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Silicene

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Silicene

Structure of a typical silicene cluster showing ripples across the surface.

Silicene is a two-dimensional allotrope of silicon, with a hexagonal honeycomb structure similar to that of graphene.

Contents

  • History 1
  • Similarities and differences with graphene 2
  • Band gap 3
  • Properties 4
    • Functionalized silicene 4.1
  • See also 5
  • References 6
  • External links 7

History

Although theorists had speculated about the existence and possible properties of silicene,[1][2][3] researchers first observed silicon structures that were suggestive of silicene in 2010.[4][5] Using a scanning tunneling microscope they studied self-assembled silicene nanoribbons and silicene sheets deposited onto a silver crystal, Ag(110) and Ag(111), with atomic resolution. The images revealed hexagons in a honeycomb structure similar to that of graphene. Density functional theory (DFT) calculations showed that silicon atoms tend to form such honeycomb structures on silver, and adopt a slight curvature that makes the graphene-like configuration more likely. However, such a model has been invalidated for Si/Ag(110): the Ag surface displays a missing-row reconstruction upon Si adsorption [6] and the honeycomb structures observed are tip artefacts.[7]

Similarities and differences with graphene

Silicon and carbon are similar atoms. They lie next to each other in the same group on the periodic table and have an s2 p2 electronic structure. The 2D structures of silicene and graphene also are quite similar but have important differences. While both form hexagonal structures, graphene is completely flat, while silicene forms a buckled hexagonal shape. Its buckled structure gives silicene a tuneable band gap by applying an external electric field. Silicene's hydrogenation reaction is more exothermic than graphene's. Another difference is that since silicon's covalent bonds do not have pi-stacking, silicene does not cluster into a graphite-like form.[8]

Silicene and graphene have similar electronic structures. Both have a Dirac cone and linear electronic dispersion around the k point. Both also have a quantum spin Hall effect. Both are expected to have the characteristics of massless Dirac fermions that carry charge, but this is only predicted for silicene and has not been observed, likely because it is expected to only occur with free-standing silicene which has not been synthesized. It is believed that the substrate silicene is made on has a substantial effect on its electronic properties.[8]

Band gap

Early studies of silicene showed that different dopants within the silicene structure provide the ability to tune its band gap.[9] With a tunable band gap, specific electronic components could be made-to-order for applications that require specific band gaps. The band gap can be brought down to 0.1eV, which is considerably smaller than the band gap (0.4eV) found in traditional field effect transistors (FETs).[9]

Inducing n-type doping within silicene requires an alkali metal dopant. Varying the amount adjusts the band gap. Maximum doping increases the band gap 0.5eV. Due to heavy doping, the supply voltage must also be ~30V. Alkali metal-doped silicene can only produce n-type semiconductors; modern day electronics require a complementary n-type and p-type junction. Neutral doping (i-type) is required to produce devices such as light emitting diodes (LEDs). LEDs use a p-i-n junction to produce light. A separate dopant must be introduced to generate p-type doped silicene. Iridium (Ir) doped silicene allows p-type silicene to be created. Through platinum (Pt) doping, i-type silicene is possible.[9] With the combination of n-type, p-type and i-type doped structures, silicene has opportunities for use in electronics.

Power dissipation within traditional metal oxide semiconductor field effect transistors (MOSFETs) generates a bottleneck when dealing with nano-electronics. Tunnel field-effect transistors (TFETs) may become an alternative to traditional MOSFETs because they can have a smaller subthreshold slope and supply voltage, which reduce power dissipation. Computational studies showed that silicene based TFETs outperform traditional silicon based MOSFETs. Silicene TFETs have an on-state current over 1mA/μm, a sub-threshold slope of 77mV/dec and a supply voltage of 1.7 V. With this much increased on-state current and reduced supply voltage, power dissipation within these devices is far below that of traditional MOSFETs and its peer TFETs.[9]

Close up of one hexagonal ring in silicene with displayed buckled structure.

Properties

2D silicene is not fully planar, apparently featuring chair-like puckering distortions in the rings. This leads to ordered surface ripples. Hydrogenation of silicenes to silicanes is exothermic. This led to the prediction that the process of conversion of silicene to silicane (hydrogenated silicene) is a candidate for hydrogen storage. Unlike graphite, which consists of weakly held stacks of graphene layers through dispersion forces, interlayer coupling in silicenes is very strong.

