Transformation of a graphene nanoribbon into a hybrid 1D nanoobject with alternating double chains and polycyclic regions

• Published in: Physical chemistry chemical physics : PCCP 2021-01, Vol.23 (1), p.425-441
• Main Authors: Sinitsa, Alexander S, Lebedeva, Irina V, Polynskaya, Yulia G, de Oteyza, Dimas G, Ratkevich, Sergey V, Knizhnik, Andrey A, Popov, Andrey M, Poklonski, Nikolai A, Lozovik, Yurii E
• Format: Article
• Language: English
• Subjects: Algorithms; Antiferromagnetism; Carbon; Chemical bonds; Chemical synthesis; Coupling (molecular); Dehydrogenation; Density functional theory; Electron energy; Electron irradiation; Graphene; Hexagons; Hydrogen; Hydrogen atoms; Macromolecules; Magnetism; Molecular chains; Molecular dynamics; Molecular structure; Nanoribbons; Precursors; Simulation
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d0cp04090h

Molecular dynamics simulations show that a graphene nanoribbon with alternating regions which are one and three hexagons wide can transform into a hybrid 1D nanoobject with alternating double chains and polycyclic regions under electron irradiation in HRTEM. A scheme of synthesis of such a nanoribbon using Ullmann coupling and dehydrogenation reactions is proposed. The reactive REBO-1990EVC potential is adapted for simulations of carbon-hydrogen systems and is used in combination with the CompuTEM algorithm for modeling of electron irradiation effects. The atomistic mechanism of formation of the new hybrid 1D nanoobject is found to be the following. Firstly hydrogen is removed by electron impacts. Then spontaneous breaking of bonds between carbon atoms leads to the decomposition of narrow regions of the graphene nanoribbon into double chains. Simultaneously, thermally activated growth of polycyclic regions occurs. Density functional theory calculations give barriers along the growth path of polycyclic regions consistent with this mechanism. The electronic properties of the new 1D nanoobject are shown to be strongly affected by the edge magnetism and make this nanostructure promising for nanoelectronic and spintronic applications. The synthesis of the 1D nanoobject proposed here can be considered as an example of the general three-stage strategy of production of nanoobjects and macromolecules: (1) precursors are synthesized using a traditional chemical method, (2) precursors are placed in HRTEM with the electron energy that is sufficient only to remove hydrogen atoms, and (3) as a result of hydrogen removal, the precursors become unstable or metastable and transform into new nanoobjects or macromolecules. Molecular dynamics simulations show that a graphene nanoribbon with alternating one- and three-hexagon wide regions can transform into a hybrid 1D nanoobject with alternating double chains and polycyclic regions under electron irradiation in HRTEM.