Solid State Communications 247 (2016) 611

Contents lists available at ScienceDirect

Solid State Communications

journal homepage: www.elsevier.com/locate/ssc

Communication

Effects of surface passivation by lithium on the mechanical and

electronic properties of silicon nanowires
F. Salazar a, L.A. Prez b, M. Cruz-Irisson a,n
a
ESIME-Culhuacn, Instituto Politcnico Nacional, Av. Santa Ana 1000, 04430 Mxico, D.F., Mexico
b
Instituto de Fsica, Universidad Nacional Autnoma de Mxico, A.P. 20-364, 01000 Mxico, D.F., Mexico

art ic l e i nf o a b s t r a c t

Article history: In this work, we present a density functional theory study of the mechanical and electronic properties of
Received 27 April 2016 silicon nanowires (SiNWs) grown along the [111] crystallographic direction with a diamond structure and
Received in revised form surface passivated with hydrogen (H) and lithium (Li) atoms. The study is performed within the local
13 July 2016
density approximation by applying the supercell method. The results indicate that the energy gap is a
Accepted 11 August 2016
function of the Li concentration and the nanowire diameter. Furthermore, the Young's modulus
Available online 11 August 2016
(Y) increases as the nanowire diameter increases, consistent with experimental reports. The increase in the
Keywords: Li concentration at the surface leads to a larger Y value compared to the Y value of the completely
Semiconductors H-passivated SiNWs, except for the thinner nanowires. Moreover, the structure of the latter nanowires
Impurities in semiconductors
experiences important changes when the Li concentration increases up to the maximum Li atoms per cell.
Electronic band structure
These results demonstrate that it is possible to simultaneously control the energy gap and the Youngs
Mechanical properties
modulus by tuning the Li concentration on the surface of the SiNWs and could help to understand the
structural changes that the silicon nanowire arrays experience during the lithiation process in Li batteries.
& 2016 Elsevier Ltd. All rights reserved.

1. Introduction incorporation in the development of alternative energy sources,

The chemical stability and the electronic and optical properties
of silicon nanowires (SiNWs) are strongly determined by the atomic
compounds on their surface. The hydrogen passivation of SiNWs is
the simplest theoretical model because it possesses a less compu-
tational cost. The study of this theoretical model is motivated by the
following: it is currently possible to synthesize SiNWs, with dia-
meters that can be as small as 7 nm [1]; experimental reports that
indicate that the morphology of the Si atoms in the nanowire is
unaltered after the hydrogen passivation process [2]; and the na-
nowires maintain their semiconductor behavior. These facts facil-
itate comparisons between experimental and theoretical results.
The passivation of SiNWs by more complex compounds, such as
CH3, where covalent bonds between CH3 and surface Si atoms are
formed; leads to nanowires with low surface defect levels and high
chemical stability [3]. The deposition of alkyl chains onto H-passi-
vated SiNWs removes the Si-H bonds and replaces them with
covalent Si-Cx bonds that increase the mobility of the carriers [4].
The passivation of SiNWs arrays with SiO2 and SiNx improves the
recombination process of converting light to electricity [5]. These
results indicate that SiNWs are important candidates for rapid
n
Corresponding author.
E-mail address: irisson.ipn@gmail.com (M. Cruz-Irisson).
such as photovoltaic cells, and large-scale energy storage devices. In
this respect, rechargeable Li ion batteries currently offer the best
performance for portable electronic devices; however, it is desirable
to use these batteries in electric vehicles. The performance of the
battery is strongly determined by the material used for the elec-
trodes, and to improve this performance, research efforts are fo-
cused on nding and designing materials with high energy den-
sities, high specic energy storages, large discharge capacities for
high electrical currents and long useful life. Semiconductors are the
most suitable materials for anodes because they present a low
working potential with respect to Li/Li . Bulk Si has a working
potential of  0.4 V [6], and its theoretical specic Li storage capa-
city is 4200 mAh g  1 [7]. However, during Li insertion, the bulk Si
volume increases approximately 400% [6,7], causing fractures in the
material, loss of electrical contact and decreased storage capacity.
Semiconductor nanowire arrays are a viable alternative to overcome
these difculties. The space in Si nanowire arrays relieves the stress
during the lithiation process, thereby solving the volume expansion
problem. The number of deposited Li atoms is increased due to the
high surface area of the nanowires, and the charge transport is
improved when they are grown on metal substrates [8,9] and by
depositing Cu layers on the nanowire arrays [10].
In batteries, the charge-discharge cycle could induce an ex-
pansion-contraction cycle of the NWs volume [11]. To have a