The buckling of the hexagonal structure of silicene is caused by pseudo-Jahn-Teller distortion (PJT). This is caused by strong vibronic coupling of unoccupied molecular orbitals (UMO) and occupied molecular orbitals (OMO). These orbitals are close enough in energy to cause the distortion to high symmetry configurations of silicene. The buckled structure can be flattened by suppressing the PJT distortion by increasing the energy gap between the UMO and OMO. This can be done by adding a lithium ion.[8]

In addition to its potential compatibility with existing semiconductor techniques, silicene has the advantage that its edges do not exhibit oxygen reactivity.[10]

In 2012 several groups independently reported ordered phases on the Ag(111) surface.[11][12][13] Results from angle-resolved photoemission spectroscopy (ARPES) appeared to show that silicene would have similar electronic properties as graphene, namely an electronic dispersion resembling that of relativistic Dirac fermions at the K points of the Brillouin zone,[11] but the interpretation was later disputed and shown to arise due to a substrate band.[14][15][16][17] The existence of Dirac fermions for silicene on Ag(111) was later reported from scanning tunneling spectroscopy measurements.[18]

Besides silver, silicene has been reported to grow on ZrB
2
,[19] and iridium.[20] Theoretical studies predicted that silicene is stable on the Al(111) surface as a honeycomb-structured monolayer (with a binding energy similar to that observed on the 4x4 Ag(111) surface) as well as a new form dubbed "polygonal silicene", its structure consisting of 3-, 4-, 5- and 6-sided polygons.[21]

The p-d hybridisation mechanism between Ag and Si is important to stabilise the nearly flat silicon clusters and the effectiveness of Ag substrate for silicene growth explained by DFT calculations and molecular dynamics simulations.[22]

Functionalized silicene

Beyond the pure silicene structure, research into functionalized silicene has yielded successful growth of organomodified silicene - oxygen-free silicene sheets functionalized with organic solvents and indicates the potential for a range of new functionalized silicon systems and organosilicon nanosheets.


