First-Principles Investigation of Bilayer Fluorographene

J. Sivek,1, ∗ O. Leenaerts,1, † B. Partoens,1, ‡ and F. M. Peeters1, §

1
Departement Fysica, Universiteit Antwerpen, Groenenborgerlaan 171, B-2020 Antwerpen, Belgium
(Dated: July 18, 2012)
Ab initio calculations within the density-functional theory formalism are performed to investigate
the stability and electronic properties of fluorinated bilayer graphene (bilayer fluorographene). A
comparison is made to previously investigated graphane, bilayer graphane and fluorographene. Bi-
layer fluorographene is found to be a much more stable material than bilayer graphane. Its electronic
band structure is similar to monolayer fluorographene but its electronic band gap is significantly
larger (about 1 eV). We also calculate the effective masses around the Γ- point for fluorographene
and bilayer fluorographene and find that they are isotropic, in contrast to earlier reports. Further-
arXiv:1109.4050v4 [cond-mat.mtrl-sci] 17 Jul 2012

more, it is found that bilayer fluorographene is almost as strong as graphene, as its 2D Young’s
modulus is approximately 300 N m−1 .

PACS numbers: 61.48.Gh, 68.43.-h, 68.43.Bc, 68.43.Fg, 73.21.Ac, 81.05.Uw

I. INTRODUCTION result from the hydrogenation and fluorination of

graphene, respectively. They are theoretically predicted
Since the first reports on the successful isolation of sta- [19–26] and experimentally observed [14–16, 18, 27, 28]
ble two-dimensional crystals consisting of a single atom to form crystalline materials in contrast to e.g. graphene
layer by Novoselov et. al. in 2004, [1, 2] researchers oxide. [29, 30]
have been looking for ways to employ these new mate- These new two-dimensional crystals are currently the
rials in real-world applications. Of particular interest is subject of a considerable amount of experimental and
graphene, a single layer derivative of graphite. Graphene theoretical work. But the process of chemical modifi-
attracts a lot of attention with its high crystal quality cation is not restricted to monolayer graphene. It has
and very promising electronic properties. [3] been proposed that this process can be expanded to bi-
layer graphene as well. [31] Ab initio calculations showed
Despite its unique characteristics which might be ex-
that the weak van der Waals forces between the graphene
ploited in future applications, [4–7] there exists a seri-
layers are replaced by much stronger covalent bonds that
ous obstacle to use graphene in electronics as we know
stabilize the structure and that, at full coverage, a bilayer
it today. Graphene is a zero-gap semiconductor and the
analogue of graphane is formed. The electronic struc-
absence of a band gap is protected by inversion and time-
ture of intrinsic monolayer and bilayer graphane are very
reversal symmetry. [8] Several approaches have been
similar, [32] but their mechanical/elastic properties are
used or proposed to open and control a band gap in
expected to be substantially different.
graphene and graphene derivatives: i) mechanical modifi-
The difference in elastomechanical qualities can be an
cation such as cutting the graphene sample into nanorib-
important issue. It was recently demonstrated [33] that
bons, [9, 10] ii) application of a potential difference over
the roughness of monolayer graphane surfaces is consid-
a bilayer of graphene [11–13] and, finally, iii) chemical
erably larger than that of graphene. This increase of
modification which confines the pz electrons into covalent
the size of the ripple formation can be explained by the
bonds. [14–18] The last approach includes the adsorption
lower stiffness of graphane [34] and its different vibra-
of radicals such as oxygen, hydrogen and fluorine atoms
tional properties as compared to graphene. [35] One way
on the surface of graphene which form chemical bonds
to reduce the increased roughness is to consider bilayers
with the carbon atoms and change their hybridization
instead of single layers. As is well known from experi-
from sp2 to sp3 . The chemical derivatives of graphene
ment the ripple formation in bilayer graphene is strongly
preserve the two-dimensional character of graphene but
reduced, i.e. they are removed by the interlayer inter-
they have vastly different electronic properties. This
action. [36] A similar effect can be expected for bilayer
makes them possibly more interesting materials for ap-
graphane where the interlayer interaction is even more
plications in electronics than intrinsic graphene.
important.
Among the possible derivatives of graphene there
In this paper we investigate whether it is also possi-
are two that have attracted special attention, namely
ble to fluorinate bilayer graphene. We perform ab ini-
graphane and fluorographene (graphene fluoride), which
tio calculations to determine the stability and structural
properties of a fluorinated bilayer of graphene, hereafter
called bilayer fluorographene (for a better notion of the
∗ Electronic address: [email protected]
chemical composition and the structure see Fig. 1). We
† Electronic address: [email protected] find that bilayer fluorographene is a much more stable
‡ Electronic address: [email protected] compound than bilayer graphane, although more fluori-
§ Electronic address: [email protected] nation is needed to induce interlayer covalent C-C bonds.
 2