http://dx.doi.org/10.1016/j.ssc.2016.08.012
0038-1098/& 2016 Elsevier Ltd. All rights reserved.
 F. Salazar et al. / Solid State Communications 247 (2016) 611 7

robust battery cycle performance, the NWs should have reversible
morphological changes [11,12] and then it is desirable that their
Young's modulus should not suffer drastic diminutions during
these cycles, as occurs in pristine SiNWs, where the nanowire
Young's modulus diminishes with the Li concentration [13]. The-
oretical and experimental studies show that the Young's modulus
value of SiNWs is lower than the bulk value and grows as a
function of the nanowire diameter [1416]. Moreover, theoretical
studies of Li diffusion in SiNWs indicate that Li atoms are more
stable at the surface [1719] than at interstitial sites, as some
studies suggest [17]. Therefore, there is still no consensus re-
garding the optimal placement of Li atoms on SiNWs. Finally, it is
worth mentioning that not only the mechanical properties but also
the energy gap of SiNWs , is a function of the nanowire diameter
and can be modied by surface passivation, substitutional or
interstitial impurities, and axial strain [14,2022].
In this work, we perform a density functional theory study of
the effects of surface Li atoms on the physical properties of
otherwise hydrogen-passivated SiNWs grown along the [111]
crystallographic direction with a diamond structure. For this pur-
pose, we present the electronic band structure, the electronic
density of states (DOS), the lithium binding energy and the
Young's modulus (Y) as functions of the nanowire diameter and
the concentration of Li atoms at the surface.
2. The model
Fig. 1 shows the initial morphologies of the SiNWs grown along
the [111] crystallographic direction. Using periodic boundary

Fig. 1. Side and cross-sectional views of the non-relaxed unit cells of SiNWs grown along [111] considered in this work. To refer to each morphology, we label (a), (b), and
(c) as M1, M2, and M3, respectively. The yellow, white and blue spheres represent Si, H, and Li atoms, respectively. The number on the Li atoms indicates the sequence in
which the Li atoms replaced the H atoms. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
8 F. Salazar et al. / Solid State Communications 247 (2016) 611

