# The electronic and magnetic properties of functionalized silicene: a first-principles study

- Fu-bao Zheng
^{1}and - Chang-wen Zhang
^{1}Email author

**7**:422

https://doi.org/10.1186/1556-276X-7-422

© Zheng and Zhang; licensee Springer. 2012

**Received: **15 June 2012

**Accepted: **16 July 2012

**Published: **28 July 2012

## Abstract

Based on first-principles calculations, we study the structural, electronic, and magnetic properties of two-dimensional silicene saturated with hydrogen and bromine atoms. It is found that the fully saturated silicene exhibits nonmagnetic semiconducting behavior, while half-saturation on only one side with hydrogen or bromine results in the localized and unpaired electrons of the unsaturated Si atoms, showing ferromagnetic semiconducting or half-metallic properties, respectively. Total energy calculations show that the half-hydrogenated silicene exhibits a ferromagnetic order, while the half-brominated one exhibits an antiferromagnetic behavior.

### Keywords

First-principles calculation Silicene Ferromagnetism Curie temperature## Background

Recently, low-dimensional honeycomb graphene has attracted much interest because of its unique electronic properties as well as its potential applications in future nanoelectronics, and therefore is one of the most investigated materials in physics and nanoscience [1]. Nevertheless, graphene is facing many challenges in its growth over large areas and, importantly, incompatibility with current silicon-based electronic technology. As the counterpart of graphene, the two-dimensional (2D) hexagonal silicene [2] recently is chemically exfoliated from calcium disilicide (CaSi_{2}). In the more recent works, Si nanoribbons are fabricated by deposition on a silver substrate [3, 4]. The synthesis of silicon-based nanomaterials opens the way for studying their physical and chemical properties, with the added advantage of being compatible with existing semiconductor devices.

The chemical functionalization is generally an efficient way to tune the electronic and magnetic properties in 2D structures, such as graphene, BN, AlN, and CdS sheets [5–8]. Especially, on-plane chemical modification with hydrogen has been reported to induce long-range ferromagnetic order without 3*d* or 4*f* element doping in such 2D carbon-based materials [9, 10], not suffering from problems related to precipitates or secondary phase formation in 3*d-* or 4*f*-element-doped materials, which are undesirable for practical applications. For Si-based nanostructures, Jose and Datta [11] reported the structures and electronic properties of silicene clusters and Si-substituted benzenes, suggesting that silicene clusters may be a promising material for FET and hydrogen storage. Since silicene has only recently been realized [4, 5], the effects of adsorption of foreign atoms on the surface of silicene on magnetism have not been thoroughly explored. In the present letter, based on first-principles calculations, we focus on the possibility of realizing ferromagnetism in silicene with adsorption of hydrogen and the halogen element bromine (Br). It can be seen that the electronic properties of silicene can be tuned, and especially, the ferromagnetic order or half-metallicity is achieved upon adsorption of H and Br atoms, which may open a new route to design the silicon-based nanostructures in spintronics.

## Methods

All the predictions have been performed using the Vienna *Ab initio* Simulation Package and density functional theory [12]. The generalized gradient approximation [13] and a 450-eV cutoff energy for the plane-wave basis set were used. Pseudopotentials with 3*s*^{2}3*p*^{2}, 1 *s*^{1}, and 4*s*^{2}4*p*^{5} valence electron configurations for Si, H, and Br atoms were used, respectively. Following the Monkhorst-Pack scheme [14], Brillouin-zone integration was carried out at 9 × 9 × 1 k-points, and 15 × 15 × 1 k-points were used to obtain the electronic properties. The symmetry-unrestricted optimizations for geometry were performed using the conjugate gradient scheme until the largest Hellmann-Feynman force is smaller than 0.01 eV/Å.

## Results and discussion

*d*

_{1}= 2.27 Å, which agrees well with the previous study [15]. Different from graphene, the larger Si-Si bond length weakens the π-π overlaps, resulting in a low-buckled structure (

*h*= 0.45 Å) with

*sp*

^{3}-like hybrid orbitals (Figure 1b). To check which site a single H atom can absorb on, we consider three different adsorption configurations on the silicene, i.e., top site (T), bridge site (B), and hollow site (H), as shown in Figure 1a. The relative stabilities of the structure are determined from the formation energy which are defined as

*E*

_{f}=

*E*(H:silicene) –

*E*(silicene) – 1/2

*nμ*

_{H}, where

*E*(H:silicene) and

*E*(silicene) are the total energies of the supercell with and without the impurities, respectively.

*μ*

_{H}is the chemical potential of H

_{2}gases, and

*n*is the concentrations of H atoms in silicene. From our calculations, the formation energy for T is found to be the lowest, as shown in Figure 1c. Thus, the T site is the stable adsorption positions for the H atom, suggesting that the growth of hydrogenated silicene can make full use of deposition techniques, which enable the control of a 2D material to avoid the formation of 3D islands.