See also

References

  1. ^ Takeda, K.; Shiraishi, K. (1994). "Theoretical possibility of stage corrugation in Si and Ge analogs of graphite". Physical Review B 50 (20): 14916.  
  2. ^ Guzmán-Verri, G.; Lew Yan Voon, L. (2007). "Electronic structure of silicon-based nanostructures". Physical Review B 76 (7).  
  3. ^ Cahangirov, S.; Topsakal, M.; Aktürk, E.; Şahin, H.; Ciraci, S. (2009). "Two- and One-Dimensional Honeycomb Structures of Silicon and Germanium". Physical Review Letters 102 (23).  
  4. ^ Aufray, B.; Kara, A.; Vizzini, S. B.; Oughaddou, H.; LéAndri, C.; Ealet, B.; Le Lay, G. (2010). "Graphene-like silicon nanoribbons on Ag(110): A possible formation of silicene". Applied Physics Letters 96 (18): 183102.  
  5. ^ Lalmi, B.; Oughaddou, H.; Enriquez, H.; Kara, A.; Vizzini, S. B.; Ealet, B. N.; Aufray, B. (2010). "Epitaxial growth of a silicene sheet". Applied Physics Letters 97 (22): 223109.  
  6. ^ Bernard, R.; Leoni, T.; Wilson, A.; Lelaidier, T.; Sahaf, H.; Moyen, E.; Assaud, L. C.; Santinacci, L.; Leroy, F. D. R.; Cheynis, F.; Ranguis, A.; Jamgotchian, H.; Becker, C.; Borensztein, Y.; Hanbücken, M.; Prévot, G.; Masson, L. (2013). "Growth of Si ultrathin films on silver surfaces: Evidence of an Ag(110) reconstruction induced by Si". Physical Review B 88 (12).  
  7. ^ Colonna, S.; Serrano, G.; Gori, P.; Cricenti, A.; Ronci, F. (2013). "Systematic STM and LEED investigation of the Si/Ag(110) surface". Journal of Physics: Condensed Matter 25 (31): 315301.  
  8. ^ a b c Jose, D.; Datta, A. (2014). "Structures and Chemical Properties of Silicene: Unlike Graphene". Accounts of Chemical Research 47 (2): 593.  
  9. ^ a b c d Ni, Z.; Zhong, H.; Jiang, X.; Quhe, R.; Luo, G.; Wang, Y.; Ye, M.; Yang, J.; Shi, J.; Lu, J. (2014). "Tunable band gap and doping type in silicene by surface adsorption: Towards tunneling transistors". Nanoscale 6 (13): 7609.  
  10. ^ Padova, P. D.; Leandri, C.; Vizzini, S.; Quaresima, C.; Perfetti, P.; Olivieri, B.; Oughaddou, H.; Aufray, B.; Le Lay, G. L. (2008). "Burning Match Oxidation Process of Silicon Nanowires Screened at the Atomic Scale". Nano Letters 8 (8): 2299–2304.  
  11. ^ a b Vogt, P.; De Padova, P.; Quaresima, C.; Avila, J.; Frantzeskakis, E.; Asensio, M. C.; Resta, A.; Ealet, B. N. D.; Le Lay, G. (2012). "Silicene: Compelling Experimental Evidence for Graphenelike Two-Dimensional Silicon". Physical Review Letters 108 (15).  
  12. ^ Lin, C. L.; Arafune, R.; Kawahara, K.; Tsukahara, N.; Minamitani, E.; Kim, Y.; Takagi, N.; Kawai, M. (2012). "Structure of Silicene Grown on Ag(111)". Applied Physics Express 5 (4): 045802.  
  13. ^ Feng, B.; Ding, Z.; Meng, S.; Yao, Y.; He, X.; Cheng, P.; Chen, L.; Wu, K. (2012). "Evidence of Silicene in Honeycomb Structures of Silicon on Ag(111)". Nano Letters 12 (7): 3507–3511.  
  14. ^ Guo, Z. X.; Furuya, S.; Iwata, J. I.; Oshiyama, A. (2013). "Absence of Dirac Electrons in Silicene on Ag(111) Surfaces". Journal of the Physical Society of Japan 82 (6): 063714.  
  15. ^ Arafune, R.; Lin, C. -L.; Nagao, R.; Kawai, M.; Takagi, N. (2013). "Comment on "Evidence for Dirac Fermions in a Honeycomb Lattice Based on Silicon"". Physical Review Letters 110 (22).  
  16. ^ Lin, C. L.; Arafune, R.; Kawahara, K.; Kanno, M.; Tsukahara, N.; Minamitani, E.; Kim, Y.; Kawai, M.; Takagi, N. (2013). "Substrate-Induced Symmetry Breaking in Silicene". Physical Review Letters 110 (7).  
  17. ^ Gori, P.; Pulci, O.; Ronci, F.; Colonna, S.; Bechstedt, F. (2013). "Origin of Dirac-cone-like features in silicon structures on Ag(111) and Ag(110)". Journal of Applied Physics 114 (11): 113710.  
  18. ^ Chen, L.; Liu, C. C.; Feng, B.; He, X.; Cheng, P.; Ding, Z.; Meng, S.; Yao, Y.; Wu, K. (2012). "Evidence for Dirac Fermions in a Honeycomb Lattice Based on Silicon". Physical Review Letters 109 (5).  
  19. ^ Fleurence, A.; Friedlein, R.; Ozaki, T.; Kawai, H.; Wang, Y.; Yamada-Takamura, Y. (2012). "Experimental Evidence for Epitaxial Silicene on Diboride Thin Films". Physical Review Letters 108 (24).  
  20. ^ Meng, L.; Wang, Y.; Zhang, L.; Du, S.; Wu, R.; Li, L.; Zhang, Y.; Li, G.; Zhou, H.; Hofer, W. A.; Gao, H. J. (2013). "Buckled Silicene Formation on Ir(111)". Nano Letters 13 (2): 685–690.  
  21. ^ Morishita, T.; Spencer, M. J. S.; Kawamoto, S.; Snook, I. K. (2013). "A New Surface and Structure for Silicene: Polygonal Silicene Formation on the Al(111) Surface". The Journal of Physical Chemistry C 117 (42): 22142.  
  22. ^ Gao, J.; Zhao, J. (2012). "Initial geometries, interaction mechanism and high stability of silicene on Ag(111) surface". Scientific Reports 2.  
  23. ^ Sugiyama, Y.; Okamoto, H.; Mitsuoka, T.; Morikawa, T.; Nakanishi, K.; Ohta, T.; Nakano, H. (2010). "Synthesis and Optical Properties of Monolayer Organosilicon Nanosheets". Journal of the American Chemical Society 132 (17): 5946–7.  

External links

  • Anthony, Sebastian (April 30, 2012). "Silicene discovered: Single-layer silicon that could beat graphene to market". 
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