conditions for these unit cell geometries and taking into account
sufcient lateral separation among neighboring wires, we simulate
an isolated, periodic and innitely long wire along this crystal-
lographic direction that we took as z direction. The left side of
Fig. 1 displays the side view of the unit cell, and the right side
shows the corresponding cross sections for each morphology. The
yellow, white and blue spheres represent Si, H and Li atoms, re-
spectively. The number on the substitutional Li atoms indicates the
sequence in which they were substituted for H atoms along the
nanowire surface. From this point, we refer to the morphologies in
Fig. 1 as (a) M1, (b) M2, and (c) M3 together with their respective Li
concentrations. For all studied morphologies, we start from the
relaxed morphology of the completely H-passivated SiNWs fol-
lowed by their optimization with substitutional Li atoms to obtain
the relaxed morphology. Note that our simulations indicate that an
odd number (greater than 1) of Li atoms along the perimeter of the
central non-planar hexagon of the unit cell leads to structures that
deviate from a symmetric nanowire. Hence, we present the results
for an even number of substitutional Li atoms together with the
case of a unit cell with a single substitutional Li atom as a re-
ference case.
This study was performed using the SIESTA code [23] within
the local density approximation (LDA) with standard norm-con-
serving pseudopotentials [24] in their fully nonlocal form [25]. The
pseudopotentials for Si and Li were generated with the atomic
valence-electron conguration s2p2. The core radii for Si are s
(1.89), p(1.89), and d(1.89). In the present calculations, we use the
double- s,p-basis and a single d orbital, an energy cutoff of at
least 300 Ry to dene the real-space grid for numerical integra-
tions, and a k-grid whose diagonals are 1, 1, and 24. All of the
studied nanowires were free to relax until the Hellmann-Feynman
forces were less than 2 meV/. The suitability of the potential was
tested by calculating the bulk bond lengths and lattice constant for
the bulk Si diamond structure; the predicted SiSi length and
lattice constant are 2.33 and 5.39 , respectively, and the cor-
responding experimental values are 2.35 for the SiSi bond
length and 5.43 for the lattice constant [26]. Both calculated
physical quantities are in good agreement with the corresponding
experimental values within an error of less than 0.8%.
3. Results
3.1. Electronic properties
The electronic band structure is obtained for the trajectory
from to /a, where is the usual crystallographic point and /a
indicates a point along the growth direction of the nanowire. Fig. 2
shows the electronic band structure, the DOS (black line) together
with the partial DOS of atomic species Si (red line), H (blue line)
and Li (gray line) for the SiNWs with the largest diameter con-
sidered in this work (M3 morphology) and with (a) 0, (b) 1, (c) 2,
(d) 4, (e) 6, (f) 8, (g) 10, and (h) 12 Li atoms per unit cell. The type
of energy gap (gray dash line) is indirect for all the cases con-
sidered. As expected, the band gap decreases as a function of the
nanowire diameter, reecting the known quantum connement

