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Synthesis and chemistry of elemental 2D materials

Nature Reviews Chemistry volume 1, Article number: 0014 (2017) Cite this article

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Abstract

2D materials have attracted considerable attention in the past decade for their superlative physical properties. These materials consist of atomically thin sheets exhibiting covalent in-plane bonding and weak interlayer and layer–substrate bonding. Following the example of graphene, most emerging 2D materials are derived from structures that can be isolated from bulk phases of layered materials, which form a limited library for new materials discovery. Entirely synthetic 2D materials provide access to a greater range of properties through the choice of constituent elements and substrates. Of particular interest are elemental 2D materials, because they provide the most chemically tractable case for synthetic exploration. In this Review, we explore the progress made in the synthesis and chemistry of synthetic elemental 2D materials, and offer perspectives and challenges for the future of this emerging field.

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Figure 1: Elements predicted to form synthetic elemental 2D materials and their known synthesis methods.
Figure 2: Borophene.
Figure 3: Silicene, germanene and stanene.
Figure 4: Black phosphorus and phosphorene.
Figure 5: Bismuth.

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Acknowledgements

This work was performed at the Center for Nanoscale Materials, a US Department of Energy Office of Science User Facility under Contract No. DE-AC02-06CH11357. The authors gratefully acknowledge funding from the Office of Naval Research (Grant No. N00014-14-1-0669) and the National Science Foundation Graduate Fellowship Program (DGE-1324585).

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Authors and Affiliations

  1. Center for Nanoscale Materials, Argonne National Laboratory, 9700 South Cass Avenue, Building 440, Argonne, 60439, Illinois, USA

    Andrew J. Mannix, Brian Kiraly & Nathan P. Guisinger

  2. Department of Materials Science and Engineering, Northwestern University, 2220 Campus Drive, Evanston, 60208, Illinois, USA

    Andrew J. Mannix, Brian Kiraly & Mark C. Hersam

  3. Department of Chemistry, Northwestern University, 2220 Campus Drive, Evanston, 60208, Illinois, USA

    Mark C. Hersam

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Glossary

Ultrahigh vacuum

Pressures less than ∼10−7 Pa (that is, 10−9 mbar or 10−9 torr), at which the rate of atomic impingement is low enough to preserve atomically clean surfaces for highly reactive samples.

n-Fold symmetry

A term to denote the degree of rotational symmetry of a 2D material with respect to the normal direction of the substrate or material basal plane. The number of equivalent rotational configurations is denoted by n (for example, triangles, squares and hexagons have 3, 4 and 6-fold symmetry, respectively).

Topologically non-trivial electronic states

Materials in which the electronic structure is modified by strong spin—orbit coupling effects to exhibit topologically protected electronic states. These states are localized to the surfaces of 3D materials or the edges of 2D materials. Electronic charge carriers in these states are intrinsically protected from scattering.

Epitaxial

A growth mode of materials, in which the overlayer material exhibits a well-defined crystallographic relationship with the substrate.

Functionalizations

Intentional chemical modifications of a material to selectively alter its properties.

Spintronics

Proposed methodology for devices based on the manipulation of electron spin (as opposed to the manipulation of charge in conventional electronics).

Dopants

Atomic or molecular species added to a material to controllably tune its properties. These may include species that modify the carrier concentration, magnetic properties, or chemical reactivity.

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Mannix, A., Kiraly, B., Hersam, M. et al. Synthesis and chemistry of elemental 2D materials. Nat Rev Chem 1, 0014 (2017). https://doi.org/10.1038/s41570-016-0014

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