Growth modes of partially fluorinated organic molecules on amorphous silicon dioxide

TL;DR

This study uses molecular dynamics simulations to show how fluorination of organic molecules influences their growth modes on amorphous silicon dioxide, enabling controlled surface layer formation.

Contribution

It reveals how partial fluorination changes growth from rough to smooth, layer-by-layer, by modifying molecule-substrate interactions and chiral island formation.

Findings

Fluorination leads to smoother, layer-by-layer growth.

Chiral structures dominate initial growth stages.

Fluorinated molecules have lower step-edge crossing barriers.

Abstract

We study the influence of fluorination on nucleation and growth of the organic para-sexiphenyl molecule (p-6P) on amorphous silicon dioxide ($\alpha$-SiO$_2$) by means of atomistically resolved classical molecular dynamics computer simulations. We use a simulation model that mimics the experimental deposition from the vapor and subsequent self-assembly onto the underlying surface. Our model reproduces the experimentally observed orientational changes from lying to upright standing configurations of the grown layers. We demonstrate that the increase in the number of fluorinated groups inside the p-6P leads to a smoother, layer-by-layer growth on the $\alpha$-SiO$_2$ surface: We observe that in the first layers, due to strong molecule-substrate interactions the molecules first grow in chiral (fan-like) structures, where each consecutive molecule has a higher angle, supported by molecules lying underneath. Subsequently deposited molecules bind to the already standing molecules of the chiral structures until all molecules are standing. The growth of chiral islands is the main mechanism for growth of the fluorinated p-6P derivative, while the p-6P, due to the lower interaction with the underlying substrate, forms less chiral structures. This leads to a lower energy barrier for step-edge crossing for the fluorinated molecules. We find that partial fluorination of the p-6P molecule can in this way significantly alter its growth behaviour by modifying the rough, 3D growth into a smooth, layer-by-layer growth. This has implications for the rational design of molecules and their functionalized forms which could be tailored for a desired growth behavior and structure formation.