A Computational Study of the Sub-monolayer Growth of Pentacene

• Published in: Advanced functional materials Vol. 16; no. 13; pp. 1768 - 1775
• Main Authors: Choudhary, D., Clancy, P., Shetty, R., Escobedo, F.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 05.09.2006; WILEY‐VCH Verlag
• Subjects: Flexible electronics; organic; Pentacene; Thin films; Thin films, organic
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.200500148

A computational study of organic thin‐film growth using a combination of ab initio based energy calculations and kinetic Monte Carlo (KMC) simulations is provided. A lattice‐based KMC model is used in which binding energies determine the relative rates of diffusion of the molecules. This KMC approach is used to present “landscapes” or “maps” that illustrate the possible structural outcomes of growing a thin film of small organic molecules, represented as a two‐site dimer, on a substrate in which the strength of organic–substrate interactions is allowed to vary. KMC provides a mesoscopic‐scale view of sub‐monolayer deposition of organic thin films on model substrates, mapped out as a function of the flux of depositing molecules and the temperature of the substrate. The morphology of the crystalline thin films is shown to be a strong function of the molecule–molecule and molecule–substrate interactions. A rich variety of maps is shown to occur in which the small organic molecules either stand up or lie down in a variety of different patterns depending on the nature of the binding to the surface. In this way, it is possible to suggest how to tailor the substrate or the small organic molecule in order to create a desired growth habit. In order to demonstrate how this set of allowable maps is reduced in the case where the set of energy barriers between substrate and organic molecule are reliably known, we have used Gaussian 98 calculations to establish binding energies for the weak van der Waals interactions between a) pairs of pentacene molecules as a function of orientation and b) pentacene and two substrates, silicon surfaces passivated with cyclopentene molecules and a crystalline model of silicon dioxide. The critical nucleation size and the mode of diffusion of this idealized two‐site dimer model for pentacene molecules are found to be in good agreement with experimental data. Organic thin‐film growth is studied by using a combination of ab initio density functional theory calculations and kinetic Monte Carlo simulations; this computational study has been used to generate morphology maps (see figure) that describe how the structure of the first layer forms when small, rigid organic molecules are deposited on a substrate.