Fig. 2. Electronic band structures and electronic density of states (DOS) of otherwise hydrogen-passivated SiNWs with the largest diameter studied in this work and with
(a) 0, (b) 1, (c) 2, (d) 4, (e) 6, (f) 8, (g) 10 and (h) 12 substitutional surface lithium atoms per unit cell. At the right of each band structure, the total (black line) and partial DOS
by atomic species Si (red line), H (blue line), and Li (gray line) are shown. The dashed line indicates the Fermi energy (shifted to zero). (For interpretation of the references to
color in this gure legend, the reader is referred to the web version of this article.)
 F. Salazar et al. / Solid State Communications 247 (2016) 611
effect [14].
Notice in Fig. 2(b) that when a Li atom replaces an H one, a new
band appears in the former energy gap of the original pure
H-passivated SiNW; this type of band is known as trap-like states,
which have been studied in systems containing impurities [27].
The main contribution to the DOS is due to the Si atoms (red line),
and the participation of the Li atoms is hardly noticeable at the
edges of the valence and conduction bands (gray line). The band
gap decreases as the Li atom concentration increases for the three
morphologies and the states of the Li and Si atoms become im-
portant at the edges of the valence and conduction bands, in
contrast to the pure H-passivated SiNWs. These results demon-
strate that when the Li atoms are at the surface of the nanowires,
more electrons are available for the electron transport process,
revealing a metallic transition. Additionally, the band gap is in-
direct for the three H-passivated SiNWs morphologies.
Fig. 3 shows the energy gap (Eg) as a function of the number
of substitutional Li atoms per unit cell. The squares, circles and
triangles correspond to the M1, M2, and M3 morphologies shown
in Fig. 1, respectively. As expected, the band gap decreases as a
function of the number of Li atoms, revealing a metallic transition.
All the energy gap values of the investigated SiNWs are greater
than the bulk value obtained with SIESTA (0.64 eV), as indicated
with a dashed gray line. The type of gap is indicated with full
symbols for a direct gap and with open symbols for an indirect
gap.
These results show that the size and nature of the band gap are
functions of the diameter, concentration and position of the Li
atoms of the SiNWs. Fig. 4 shows the nal relaxed structures of the
SiNWs with the maximum concentration of surface Li atoms per
unit cell for the same morphologies shown in Fig. 1. Note that the
Li atoms modify the morphology of the SiNWs in different ways,
which must be reected in the mechanical properties of the na-
nowires, as discussed in the next section.
Finally, the lithium binding energy (b) and its dependence on
surface coverage is relevant for Li storage applications. b(n) for a
SiNW, with N-n passivating hydrogen atoms and n substitutional Li
surface atoms per unit cell, can be calculated as follows:
Fig. 3. Energy band gap (Eg) of SiNWs as a function of the number of Li atoms per
unit cell. The full and open symbols indicate direct and indirect energy gaps, re-
spectively. The squares, circles, triangles correspond to the M1, M2, and M3
morphologies shown in Fig. 1, respectively. The gray dashed line corresponds to the
calculated energy gap of bulk Si.
9
1
b (n) = E (SiNW + NH ) + nE (Li) n E (H2 )
2
E (SiNW + nLi + [N n] H )
where E(X) denotes the calculated total energy of system X. In this
scheme, the larger the value of b, the stronger the binding of Li to
the NW.
Fig. 5 shows the Li binding energy per lithium atom (b(n)/n) as
a function of the number of lithium atoms per unit cell (n) for the
three morphologies considered in this work. Notice that for the
nanowire with the largest diameter (M3), b(n)/n is 2 eV and
nearly constant with respect to Li content, in agreement with
previous theoretical studies performed in silicine layers [30,31].
3.2. Mechanical properties
Young's modulus (Y) is the ratio between the stress and strain,
and it can be calculated as follows:
1 2E
Y=
V 2 = 0
where E is the total energy, V is the equilibrium volume, and L
