Controlled catalyst-transfer polymerization in graphene nanoribbon synthesis

Pun, Sai Ho; Delgado, Aidan; Dadich, Christina; Cronin, Adam; Fischer, Felix Raoul

doi:10.1016/j.chempr.2023.11.002

Title: Controlled catalyst-transfer polymerization in graphene nanoribbon synthesis

Journal Article · 06 December 2023 · Chem

DOI: https://doi.org/10.1016/j.chempr.2023.11.002 · OSTI ID:2228768

Pun, Sai Ho ^[1]; Delgado, Aidan ^[1]; Dadich, Christina ^[1]; Cronin, Adam ^[1];

^[2]

University of California, Berkeley, CA (United States)
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)

Exercising direct control over the unusual electronic structures arising from quantum confinement effects in graphene nanoribbons (GNRs) is intimately linked to geometric boundary conditions imposed by the structure of the ribbon. Besides composition and position of substitutional dopant atoms, the symmetry of the unit cell, width, length, and termination of a GNR govern its electronic structure. Here, we present a rational design that integrates each of these interdependent variables within a modular bottom-up synthesis. Our hybrid chemical approach relies on a catalyst-transfer polymerization that establishes excellent control over length, width, and end groups. Complemented by a surface-assisted cyclodehydrogenation step, uniquely enabled by matrix-assisted direct (MAD) transfer protocols, geometry and functional handles encoded in a polymer template are faithfully mapped onto the structure of the corresponding GNR. Bond-resolved scanning tunneling microscopy (BRSTM) and spectroscopy (STS) validate the robust correlation between polymer template design and GNR electronic structure.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0023105; KC1203; AC02-05-CH11231

OSTI ID:: 2228768

Alternate ID(s):: OSTI ID: 2433795

Journal Information:: Chem, Vol. 10, Issue 2; ISSN 2451-9294

Publisher:: Cell PressCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
graphene nanoribbons
GNRs
Suzuki chain transfer polymerization
matrix-assisted direct transfer
MAD transfer
on-surface synthesis
scanning tunneling microscopy
STM
scanning tunneling spectroscopy
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Title: Controlled catalyst-transfer polymerization in graphene nanoribbon synthesis

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