On adatomic-configuration-mediated correlation between electrotransport and electrochemical properties of graphene

TL;DR

This study investigates how different arrangements of potassium adatoms on graphene influence its electronic and electrochemical properties, revealing that order and correlation significantly enhance conductivity and can induce band gaps.

Contribution

It provides a detailed analysis of how adatom configuration affects graphene's electronic structure and electrochemical behavior, highlighting the role of order and correlation effects.

Findings

Ordered adatoms can open a band gap in graphene.

Correlated and ordered adatoms greatly enhance conductivity.

Adsorption height influences conductivity linearly.

Abstract

The electron-transport properties of adatom-graphene system are investigated for different (random, correlated, and ordered) spatial configurations of adatoms over different types of high symmetry sites with various adsorption heights. K adatoms in monolayer graphene are modeled by the scattering potential adapted from the independent self-consistent ab initio calculations. The results are obtained numerically using the quantum-mechanical Kubo-Greenwood formalism. A band gap may be opened only if ordered adatoms act as substitutional atoms, while there is no band gap opening for adatoms acting as interstitial atoms. The type of adsorption sites strongly affect the conductivity for random and correlated adatoms, but practically does not change the conductivity when they form ordered superstructures with equal periods. Depending on electron density and type of adsorption sites, the conductivity for correlated and ordered adatoms is found to be enhanced in dozens of times as compared to the cases of their random positions. These the correlation and ordering effects manifest weaker or stronger depending on whether adatoms act as substitutional or interstitial atoms. The conductivity approximately linearly scales with adsorption height of random or correlated adatoms, but remains practically unchanged with adequate varying of elevation of ordered adatoms. Correlations between electron transport properties and heterogeneous electron transfer kinetics through K-doped graphene and electrolyte interface are investigated as well. The ferri-/ferrocyanide redox couple is used as an electrochemical benchmark system. K adsorption of graphene electrode results to only slight suppress of the heterogeneous standard rate constant. Band gap, opening for ordered and strongly short-range scatterers, has a strong impact on the dependence of the electrode reaction rate as a function of electrode potential.