Tuning electronic and magnetic properties of partially hydrogenated graphene by biaxial tensile strain: a computational study
© Song et al.; licensee Springer. 2014
Received: 14 August 2014
Accepted: 5 September 2014
Published: 13 September 2014
Using density functional theory calculations, we have investigated the effects of biaxial tensile strain on the electronic and magnetic properties of partially hydrogenated graphene (PHG) structures. Our study demonstrates that PHG configuration with hexagon vacancies is more energetically favorable than several other types of PHG configurations. In addition, an appropriate biaxial tensile strain can effectively tune the band gap and magnetism of the hydrogenated graphene. The band gap and magnetism of such configurations can be continuously increased when the magnitude of the biaxial tensile strain is increased. This fact that both the band gap and magnetism of partially hydrogenated graphene can be tuned by applying biaxial tensile strain provides a new pathway for the applications of graphene to electronics and photonics.
Graphene has recently attracted considerable attention owing to its remarkable electronic and structural properties in many emerging application areas such as electronic devices [1–3]. However, graphene exhibits a zero band gap and nonmagnetic behavior, which limits its application in electronics and photonics . Earlier investigations, both theoretically [5–33] and experimentally [34–43], have been made to adjust electronic and magnetic properties of graphene. There are two basic mechanisms cataloged among these schemes, either to disturb the band crossing at Dirac points via breaking the equivalence of the two sublattices of graphene or to transform the carbon hybridization from sp2 into sp3 via chemical functionalization.
The first mechanism can be achieved by substrate-graphene interaction [5, 6, 35], applying external electric field [36, 37], uniaxial strain [7, 8], cutting graphene into nanoribbons [9–11, 38] and adsorption of molecules on graphene surface [12–14]. However, the efforts of the abovementioned approaches are limited and can only open a tiny band gap because of the robust π bands of graphene. Another mechanism can be realized via chemical functionalization of graphene, such as H, F, OH, COOH, and O chemisorbed on either one side or both sides of graphene [15–23]. At present, this approach can induce a large band gap opening of graphene: for example, fully hydrogenated graphene has been shown to be a wide band gap semiconductor , whereas half-hydrogenated graphene results in an indirect gap and ferromagnetism .
Motivated by the above results, we have carried out a systematic investigation to explore the stability and electronic and magnetic properties of partially hydrogenated graphene (PHG) by applying biaxial tensile strain using density functional theory. The calculated results indicate that the configuration with removing H-hexagon is the most energetically favorable in several types of HG configurations, while the appropriate biaxial tensile strain can effectively tune the band gap and magnetism of the partially hydrogenated graphene.
All calculations in this study were performed using the spin-polarized first-principle method as implemented in the DMol3 code . The generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional was used , in combination with the double numerical plus polarization (DNP). The empirically corrected density functional theory (DFT + D) method within the Grimme scheme was employed in all the calculations to consider the van der Waals forces . All-electron core treatment was adopted, and the real space global cutoff radius was set to be 4.6 Å to achieve high accuracy. We used the smearing techniques with a smearing value of 0.005 Ha.
where Etotal(n) is the cohesive energy of the system, n was the number of H atoms removed from a graphane sheet, and μH (μgraphane) is the chemical potential of the constituent H (graphane) at a given state. Here, we chose the binding energy per atom of H2 molecule as μH. And μgraphane was taken as the cohesive energy of a single graphane sheet.
Results and discussion
According to the previous reports [16, 47], two favorable structures of fully hydrogenated graphene (graphene), chair and boat conformations, exist. In the chair configuration, every two adjacent C atoms are hydrogenated from the opposite sides of the graphene sheet. The induced strains compensate each other and thereby the energy of graphane is low. While in the boat conformation, H atoms are alternately bonded to C atoms on both sides in pairs. Due to the repulsion of two neighboring H on the same side, the boat configuration is less stable than the chair one. Therefore, we only consider the chair configuration. For the case of graphane, the obtained lattice parameter, C-C bond length, and C-H bond length of graphane are 2.54, 1.54, and 1.11 Å, respectively, which are in good agreement with previous reported data .
From the above results, we conclude that the electronic and magnetic properties of graphane can be efficiently tuned from insulator to semiconductor (from non-magnetism to ferromagnetism) via selective dehydrogenation, whereas the band gap and magnetism moment of partially hydrogenated graphene can be enhanced by imposing a biaxial tensile strain.
In summary, DFT calculations with biaxial tensile strain are carried out to investigate the effects of biaxial tensile strain on the electronic and magnetic properties of PHG structures. It is found that the configuration with removing H-hexagon is the most energetically favorable in the several types of HG configurations. In addition, the appropriate biaxial tensile strain can effectively increase the band gap and magnetism of PHG. Overall, tuning both band gap and magnetism of hydrogenated graphene by applying biaxial tensile strain provides a new perspective for wide applications of graphene in electronics and photonics.
This work was supported by a National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2012–0009523).
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