Structural, Electronic, and Vibrational Properties of 2D Graphdiyne-Like Carbon Nanonetwork Synthesized on Au(111): Implications for the Engineering of sp-sp2 Carbon Nanostructures

TL;DR

This study investigates the atomic structure, electronic, and vibrational properties of a 2D graphdiyne-like carbon nanonetwork grown on Au(111), revealing substrate effects and potential for advanced nanomaterial applications.

Contribution

It provides the first detailed atomic-scale analysis of a graphdiyne-like nanonetwork on gold, combining experimental and theoretical methods to understand substrate interactions.

Findings

Substrate hybridization significantly alters electronic density of states.

Raman spectra are sensitive to bond nature and structural changes.

The nanonetwork shows potential for catalysis and nanoelectronic applications.

Abstract

Graphdiyne, atomically-thin 2D carbon nanostructure based on sp-sp2 hybridization, is an appealing system potentially showing outstanding mechanical and optoelectronic properties. Surface-catalyzed coupling of halogenated sp-carbon-based molecular precursors represents a promising bottom-up strategy to fabricate extended 2D carbon systems with engineered structure on metallic substrates. Here, we investigate the atomic-scale structure and electronic and vibrational properties of an extended graphdiyne-like sp-sp2 carbon nanonetwork grown on Au(111) by means of on-surface synthesis. The formation of such 2D nanonetwork at its different stages as a function of the annealing temperature after the deposition is monitored by scanning tunneling microscopy (STM), Raman spectroscopy and combined with density functional theory (DFT) calculations. High-resolution STM imaging and the high sensitivity of Raman spectroscopy to the bond nature provide a unique strategy to unravel the atomic-scale properties of sp-sp2 carbon nanostructures. We show that hybridization between the 2D carbon nanonetwork and the underlying substrate states strongly affects its electronic and vibrational properties, modifying substantially the density of states and the Raman spectrum compared to the free standing system. This opens the way to the modulation of the electronic properties with significant prospects in future applications as active nanomaterials for catalysis, photoconversion and carbon-based nanoelectronics.