L is the axial strain; L is the change in the nanowire's equilibrium
length L [28,29]. The general procedure consists of taking a section
of nanowire and using periodic boundary conditions on a supercell
geometry with sufcient lateral separation among neighboring
wires to simulate an isolated, innitely long wire. Then, the na-
nowire is subjected to strain along the axial direction. At each
strain, the positions of all atoms in the supercell are fully relaxed
without constrains using a conjugated gradient minimization
technique. From these calculations, the total energy and atomic
positions as a function of the axial strain imposed on the nanowire
are obtained, from which the Young's modulus can be calculated
by tting a second-degree polynomial to E(). After the relaxation
process, the cross section of the nanowire is obtained by project-
ing the spatial coordinates in the xy plane and considering it as a
circumference whose radius is the average of the distances from
the geometrical center to the external atoms H and Li. Fig. 6 shows
the Young's modulus of the SiNWs as a function of the con-
centration of Li atoms. The blue triangles and the red circles cor-
respond to morphologies M3 and M2 shown in Fig. 1(c) and (b),
respectively.
Note that the Young's modulus for both morphologies increases
as a function of the concentration of Li atoms, and their values
increase by approximately 10 GPa for the maximum concentration
of Li compared with the pure H-passivated SiNWs. This result
contrasts with theoretical and experimental results regarding
pristine SiNWs, where the nanowire Young's modulus diminishes
with the Li concentration [13]. Then H-passivated SiNWs could be
incorporated as anodes in Li ion batteries instead of pristine
SiNWs.
Finally, the black squares correspond to morphology M1 shown
in Fig. 1(a). For this case, Y monotonically decreases as the number
of Li atoms per unit cell increases from 1 to 4, but when there are
6 Li atoms per cell, Y increases again to a value similar to that of
the completely hydrogenated SiNW. The explanation of this be-
havior is related to structural changes occurring at the central non-
planar hexagon of Si atoms. Fig. 6 also shows the relaxed geo-
metries for each concentration, all of which have the same spatial
orientation. First, we observe that in all cases, the Li atoms (blue
spheres) do not remain at the central non-planar hexagon of Si
atoms (yellow spheres) but are rather displaced along the axial
direction and remain close to the nanowire. Despite the dis-
placement of the Li atoms, the LiSi bonds remain, and the
structure is apparently symmetric. The SiNWs that present this
10 F. Salazar et al. / Solid State Communications 247 (2016) 611
Fig. 4. Optimized structures of SiNWs with the maximum concentration of surface Li atoms per unit cell for the same morphologies shown in Fig. 1.
Fig. 5. Lithium binding energy per lithium atom (b(n)/n) as a function of the
number of Li atoms per unit cell (n) for the three morphologies considered in this
work.
non-planar hexagonal morphology of Si atoms have 0 (completely
H passivated), 1, 2 and 4 Li atoms per cell. When the central non-
planar hexagonal morphology is completely passivated with 6 Li
atoms, the relaxed structure becomes a central planar hexagonal
structure of Si atoms, as shown in Fig. 6. Then, an important
change in the geometry occurs, in which the nal morphology
belongs to a different crystallographic group with different me-
chanical properties.
A further systematic study is necessary to classify the different
structures that can be present during the lithiation process;
moreover, it is necessary to consider different concentrations and
locations of Li atoms to obtain a better understanding of the effect
of the supercial Li atoms on the band gap and the mechanical
properties of SiNWs. These results indicate that the Young's
modulus of the SiNWs can be controlled varying the Li con-
centration and could provide information related to the stress on
the NWs during the lithiation process.
Furthermore, this analysis also indicates that if the Young's
modulus increases when the diameter and concentration of Li
atoms change, then there is a critical concentration of Li atoms
