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

Edmondson, Matthew; Saywell, Alex


Matthew Edmondson


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.


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.

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
Keywords Mechanical Engineering; Condensed Matter Physics; General Materials Science; General Chemistry; Bioengineering
Public URL
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