_{1}), where the top of Si

_{1}atoms are hydrogenated and Si

_{2}atoms remain unsaturated (Figure 2a) [16]. In the case of pure silicene, the

*p*

_{ z }orbitals perpendicular to the plane of the Si ring system hybridize to form a weak and extensive π-bonding network. When half of the silicon (Si

_{1}) atoms are hydrogenated, the H atoms would form strong σ bonds with Si

_{1}atoms, resulting in

*sp*

^{3}hybridization between hydrogen and Si atoms, while the Si

_{2}atoms remain

*sp*

^{2}hybridized. These make the electrons in the unsaturated Si

_{2}atoms localized and unpaired, leading to Si

_{2}being spin-polarized with an integer magnetic moment per unit cell. To check whether the magnetic order is collective, the energy difference, between ferromagnetic and antiferromagnetic, is found to be 0.068 eV, and thus the ferromagnetic order is the stable ground state. We predicted the Curie temperature with the formula of $\gamma {k}_{\text{B}}{\text{T}}_{\text{C}}/2\phantom{\rule{0.25em}{0ex}}={E}_{\text{AFM}}\u2013{E}_{\text{FM}}$ from mean-field approximation [17], where

*γ*is the structural dimension, and

*k*

_{B}is the Boltzmann constant. We found that the calculated Curie temperature of the configuration H@Si

_{1}is about 300 K, which is ideal in practical applications in spintronics.

In the case of half-brominated silicene (Br@Si_{1}), Bader analysis shows that it is spin-polarized with a local magnetic moment of 1.0 *μ*_{B} per unit cell, similar with that of H@Si_{1}. More interestingly, the energy bands close to the Fermi level show a metallic spin-down channel and a semiconducting spin-up one with a 1.73-eV bandgap, and thus a half-metallic behavior with 100% spin-polarized current is obtained, suggesting a feasible way of building spin devices based on silicene. To determine the magnetic stability of Br-induced half-metallicity in Br@Si_{1}, the total energy differences of ferromagnetic, antiferromagnetic, and nonmagnetic orders are calculated. We find that the antiferromagnetic state lies 0.17 and 0.51 eV lower per unit cell in energy than ferromagnetic and nonmagnetic states, respectively, indicating that Br@Si_{1}exhibits an antiferromagnetic behavior.

*M*@Si

_{1}(

*M*= H or Br) sheets, the project density of states (PDOS) and isosurface of spin density are presented in Figure 4. The local magnetic moments are mainly contributed by the 3

*p*electrons near the Fermi level of unsaturated Si

_{2}atoms, i.e., 0.27 and 0.24

*μ*

_{B}for H@Si

_{1}and Br@Si

_{1}, respectively, while the saturated Si

_{1}atom carries a very small magnetic moment (Figure 4). However, the adsorbed Br atom in Br@Si

_{1}provides a magnetic moment of 0.11

*μ*

_{B}, larger than that (0.05

*μ*

_{B}) of the H atom in H@Si

_{1}. Recently, John et al. [22] investigated the magnetic interactions in layered nickel alkanethiolates and a dinuclear Ni(II) complex. They found that the overall magnetic behavior of the system depends on the delicate balance between the competing ferromagnetic and antiferromagnetic interactions. However, in H@Si

_{1}, since the valence electrons in 3

*p*-states on Si

_{2}are more delocalized than those in

*d*- or

*f*-states, the larger spatial extension promotes long-range exchange ferromagnetic coupling, due to the extended

*p-p*interactions. In fact, the extended tails of wave functions have also been proposed to mediate long-range ferromagnetism in nonmagnetic element-doped nanostructures 5.

## Conclusions

In summary, based on first-principles calculations, we study the electronic structure and magnetic properties of 2D hexagonal silicene adsorbed with H and Br atoms. We find that the fully saturated silicene on both sides exhibits nonmagnetic semiconducting behaviors. For half-saturation on only one side of silicene, H@Si_{1} exhibits a ferromagnetic behavior, while Br@Si_{1} shows a half-metallic property due to the localized and unpaired electrons of unsaturated Si_{2} atoms. Calculations of total energies show that Br@Si_{1} exhibits an antiferromagnetic behavior, while H@Si_{1} shows a long-range ferromagnetic order with a Curie temperature at about room temperature. Once combined with advanced Si nanotechnology, these predicted properties may be very useful as a promising nanoscale technological application in spintronics. Therefore, our work suggests that it may be possible to realize long-range room-temperature ferromagnetism in silicene sheets and may motivate potential applications of Si-based nanostructures in spintronics.

## Authors’ information

FBZ is a graduate student and CWZ is a professor in the School of Physics and Technology, University of Jinan, Shandong, People's Republic of China.

## Declarations

### Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant no. 61076088), Foundation for Young Scientist in Shandong Province (grant no. BS2009BR012), and Technological Development Program in Shandong Education Department (grant no. J10LA16).

