Efficient Hierarchical Models for Reactivity of Organic Layers on Semiconductor Surfaces

12 February 2021, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Computational modeling of organic interface formation on semiconductors poses a challenge to a density functional theory-based description due to structural and chemical complexity. A hierarchical approach is presented, where parts of the interface are successively removed in order to increase computational efficiency while maintaining the necessary accuracy. First, a benchmark is performed to probe the validity of this approach for three model reactions and five dispersion corrected density functionals. Reaction energies are generally well reproduced by GGA-type functionals but accurate reaction barriers require the use of hybrid functionals. Best performance is found for the model system that does not explicitly consider the substrate but includes its templating effects. Finally, this efficient model is used to provide coverage dependent adsorption energies and suggest synthetic principles for the prevention of unwanted growth termination reactions for organic layers on semiconductor surfaces.


density functional theory
model hierarchy
hybrid organic-inorganic materials
semiconductor functionalization

Supplementary materials

SI revision


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