Fig. 6. Young's modulus (Y) as a function of the number of lithium atoms per unit
cell. The black squares, red circles and blue triangles correspond to the M1, M2, and
M3 morphologies shown in Fig. 1, respectively. The optimized structures for the
thinner SiNWs, with the different Li concentrations considered, are also shown. The
yellow, white and blue spheres correspond to Si, H and Li atoms, respectively. (For
interpretation of the references to color in this gure legend, the reader is referred
to the web version of this article.)
that maximizes the Young's modulus before the SiNW experiences
a fracture. Consequently, it could be possible to control the specic
energy to insert Li ions at a concentration that allows the useful
life of the battery to be increased without reaching the fracture
limit.
4. Summary
In this work, we investigated the electronic and mechanical
properties of SiNWs grown along the [111] crystallographic di-
rection and passivated with H and substitutional Li atoms. The
results indicate that the size and nature of the energy band gap, as
well as the Young's modulus, depend on the nanowire diameter
and on the concentration and positions of Li atoms at the SiNW
surface. For stable morphologies, the addition of substitutional Li
atoms leads to an enhancement of Y, except for the thinner Si
nanowire, revealing the role of the morphology in the mechanical
 F. Salazar et al. / Solid State Communications 247 (2016) 611
properties of the SiNWs. Finally, these results open new possibi-
lities for simultaneously controlling the electronic and mechanical
properties of the potential anodic nanomaterials that could be
incorporated in the next generation of Li batteries.
Acknowledgments
This work was supported by multidisciplinary projects 2016-
1770 and 2016-1771 from SIP-Instituto Politcnico Nacional,
CONACyT-252749, and DGAPA-UNAM-PAPIIT IN106714. L.A.P. ac-
knowledges partial support from Ctedra Marcos Moshinsky and
PIIF No. 3. Computing resources from the Supercomputing De-
partment of DGTIC-UNAM were given by project SC16-1-IG-32.
References
[1] D.D.D. Ma, C.S. Lee, F.C.K. Au, S.Y. Tong, S.T. Lee, Small-diameter silicon nano-
wire surfaces, Science 299 (2003) 18741877, http://dx.doi.org/10.1126/
science.1080313.
[2] Y.F. Zhang, L.S. Liao, W.H. Chan, S.T. Lee, R. Sammynaiken, T.K. Sham, Electronic
structure of silicon nanowires: a photoemission and x-ray absorption study,
Phys. Rev. B 61 (2000) 82988305, http://dx.doi.org/10.1103/
PhysRevB.61.8298.
[3] H. Haick, P.T. Hurley, A.I. Hochbaum, P. Yang, N.S. Lewis, Electrical character-
istics and chemical stability of non-oxidized, methyl-terminated silicon na-
nowires, J. Am. Chem. Soc. 128 (2006) 89908991, http://dx.doi.org/10.1021/
ja056785w.
[4] M.Y. Bashouti, T. Stelzner, A. Berger, S. Christiansen, H. Haick, Chemical pas-
sivation of silicon nanowires with C1  C6 alkyl chains through covalent Si  C
bonds, J. Phys. Chem. C 112 (2008) 1916819172, http://dx.doi.org/10.1021/
jp8077437.
[5] A.D. Mallorqu, E. Alarcn-Llad, I.C. Mundet, A. Kiani, B. Demaurex, S. De Wolf,
A. Menzel, M. Zacharias, A.F. Morral, Field-effect passivation on silicon nano-
wire solar cells, Nano Res. 8 (2015) 673681, http://dx.doi.org/10.1007/
s12274-014-0551-7.
[6] N. Liu, W. Li, M. Pasta, Y. Cui, Nanomaterials for electrochemical energy sto-
rage, Front. Phys. 9 (2014) 323350, http://dx.doi.org/10.1007/
s11467-013-0408-7.
[7] B.A. Boukamp, G.C. Lesh, R.A. Huggins, Allsolid lithium electrodes with mixed
conductor Matrix, J. Electrochem. Soc. 128 (1981) 725729, http://dx.doi.org/
10.1149/1.2127495.
[8] C.K. Chan, H. Peng, G. Liu, K. McIlwrath, X.F. Zhang, R.A. Huggins, Y. Cui, High-
performance lithium battery anodes using silicon nanowires, Nat. Nano-
technol. 3 (2008) 3135, http://dx.doi.org/10.1038/nnano.2007.411.
[9] H. Fll, H. Hartz, E. Ossei-Wusu, J. Carstensen, O. Riemenschneider, Si nano-
wire arrays as anodes in Li ion batteries, Phys. Stat. Sol. R. 4 (2010) 46,
http://dx.doi.org/10.1002/pssr.200903344.
[10] M. Leisner, A. Cojocaru, E. Ossei-Wusu, J. Carstensen, H. Fll, New applications
of electrochemically produced porous semiconductors and Nanowire arrays,