The structural properties of bilayer fluorographene are in

between those of monolayer fluorographene and diamond,
other characteristics are closer to initial fluorographene.
This paper is organized as follows: first we describe
the computational details of our ab initio calculations,
followed by an investigation of the stability and the
formation conditions of interlayer covalent C-C bonds.
Next, the overall stability and the geometrical proper-
ties of fully fluorinated bilayer graphene (i.e. bilayer flu-
orographene) are examined. These properties are sub-
sequently compared with those of diamond and fluoro-
FIG. 1: Top (left) and side (right) view of bilayer fluoro-
graphene. To conclude, we investigate the electronic graphene. The carbon atoms of the two layers are given by
band structure and band gaps of single layer and bilayer different colors (shades) for clarity and the fluorine atoms are
fluorographene, together with the effective masses of the in light green (open circles with the smallest diameter).
various possible charge carriers and elastic properties rep-
resented by their 2D Young’s moduli.
III. RESULTS AND DISCUSSION

A. Fluorination of bilayer graphene

The main objective of this paper is to investigate

II. CALCULATIONS
chemisorption of fluorine atoms on both sides of bilayer
graphene. Hydrogenation and fluorination of the carbon
All our calculations were done within the density func- atoms of graphene changes their hybridization from sp2
tional theory (DFT) formalism as implemented in the to sp3 . In the case of hydrogenation of bilayer graphene,
VASP package with usage of the local-density approx- it was demonstrated that stable interlayer C-C bonds are
imation (LDA) and the Perdew, Burke and Ernzerhof induced at high concentrations of adsorbates.[31] In this
[37] generalized gradient approximation (GGA) for the section, we perform a similar study for the case of fluo-
exchange-correlation functional. We made use of the pro- rination and highlight the similarities and differences as
jector augmented wave method [38] and a plane-wave ba- compared to hydrogenated bilayer graphene. We make
sis set with an energy cutoff of 500 eV. The relaxation of use of the local density approximation, because this ap-
atomic positions was performed with forces smaller than proximation gives a better description of the interlayer
0.01 eV Å−1 . interaction in bilayer graphene over the generalized gra-
dient approximation.[41]
Three types of supercells were used in our calculations:
3 × 3 and 2 × 2 supercells to study the adsorption proper-
ties of fluorine on a graphene bilayer for different concen-
trations and configurations of fluorine, and a 1 × 1 unit
cell for the calculation of the properties and electronic
band structure of fully fluorinated graphene and bilayer
graphene.
The sampling of the Brillouin zone was done for the
different supercells with the equivalent of a 24 × 24 × 1
Monkhorst-Pack [39] k-point grid for the monolayer or bi-
layer graphene unit cell (containing 2 carbon atoms per
layer). Spin polarization was not included in the cal- FIG. 2: Bilayer of AB stacked graphene with the 4 different
culations because fluorination is not expected to induce sublattices indicated by different shades (colors). The A and
B’ sublattice are situated on top of each other as illustrated
magnetism in graphene. [40]
by the dotted lines. The carbon atoms at the corners of the
Since periodic boundary conditions were applied in all light triangles indicate the 6 neighbors to be fluorinated.
three dimensions the height of the supercell was set to
20 Å to include enough vacuum to minimize the inter- We only consider chemisorption on bilayer graphene
action between adjacent layers. Additionally we have with AB-stacking because this is the most energetically
performed a convergence test with respect to the planar favorable way of stacking graphene layers. As indicated
size of the supercell. We obtain an accuracy in binding in Fig. 2, this gives rise to four sublattices (2 in each
energies of less than 0.1 eV and in bond lenghts of less layer) of which two, namely the A and B’ sublattice, are
than 0.01 Å with the chosen 3 × 3 supercell. exactly aligned on top of each other while the sublattices
 3