## Authors’ Affiliations

## References

- Geim AK, Novoselov KS: The rise of graphene.
*Nature Mater*2007, 6: 183–191. 10.1038/nmat1849View ArticleGoogle Scholar - Nakano H, Mitsouka T, Harada M, Horibuchi K, Nozaki H, Takahashi N, Nonaka T, Seno Y, Nakamura H: Soft synthesis of single-crystal silicon monolayer sheets.
*Angew Chem*2006, 118: 6451–6454. 10.1002/ange.200600321View ArticleGoogle Scholar - Aufray B, Kara A, Vizzini S, Oughaddou H, Léandri C, Ealet B, Lay GL: Graphene-like silicon nanoribbons on Ag (110): a possible formation of silicene.
*Appl Phys Lett*2010, 96: 183102. 10.1063/1.3419932View ArticleGoogle Scholar - De Padova P, Quaresima C, Ottaviani C, Sheverdyaeva PM, Moras P, Carbone C, Topwal D, Olivieri B, Kara A, Oughaddou H, Aufray B, Lay GL: Evidence of graphene-like electronic signature nanoribbons.
*Appl Phys Lett*2010, 96: 261905. 10.1063/1.3459143View ArticleGoogle Scholar - Zhang CW, Yan SS, Wang PJ, Li P, Zheng FB: First-principles study on the electronic and magnetic properties of hydrogenated CdS nanosheets.
*J Appl Phys*2011, 109: 094304. 10.1063/1.3583659View ArticleGoogle Scholar - Golberg D, Bando Y, Huang Y, Terao T, Mitome M, Tang CC, Zhi CY: Boron nitride nanotubes and nanosheets.
*ACS Nano*2010, 4(6):2979–2993. 10.1021/nn1006495View ArticleGoogle Scholar - Zhou J, Wang Q, Sun Q, Jena P: Electronic and magnetic properties of a BN sheet decorated with hydrogen and fluorine.
*Phys Rev B*2010, 81: 085442.View ArticleGoogle Scholar - Zhang CW, Zheng FB: First-principles prediction on electronic and magnetic properties of hydrogenated AlN nanosheets.
*J Comput Chem*2011, 32: 3122–3128. 10.1002/jcc.21902View ArticleGoogle Scholar - Wang Y, Ding Y, Shi S, Tang W: Electronic structures of graphane sheets with foreign atom substitutions.
*Appl Phys Lett*2011, 98: 163104. 10.1063/1.3574906View ArticleGoogle Scholar - Lu N, Li ZY, Yang JL: Electronic structure engineering via on-plane chemical functionalization: a comparison study on two-dimensional polysilane and graphane.
*J Phys Chem C*2011, 113: 16741–16746.View ArticleGoogle Scholar - Jose D, Datta A: Molecular rotor inside a phosphonate cavitand: role of supramolecular interactions.
*Phys Chem Chem Phys*2010, 13: 7237.Google Scholar - Kresse G, Hafner J: Ab initio molecular dynamics for liquid metals.
*Phys Rev B*1993, 47: 558–561. 10.1103/PhysRevB.47.558View ArticleGoogle Scholar - Kresse G, Joubert D: From ultrasoft pseudopotentials to the projector augmented-wave method.
*Phys Rev B*1999, 59: 1758–1775. 10.1103/PhysRevB.59.1758View ArticleGoogle Scholar - Monkhorst HJ, Pack JD: Special points for Brillouin-zone integrations.
*Phys Rev B*1976, 13: 5188–5192. 10.1103/PhysRevB.13.5188View ArticleGoogle Scholar - Lebègue S, Eriksson O: Electronic structure of two-dimensional crystals from ab initio theory.
*Phys Rev B*2009, 79: 115409(1)-115409(4).Google Scholar - Cahangirov S, Topsakal M, Akturk E, Sahin H, Ciraci S: Two- and one-dimensional honeycomb structures of silicon and germanium.
*Phys Rev Lett*2009, 102: 236804(1)-236804(4).View ArticleGoogle Scholar - Kudrnovsky J, Turek I, Drchal V, Maca F, Weinberger P, Bruno P: Exchange interactions in III-V and group-IV diluted magnetic semiconductors.
*Phys Rev B*2004, 69: 115208(1)-115208(11).View ArticleGoogle Scholar - Zhou J, Wang Q, Sun Q, Chen XS, Kawazoe Y, Jena P: Ferromagnetism in semihydrogenated graphene sheet.
*Nano Lett*2009, 9: 3867–3870. 10.1021/nl9020733View ArticleGoogle Scholar - Zhou J, Wu M, Zhou X, Sun Q: Tuning electronic and magnetic properties of graphene by surface modification.
*Appl Phys Lett*2009, 95: 103108. 10.1063/1.3225154View ArticleGoogle Scholar - Yaya A, Ewels CP, Suarez-Martinez I, Wagner P, Lefrant S, Okotrub A, Bulusheva L, Briddon PR: Bromination of graphene and graphite.
*Phys Rev B*2011, 83: 045411.View ArticleGoogle Scholar - Gao N, Zheng WT, Jiang Q: Density functional theory calculations for two-dimensional silicene with halogen functionalization.
*Phys Chem Chem Phys*2012, 14: 257–261.View ArticleGoogle Scholar - John NS, Kulkarni GU, Datta A, Pati SK, Komori F, Kavitha G, Narayana C, Sanyal MK: Magnetic interactions in layered nickel alkanethiolates.
*J Phys Chem C*2007, 111: 1868–1870. 10.1021/jp0675072View ArticleGoogle Scholar

## Copyright

This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.