A few-layer covalent network of fullerenes

Authors

Elena Meirzadeh, Department of Chemistry, Columbia University, New York, NY, USA. em3428@columbia.edu.
Austin M. Evans, Department of Chemistry, Columbia University, New York, NY, USA.
Mehdi Rezaee, School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA.
Milena Milich, Department of Mechanical and Aerospace Engineering, University of Virginia, Charlottesville, VA, USA.
Connor J. Dionne, University of Rhode Island
Thomas P. Darlington, Department of Mechanical Engineering, Columbia University, New York, NY, USA.
Si Tong Bao, Department of Chemistry, Columbia University, New York, NY, USA.
Amymarie K. Bartholomew, Department of Chemistry, Columbia University, New York, NY, USA.
Taketo Handa, Department of Chemistry, Columbia University, New York, NY, USA.
Daniel J. Rizzo, Department of Physics, Columbia University, New York, NY, USA.
Ren A. Wiscons, Department of Chemistry, Amherst College, Amherst, MA, USA.
Mahniz Reza, Department of Chemistry, Barnard College, New York, NY, USA.
Amirali Zangiabadi, Department of Applied Physics and Applied Mathematics, Columbia University, New York, NY, USA.
Natalie Fardian-Melamed, Department of Mechanical Engineering, Columbia University, New York, NY, USA.
Andrew C. Crowther, Department of Chemistry, Barnard College, New York, NY, USA.
P James Schuck, Department of Mechanical Engineering, Columbia University, New York, NY, USA.
D N. Basov, Department of Physics, Columbia University, New York, NY, USA.
Xiaoyang Zhu, Department of Chemistry, Columbia University, New York, NY, USA.
Ashutosh Giri, University of Rhode Island
Patrick E. Hopkins, Department of Mechanical and Aerospace Engineering, University of Virginia, Charlottesville, VA, USA.
Philip Kim, Department of Physics, Harvard University, Cambridge, MA, USA.
Michael L. Steigerwald, Department of Chemistry, Columbia University, New York, NY, USA. mls2064@columbia.edu.
Jingjing Yang, Department of Chemistry, Columbia University, New York, NY, USA. yjj0412@berkeley.edu.
Colin Nuckolls, Department of Chemistry, Columbia University, New York, NY, USA. cn37@columbia.edu.
Xavier Roy, Department of Chemistry, Columbia University, New York, NY, USA. xr2114@columbia.edu.

Document Type

Article

Date of Original Version

1-1-2023

Abstract

The two natural allotropes of carbon, diamond and graphite, are extended networks of sp-hybridized and sp-hybridized atoms, respectively. By mixing different hybridizations and geometries of carbon, one could conceptually construct countless synthetic allotropes. Here we introduce graphullerene, a two-dimensional crystalline polymer of C that bridges the gulf between molecular and extended carbon materials. Its constituent fullerene subunits arrange hexagonally in a covalently interconnected molecular sheet. We report charge-neutral, purely carbon-based macroscopic crystals that are large enough to be mechanically exfoliated to produce molecularly thin flakes with clean interfaces-a critical requirement for the creation of heterostructures and optoelectronic devices. The synthesis entails growing single crystals of layered polymeric (MgC) by chemical vapour transport and subsequently removing the magnesium with dilute acid. We explore the thermal conductivity of this material and find it to be much higher than that of molecular C, which is a consequence of the in-plane covalent bonding. Furthermore, imaging few-layer graphullerene flakes using transmission electron microscopy and near-field nano-photoluminescence spectroscopy reveals the existence of moiré-like superlattices. More broadly, the synthesis of extended carbon structures by polymerization of molecular precursors charts a clear path to the systematic design of materials for the construction of two-dimensional heterostructures with tunable optoelectronic properties.

Publication Title, e.g., Journal

Nature

Volume

613

Issue

7942

Citation/Publisher Attribution

Meirzadeh, Elena, Austin M. Evans, Mehdi Rezaee, Milena Milich, Connor J. Dionne, Thomas P. Darlington, Si T. Bao, Amymarie K. Bartholomew, Taketo Handa, Daniel J. Rizzo, Ren A. Wiscons, Mahniz Reza, Amirali Zangiabadi, Natalie Fardian-Melamed, Andrew C. Crowther, P J. Schuck, D N. Basov, Xiaoyang Zhu, Ashutosh Giri, Patrick E. Hopkins, Philip Kim, Michael L. Steigerwald, Jingjing Yang, Colin Nuckolls, and Xavier Roy. "A few-layer covalent network of fullerenes." Nature 613, 7942 (2023). doi: 10.1038/s41586-022-05401-w.