B and A’, are not. Since the adsorbates under investiga-

TABLE I: Interlayer chemical bond formation in a 3 × 3
tion always chemisorb on top of a single C atom, there
supercell. The binding energy per F atom (Eb ), the formation
are two (inequivalent) adsorption sites, namely on the A energy per F atom (Ef ) and the average (davg ) and minimum
(or B’) sublattice and on the B (or A’) sublattice. It distance (dmin ) between the C atoms of the two layers are
was found in an earlier study of hydrogen adsorption on shown for different number of adsorbed fluorine atoms and
bilayer graphene that there is a difference in adsorption different configurations. Presence of interlayer bond is marked
energy of approximately 0.03 eV in favor of the B sub- as chemical bond. Energies are given in eV and distances in Å.
lattice. [31] The H atoms are therefore likely to attach
to those carbon atoms which have no direct neighbors in # F configuration Eb Ef davg dmin chem.
the other layer. For F atoms, we find the same preference atoms bond
for adsorption on the B sublattice. However, the differ-
1 B -2.525 -0.819 3.326 3.256 no
ence in adsorption energy for the two sublattices is only
0.3 meV, which is about 100 times smaller than in the 2 BB -2.405 -0.700 3.326 3.190 no
0
case of hydrogen. This is caused by the different nature 2 BA -2.555 -0.850 3.213 3.085 no
of C-F bonds as compared to C-H bonds: C-H bonds 3 BBB -2.290 -0.585 3.332 3.126 no
are purely covalent, but C-F bonds have a partially ionic 3 BBA0 -2.487 -0.782 3.176 2.979 no
character because of the large difference in electronega- 4 BBBA0 -2.384 -0.679 3.150 2.903 no
tivity between C and F. 4 BBA0 A0 -2.479 -0.773 3.061 2.821 no
The formation of a chemical bond between an adsor- 5 0 0
BBBA A -2.450 -0.745 2.678 1.757 yes
bate and a C atom of the bilayer of graphene induces 6 BBBA0 A0 A0 -2.560 -0.854 2.598 1.737 yes
a change in the hybridization of this C atom from sp2
to sp3 . If the concentration of attached adsorbates on
the preferred sublattice increases, the carbon atoms of with respect to intrinsic bilayer graphene and the di-
the other sublattice also change their hybridization to atomic molecule F2 . The binding energy (Eb ), on the
sp3 . This allows for the formation of covalent bonds be- other hand, is defined as the energy per fluorine atom
tween the two graphene layers. These interlayer bonds (or CF pair) with respect to intrinsic bilayer graphene
are formed between carbon atoms of the A and B’ sub- and atomic fluorine. Both energies are given in Table I.
lattices that are pushed to one another because of the The formation energy, Ef , is negative in all cases
changed hybridization of their neighbors. which means that all the configurations are stable against
For a single interlayer C-C bond there are six neighbors molecular desorption from the graphene surface. This
- three atoms in the B and three in the A’ sublattice (Fig. should be contrasted to the same concentrations of hy-
2). However, it is not necessary for all these neighbors drogen atoms on the surface of bilayer graphene, where
to change their hybridization in order for the interlayer the energy becomes negative only in the case of almost
bond to be formed, as in the case of hydrogen chemisorp- fully hydrogenated bilayer graphene.[31] The value of
tion on bilayer graphene where only four of the neighbor- the formation energies in the case of fluorination is sig-
ing carbon atoms need to be hydrogenated to induce a nificantly lower (almost 1 eV) than in the case of hy-
covalent interlayer bond. [31] drogen chemisorption. This can be attributed to the
In order to study the formation of interlayer bonds weaker bond in the F2 as compared to the H2 molecule
upon fluorination in more detail, we gradually increase and is similar to the previous studied case of monolayer
the number of attached fluorine atoms on neighboring graphane and fluorographene.[23] The calculated bind-
carbon atoms from 1 to 6. We completely relax the re- ing energies also show that it is energetically favorable
sulting systems and calculate the average and minimum for the fluorine atoms to attach themselves on both sides
distance between the C atoms of the two layers. The re- of the bilayer: for the same number of chemisorbed F
sults of these computations are summarized in Table I. atoms, the configuration in which these atoms are dis-
From this table, a gradual decrease of the interlayer dis- tributed as equally as possible between the two layers
tance can be seen upon increasing the concentration of F is lower in energy and thus more stable. The fact that
atoms. At higher concentrations, however, a substantial adsorbed F atoms on one side of the bilayer make it fa-
jump in the minimum distance, dmin , occurs when going vorable for other F atoms to adsorb on the other side, in-
from 4 to 5 fluorinated neighbors. This jump is about creases the chance of interlayer bond formation. Because
1 Å in size and clearly indicates the formation of an in- these bonds are stable, we can imagine this process of flu-
terlayer bond. It is thus necessary to fluorinate 5 of the orination and interlayer bond formation to continue until
6 neighbors to induce an interlayer bond, in contrast to a fully covered bilayer of graphene fluoride is formed.
hydrogenation where 4 hydrogenated neighbors suffice. To test if the aforementioned interlayer bond creation
Additional information about the stability of the inter- scenario is truly energetically favorable we considered a
layer bond can be obtained by examining the formation 2 × 2 supercell for a gradual fluorination with different
and binding energy of the system at different concen- configuration patterns. To be able to choose from the
trations of adsorbed F atoms. We define the formation large number of different possible configurations we need
energy (Ef ) as the energy per attached fluorine atom some guidelines for further investigation. As a first guide-
 4

