Chemi-Inspired Silicon Allotropes—Experimentally Accessible Si9 Cages as Proposed Building Block for 1D Polymers, 2D Sheets, Single-Walled Nanotubes, and Nanoparticles

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Journal Title
Journal ISSN
Volume Title
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Date
2022-02-01
Major/Subject
Mcode
Degree programme
Language
en
Pages
15
Series
Molecules, Volume 27, issue 3
Abstract
Numerous studies on silicon allotropes with three-dimensional networks or as materials of lower dimensionality have been carried out in the past. Herein, allotropes of silicon, which are based on structures of experimentally accessible [Si9 ]4− clusters known as stable anionic molecular species in neat solids and in solution, are predicted. Hypothetical oxidative coupling under the formation of covalent Si–Si bonds between the clusters leads to uncharged two-, one-and zero-dimensional silicon nanomaterials not suffering from dangling bonds. A large variety of structures are derived and investigated by quantum chemical calculations. Their relative energies are in the same range as experimentally known silicene, and some structures are even energetically more favorable than silicene. Significantly smaller relative energies are reached by the insertion of linkers in form of tetrahedrally connected Si atoms. A chessboard pattern built of Si9 clusters bridged by tetrahedrally connected Si atoms represents a two-dimensional silicon species with remarkably lower relative energy in comparison with silicene. We discuss the structural and electronic properties of the predicted silicon materials and their building block nido-[Si9 ]4– based on density functional calculations. All considered structures are semiconductors. The band structures exclusively show bands of low dispersion, as is typical for covalent polymers.
Description
Funding Information: Funding: This research was funded by SolTech (Solar Technologies go Hybrid) program of the Bavarian State Ministry of Education, Science and the Arts. Publisher Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland.
Keywords
Allotropy, Clusters, Computational chemistry, Density functional theory, Nanotubes, Silicon
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Citation
Jantke , L-A , Karttunen , A J & Fässler , T F 2022 , ' Chemi-Inspired Silicon Allotropes—Experimentally Accessible Si 9 Cages as Proposed Building Block for 1D Polymers, 2D Sheets, Single-Walled Nanotubes, and Nanoparticles ' , Molecules , vol. 27 , no. 3 , 822 . https://doi.org/10.3390/molecules27030822