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Review
. 2023 Oct 20;15(20):4176.
doi: 10.3390/polym15204176.

Manipulating Molecular Self-Assembly Process at the Solid-Liquid Interface Probed by Scanning Tunneling Microscopy

Zhi Li  1 , Yanan Li  1 , Chengjie Yin  1
Affiliations
Review

Manipulating Molecular Self-Assembly Process at the Solid-Liquid Interface Probed by Scanning Tunneling Microscopy

Zhi Li et al. Polymers (Basel). .

Abstract

The phenomenon of ordered self-assembly on solid substrates is a topic of interest in both fundamental surface science research and its applications in nanotechnology. The regulation and control of two-dimensional (2D) self-assembled supra-molecular structures on surfaces have been realized through applying external stimuli. By utilizing scanning tunneling microscopy (STM), researchers can investigate the detailed phase transition process of self-assembled monolayers (SAMs), providing insight into the interplay between intermolecular weak interactions and substrate-molecule interactions, which govern the formation of molecular self-assembly. This review will discuss the structural transition of self-assembly probed by STM in response to external stimuli and provide state-of-the-art methods such as tip-induced confinement for the alignment of SAM domains and selective chirality. Finally, we discuss the challenges and opportunities in the field of self-assembly and STM.

Keywords: external stimuli; phase transition; scanning tunneling microscopy; self-assembly.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Temperature-induced structure transformation of SAMs of DBA derivative on a graphite substrate. (a) The chemical structure of DBA-OC16; (b) the molecular model demonstrates the interlocking arrangement of alkoxy chains between neighboring DBA-OC16 molecules; (c) the temperature and concentration-induced structure transition between the linear and porous phase of DBA-OC16. Reproduced with permission from ref. [20]. Copyright 2013, American Chemical Society.
Figure 2
Figure 2
The photo-induced guest adsorption and desorption in a host–guest system. (a) The schematic illustration photo-induced guest adsorption and desorption in DBA pores; STM images of (b) the trans-DBA pores without coronene guest; (c) the trans-DBA/coronene host-guest system; (d) the cis-DBA/coronene host-guest system. The white arrows correspond to the main symmetric axes of graphite. The colored hexagons indicate the pores containing four CORs (red), two CORs (yellow), and those with fuzzy images (blue). Reproduced with permission from ref. [49]. Copyright 2013, John Wiley and Sons.
Figure 3
Figure 3
EC-STM images of picric acid on Au (111) in 0.1 M HClO4 with the substrate potential at (A) 500 mV, (B) 360 mV, (C) 250 mV, and (D) 200 mV. Reproduced with permission from ref. [55]. Copyright 2008, American Chemical Society.
Figure 4
Figure 4
The scheme of two-step flow induced fabrication of long-range ordered HDI thin films on HOPG. (a) Without flow; (b) after flow I; (c) after flow II. Cyan arrows indicate graphite symmetry axes. The rectangles with different colors represent molecules adsorbed in different layers. Red arrows indicate flow direction. Reproduced with permission from ref. [64]. Copyright 2014, American Chemical Society.
Figure 5
Figure 5
The scheme showing (a) ISA-OC18 S and R chirality and (b) L and R domain with respect to the HOPG surface lattice direction [210]; STM images of (c) large-area and (d) small-area SAM of ISA-OC18 on HOPG without confinement; STM images of (e) SAM of ISA-OC18 in L chiral square, (f) R chiral square and (g) achiral square. The yellow arrows point at the occasional imperfections at nanocorral borders. Reproduced with permission from ref. [70]. Copyright 2018, American Chemical Society.
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