line we distribute the F atoms equally on both sides of the leads to interlayer bonding and in which a high fluorine
bilayer because it is more energetically favorable as dis- concentration can be reached.
cussed above. Four prevalent configurations are known
for the fluorination of graphene: chair, boat, zigzag and
0
armchair. The chair configuration can be readily ex- a)
-0.2
tended to the fluorination of bilayer graphene discussed
-0.4
above. The remaining three configurations share as a

formation energy (eV)

-0.6 b)
common feature that they contain dimers, as depicted in
-0.8
the inset of Fig. 3. Those dimers are used as the second
-1
guideline to reduce configuration space. The dimer a is
composed of F atoms bonded with directly neighboring -1.2 c)

C atoms whereas the dimer b consists of F atoms bonded -1.4 dimer a

with distant C atoms on the opposite sides of the hexag- -1.6 dimer b
onal ring. For higher fluorine concentration (above two -1.8 B-A' sublattice

dimers, one at each side of the bilayer) dimers a and b are -2

combined and create a trimer configuration, as depicted 5 10 15 20 25 30 35 40 45 50 55
in the inset c of Fig. 3. atomic % F
The calculated results are given in Fig. 3. In this figure
we present the formation energy per adatom for the dif- FIG. 3: Gradual fluorination of a 2 × 2 supercell of bilayer
ferent fluorination pathways. These results show that for graphene. For increasing F concentration the formation en-
low concentrations of F atoms the dimer b configuration ergy per fluorine atom is shown. The curves show different
is more stable (carbon atoms from both sublattices are distributions of the F atoms - according to dimer configura-
fluorinated and no interlayer bonds are created). How- tion a (inset a) and b (inset b), only on sublattices B and A’,
ever, higher concentrations of F atoms are not feasible and the placement of the F atoms only on sublattices A and
B’. Dimers a and b can not be preserved for higher levels of
with the dimer configurations as the formation energy
fluorination, instead they transform into the trimer configu-
increases. But if only the B and A’ sublattices are flu- ration (inset c).
orinated, the formation energy can decrease even more,
finally creating bilayer fluorographene, with completely
saturated C atoms as can be seen in Fig. 1. It is also
important to point out that the total formation energy
for all adsorbed F atoms (not shown in the figure) is a B. Properties of bilayer fluorographene
monotonically decreasing function of the F atom concen-
tration and therefore the local minimum for dimer b will In this section we examine the properties of bilayer
not result in an interruption of the adsorption. fluorographene in more detail and compare them with
Our calculations also showed that for both dimer con- those of monolayer fluorographene and diamond. For
figurations no interlayer bonding was formed. The dimers the study of the geometrical properties we include also
a and b transform for higher coverage into the trimer GGA calculations because they give more accurate bond
configuration as indicated by the connection of the plots. lengths and angles. A summary of the geometrical and
For the adsorption on B and A’ sublattices the interlayer electronic properties is given in Tables II and III. The
bond is created already with only four F atoms. This ap- results for monolayer fluorographene compare well with
parently different result from the previous 3 × 3 supercell previous calculations on this system. [21] As can be ex-
calculations is due to the choice of the size of supercell. pected, the cell size, bond lengths and angles of bilayer
Four adatoms in a 2 × 2 supercell correspond to a higher fluorographene have values between those of monolayer
percentage of F per C atoms than five adatoms in the fluorographene and diamond. Overall the geometrical
3 × 3 supercell. properties are close to the one of bulk diamond due to
We also performed calculations for the case when the the same hybridization of the carbon atoms. [25]
A and B’ sublatices, lying on top of each other, were The calculated C-C bond lengths are larger than the
fluorinated. As already mentioned the preference for B ones in diamond. This difference can be explained from
(A’) over A (B’) sublattice for a single adatom is very a chemical point of view as a result of the depopulation
small and unlikely to conduct the adsorption pattern. of the bonding orbitals between the carbon atoms after
With increased F atom coverage the formation energy substantial charge transfer to the F atom, which is the
per adatom for fluorination of the A and B’ sublattice result of the difference in electronegativity between C and
was found to be an increasing function of the total cover- F atoms.
age. This results in a very unfavourable alternative over Additionally we have observed the shortening of the C-
fluorination of B and A’ sublattice. F bond with increasing amount of fluorination on both
From the calculations on the F adsorption in a 2×2 su- sides of bilayer fluorographene. In a 3 × 3 supercell, the
percell we can conclude that the chair configuration is the C-F bond length varies from 1.50 Å for configuration B
lowest energy configuration, the only configuration that to 1.43 Å for configuration BBBA0 A0 A0 . As can be seen
 5

