Molecular and Ionic Dipole Effects on the Electronic Properties of Si/SiO2 Grafted Alkylamine Monolayers

TL;DR

This study demonstrates how molecular and ionic surface modifications can precisely tune the electronic properties of Si/SiO2 substrates, with experimental and theoretical insights revealing the influence of ionic dipoles and surface organization.

Contribution

It introduces a method to modify electronic properties of Si/SiO2 via ionic surface dipoles, supported by experimental measurements and DFT calculations, highlighting the role of halide ions.

Findings

Ionic dipoles increase work function with larger polarizability.

Surface organization affects ionic dipole strength and electronic properties.

Experimental and theoretical data show consistent trends in dipole effects.

Abstract

In this work, we demonstrate the tunability of electronic properties of Si/SiO2 substrate by molecular and ionic surface modifications. The change in the electronic properties such as the work function (WF) and electron affinity (EA), were experimentally measured by contact potential difference (CPD) technique and theoretically supported by DFT calculations. We attribute these molecular electronic effects mainly to the variations of molecular and surface dipoles of the ionic and neutral species. We have previously showed that for the alkylhalide monolayers, changing the tail group from Cl to I decreased the work function of the substrate. Here we report on the opposite trend of WF changes, i.e. increase of the WF, obtained by using the anions of those halides from Cl$^{-}$ to I$^{-}$. This trend was observed on self-assembled alkylamonium halide (-NH3$^{+}$ X$^{-}$, where X$^{-}$=Cl$^{-}$, Br$^{-}$, I$^{-}$) monolayers modified substrates. The monolayer' formation was supported by Ellipsometry measurements, X-Ray Photoelectron Spectroscopy and Atomic Force Microscopy. Comparison of the theoretical and experimental data suggests that ionic surface dipole depends mainly on the polarizability and the position of the counter halide anion along with the organization and packaging of the layer. The described ionic modification can be easily used for facile tailoring and design of the electronic properties Si/SiO2 substrates for various device applications.