Nanoscale Res. Lett. 5 (2010) 15021506, http://dx.doi.org/10.1007/
s11671-010-9669-z.
[11] T. Song, L. Hu, U. Paik, One-dimensional silicon nanostructures for Li ion bat-
teries, J. Phys. Chem. Lett. 5 (2014) 720731, http://dx.doi.org/10.1021/
11
jz4027979.
[12] X. Ma, W. Luo, M. Yan, L. He, L. Mai, In situ characterization of electrochemical
processes in one dimensional nanomaterials for energy storages devices, Nano
Energy 24 (2016) 165188, http://dx.doi.org/10.1016/j.nanoen.2016.03.023.
[13] A. Kushima, J.Y. Huang, J. Li, Quantitative fracture strength and plasticity
measurements of lithiated silicon nanowires by in situ TEM tensile experi-
ments, ACS Nano 6 (2012) 94259432, http://dx.doi.org/10.1021/nn3037623.
[14] F. Salazar, L.A. Prez, Theoretical study of electronic and mechanical properties
of GeC nanowires, Comput. Mater. Sci. 63 (2012) 4751, http://dx.doi.org/
10.1016/j.commatsci.2012.05.066.
[15] D. Tang, C. Ren, M. Wang, X. Wei, N. Kawamoto, C. Liu, Y. Bando, M. Mitome,
N. Fukata, D. Golberg, Mechanical properties of Si nanowires as revealed by
in situ transmission electron microscopy and molecular dynamics simulations,
Nano Lett. 12 (2012) 18981904, http://dx.doi.org/10.1021/nl204282y.
[16] C. Rhlig, M. Niebelschtz, K. Brueckner, K. Tonisch, O. Ambacher, V. Cimalla,
Elastic properties of nanowires, Phys. Stat. Sol. B 247 (2010) 25572570, http:
//dx.doi.org/10.1002/pssb.201046378.
[17] Q. Zhang, W. Zhang, W. Wan, Y. Cui, E. Wang, Lithium insertion in silicon
nanowires: an ab initio study, Nano Lett. 10 (2010) 32433249, http://dx.doi.
org/10.1021/nl904132v.
[18] Q. Zhang, Y. Cui, E. Wang, First-principles approaches to simulate lithiation in
silicon electrodes, Model. Simul. Mater. Sci. Eng. 21 (2013) 074001074029,
http://dx.doi.org/10.1088/09650393/21/7/074001.
[19] P. Kaghazchi, Theoretical studies of Li incorporation into Si(111), J. Phys.:
Condens. Matter 25 (2013) 095008, http://dx.doi.org/10.1088/09538984/25/
9/095008.
[20] P.G. Bruce, B. Scrosati, J.M. Tarascon, Nanomaterials for rechargeable lithium
batteries, Angew. Chem. Int. Ed. 47 (2008) 29302946, http://dx.doi.org/
10.1002/anie.200702505.
[21] Y. Guo, J. Hu, L. Wan, Nanostructured materials for electrochemical energy
conversion and storage devices, Adv. Mater. 20 (2008) 28782887, http://dx.
doi.org/10.1002/adma.200800627.
[22] M.A. Sk, M. Ng, L. Huang, K.H. Lim, Modulating the electronic properties of
germanium nanowires via applied strain and surface passivation, Phys. Chem.
Chem. Phys. 15 (2013) 59275935, http://dx.doi.org/10.1039/c3cp43530j.
[23] J.M. Soler, E. Artacho, J.D. Gale, A. Garca, J. Junquera, P. Ordejn, D. Snchez-
Portal, The SIESTA method for ab initio order-N materials simulation, J. Phys.:
Condens. Matter 14 (2002) 27452779, http://dx.doi.org/10.1088/09538984/
14/11/302.
[24] N. Troullier, J.L. Martins, Efcient pseudopotentials for plane-wave calcula-
tions, Phys. Rev. B 43 (1991) 19932006, http://dx.doi.org/10.1103/
PhysRevB.43.1993.
[25] L. Kleinman, D.M. Bylander, Efcacious form for model pseudopotentials, Phys.
Rev. Lett. 48 (1982) 14251428, http://dx.doi.org/10.1103/PhysRevLett.48.1425.
[26] C. Kittel, Solid State Physics, 7th ed, John Wiley & Sons, New York, 1996.
[27] A. Miranda, J.L. Cuevas, A.E. Ramos, M. Cruz-Irisson, Effects of morphology on
the electronic properties of hydrogenated silicon carbide nanowires, J. Nano
Res. 5 (2009) 161167, http://dx.doi.org/10.4028/www.scientic.net/
JNanoR.5.161.
[28] B. Lee, R.E. Rudd, First-principles study of the Young's modulus of Si 001
nanowires, Phys. Rev. B 75 (2007) 041305, http://dx.doi.org/10.1103/
PhysRevB.75.041305.
[29] W.W. Zhang, Q.A. Huang, H. Yu, L.B. Lu, Size-dependent elasticity of silicon
nanowires, Adv. Mat. Res. 6061 (2009) 315319, http://dx.doi.org/10.4028/
www.scientic.net/AMR.60-61.315.
[30] T.H. Osborn, A.A. Farajian, Stability of lithiated silicene from rst principles, J.
Phys. Chem. C 116 (2012) 2291622920, http://dx.doi.org/10.1021/jp306889x.
[31] G.A. Tritsaris, E. Kaxiras, S. Meng, E. Wang, Adsorption and diffusion of lithium
on layered silicon for Li-ion storage, Nano Lett. 13 (2013) 22582263,
http://dx.doi.org/10.1021/nl400830u.