Templating low dimensional metal organic chalcogenide crystals via diamondoid self-assembly
- Low dimensional metal chalcogenides have emerged in the spotlight in recent years and have become principal targets for new material discovery. In my dissertation, I explore a new way to synthesize single crystal metal chalcogenides in low dimensions, by templating their growth using 'diamondoid' self-assembly. Diamondoids are hydrogen-terminated molecular diamonds that share the basic building blocks of bulk diamond. These molecules exhibit unusually strong intermolecular van der Waals interactions. The diamondoids present an unexplored class of 'structure-directing agents' that can be used to direct the synthesis of low dimensional metal chalcogenides, with new structures previously not accessible. Using diamondoids, we have synthesized 1D metal-organic chalcogenide (MOC) single crystals through directed self-assembly. The Copper Adamantylthiolate (1ADCu) MOC crystal shows the smallest copper sulfide nanowire structure with a 3-atom cross-section. We performed density functional theory and molecular dynamics calculations on the 1ADCu MOC crystal, and found that the formation of the copper sulfide nanowire is guided by strong van der Waals attraction between diamondoid ligands, enabling a unique "face-on" growth mechanism for forming extended 1D structures. The same synthetic route can be applied to grow 1D selenium-based MOC crystals. Lastly, we have successfully doped the MOC crystals with different chalcogens, without affecting the overall crystal structure, and demonstrated that these MOC crystals can be optically tuned. Our method to synthesize crystalline metal chalcogenides through diamondoid self-assembly presents a promising route to grow 1D metal chalcogenide structures with tailorable properties. The wide range of low dimensional metal chalcogenide crystals that can be synthesized using diamondoids as structure-directing agents could offer potential candidates in a variety of applications.
|Type of resource
|electronic; electronic resource; remote
|1 online resource.
|Li, Fei Hua
|Stanford University, Department of Materials Science and Engineering.
|Melosh, Nicholas A
|Melosh, Nicholas A
|Statement of responsibility
|Fei Hua Li.
|Submitted to the Department of Materials Science and Engineering.
|Thesis (Ph.D.)--Stanford University, 2017.
- © 2017 by Fei Hua Li
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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