Molecular Diffusion and Self-Assembly: Quantifying the Influence of Substrate hcp and fcc Atomic Stacking

Edmondson, Matthew; Saywell, Alex

Abstract

Molecular diffusion is a fundamental process underpinning surface-confined molecular self-assembly and synthesis. Substrate topography influences molecular assembly, alignment, and reactions with the relationship between topography and diffusion linked to the thermodynamic evolution of such processes. Here, we observe preferential adsorption sites for tetraphenylporphyrin (2H-TPP) on Au(111) and interpret nucleation and growth of molecular islands at these sites in terms of spatial variation in diffusion barrier driven by local atomic arrangements of the Au(111) surface (the 22× √3 "herringbone"reconstruction). Variable-temperature scanning tunnelling microscopy facilitates characterization of molecular diffusion, and Arrhenius analysis allows quantitative characterization of diffusion barriers within fcc and hcp regions of the surface reconstruction (where the in-plane arrangement of the surface atoms is identical but the vertical stacking differs). The higher barrier for diffusion within fcc locations underpins the ubiquitous observation of preferential island growth within fcc regions, demonstrating the relationship between substrate-structure, diffusion, and molecular self-assembly.

Citation

Edmondson, M., & Saywell, A. (2022). Molecular Diffusion and Self-Assembly: Quantifying the Influence of Substrate hcp and fcc Atomic Stacking. Nano Letters, 22(20), 8210-8215. https://doi.org/10.1021/acs.nanolett.2c02895

• Journal Article Type: Article
• Acceptance Date: Oct 4, 2022
• Online Publication Date: Oct 5, 2022
• Publication Date: Oct 26, 2022
• Deposit Date: Oct 5, 2022
• Publicly Available Date: Oct 6, 2023
• Journal: Nano Letters
• Print ISSN: 1530-6984
• Electronic ISSN: 1530-6992
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 22
• Issue: 20
• Pages: 8210-8215
• DOI: https://doi.org/10.1021/acs.nanolett.2c02895
• Keywords: Mechanical Engineering; Condensed Matter Physics; General Materials Science; General Chemistry; Bioengineering
• Public URL: https://nottingham-repository.worktribe.com/output/12029238
• Publisher URL: https://pubs.acs.org/doi/10.1021/acs.nanolett.2c02895