Stacking-Tunable Electronic Properties in Recently Synthesized Hydrogen-Substituted Graphdiyne

TL;DR

This study uses first-principles calculations to explore how stacking sequences affect the structure, electronic, and optical properties of hydrogen-substituted graphdiyne, revealing stable configurations and promising optoelectronic features.

Contribution

It provides the first comprehensive theoretical analysis of stacking-dependent properties in HsGDY, identifying stable configurations and their electronic characteristics.

Findings

AA stacking is the most energetically favorable configuration.

HsGDY is an indirect semiconductor with a 0.89 eV band gap.

The material shows strong visible to ultraviolet optical absorption.

Abstract

Recent progress in porous carbon materials has highlighted the importance of structural design in controlling emergent physicochemical properties. In this context, hydrogen-substituted graphdiyne (HsGDY), a three-dimensional framework derived from graphdiyne (GDY), has recently emerged as a promising architecture whose stacking-dependent behavior remains largely unexplored. Here, we present a comprehensive first-principles investigation of the structural, electronic, and optical properties of HsGDY across distinct stacking sequences. Our results identify the AA and ABC configurations as the most energetically favorable, with AA corresponding to the global minimum, consistent with recent experimental observations. Electronic-structure analysis reveals that HsGDY is an indirect semiconductor with an electronic band gap of 0.89 eV (optB88-vdW), primarily governed by interlayer coupling and van der Waals interactions. The optical response exhibits pronounced absorption features spanning the visible to ultraviolet regions, highlighting strong potential for optoelectronic applications. \textit{Ab initio} molecular dynamics (AIMD) simulations at 700 K confirm the thermal robustness of the framework, with negligible structural distortions. Collectively, these findings elucidate the stacking-dependent stability and semiconducting character of HsGDY, providing a solid theoretical foundation for its integration into next-generation nanoelectronic and energy-harvesting technologies.