for new 2D layered materials in various compounds, enabling unlimited expansion of 2D libraries and corresponding physical properties.

Surface functionalization of the honeycomb structure of zinc antimonide (ZnSb) monolayer: A first-Principles study

“…Recently, the effort on the synthesis of 2D structures of non-layered bulk materials has increased exponentially. With this regard, the 2D forms of Cr 2 S 3 [24], hematite [25,26], gallenene [27], and very recently ZnSb [28] have been demonstrated using different experimental techniques. Among the non-layered bulk materials, ZnSb has been extensively studied due to it promising thermoelectric properties.…”

“…[35,36] The β-Zn 4 Sb 3 phase has been reported to possess a low thermal conductivity due to disordered Zn atoms in its crystalline structure. [37][38][39] In a recent experiment, a 2D form of the ZnSb phase has been demonstrated as a new member of 2D family [28]. Synthesis of ZnSb ultra-thin layers has been been realized by a change of the hybridization from sp 3 to sp 2 .…”

“…[44][45][46][47][48][49][50] In addition to freestanding stable 2DMs, the 2D forms of non-layered bulk materials offer a rich variety of advantages for their surface functionalization due to the unsaturated surface orbitals. It was revealed theoretically that the surface functionalization may lead to dynamical stability of the 2D layer, synthesized from a nonlayered bulk material, as a free-standing crystal [28].…”

Data-driven computational prediction and experimental realization of exotic perovskite-related polar magnets

“…However, recent rapid development of data accumulation and computational power has enabled rapid materials innovation via synergetic integration of experiment, computation, and theory [1][2][3][4] . The emerging data-driven prediction and experimental realization have been extensively applied to solid-state materials with designed combinations of crystal structures and technical applications 5 , such as battery materials 6 , superhard materials 7 , transparent conducting oxides 8,9 , and photovoltaic materials 10 . One rational design approach is to determine the ground state, or relevant property of interest, for possible structure archetypes with a user-confined threshold, followed by a composition screening for optimized targets 11,12 .…”

First principle investigations of the structural, electronic, and phase stability in 2D layered ZnSb

“…In a view to explore graphene like properties in 2D-ZnSb; recently, Junseong Song et al successfully synthesized sp 2 hybridized 2D-ZnSb via the dimensional manipulation of sp 3 hybridized 3D-ZnSb (bulk), and the selective etching of alkali metals. 32 They mentioned the structural stability of the 2D-ZnSb in an ambient atmosphere, and reported the structural phase transformation from 3D-ZnSb to 2D-ZnSb. Such type of transformation of crystal structure between two different dimensions is the key factor for the recognition of new material or switching the properties of 2D materials.…”