from Table II, the C-F bond length decreases even more So the band gap of bilayer fluorographene has been found
to 1.38 Å for fully fluorinated bilayer graphene. The to be intermediate between fluorographene and bulk di-
source of this behaviour can be attributed to the ionic amond. In this sense diamond can be considered as the
character of the C-F bond and a gradual transformation limit of multilayer fluorographene. This tendency was
from sp2 to sp3 hybridization of the C atoms. [40] observed before — for theoretically proposed graphite
fluoride materials involving carbon atoms with sp3 hy-
bridization. [46]
TABLE II: Properties of single layer and bilayer fluoro- The absolute value of the formation energy of bilayer
graphene: the unit cell length (a), the distances (d) and angles fluorographene is smaller than the one of the monolayer
(θ) between neighboring atoms. Distances are given in Å and
but still larger than the one of diamond. The main rea-
angles in deg.
son for the observed weakening of the formation energy
fluorographene bilayer diamond is the drop of the ratio of the amount of fluorine atoms
fluorographene per carbon atom in going from monolayer to bilayer fluo-
LDA GGA LDA GGA LDA GGA rographene. Overall, the qualitative image of the sta-
a 2.555 2.596 2.525 2.563 2.499 2.527 bility of the fluorinated materials corresponds to that
of graphane and bilayer graphane in terms of the afore-
dC−C 1.553 1.576 1.541 1.563 1.531 1.547
mentioned formation energy and the presence of covalent
dC−C 0 n/a n/a 1.537 1.554 1.531 1.547
bonds between the graphene layers which stabilize the
dC−F 1.365 1.382 1.361 1.377 n/a n/a structure. Nevertheless there is a large quantitative dif-
θCCC 110.7 110.9 110.0 110.2 109.5 109.5 ference, the fluorinated materials are much more stable
θCCC 0 n/a n/a 108.9 108.7 109.5 109.5 structures than the hydrogenated ones. [20]
θCCF 108.2 108.0 108.9 108.7 n/a n/a
TABLE III: Electronic band gap Egap and formation energy
The electronic properties of monolayer and bilayer fluo- per atom (Ef /atom) of monolayer and bilayer fluorographene
rographene are given in Table III: we calculated the band and diamond using LDA and GGA calculations. All the en-
gap of these materials together with the formation energy ergies are given in eV.
per atom (in contrast to previously used formation en- fluorographene bilayer diamond
ergies per fluorine atom). For comparison, the values of
fluorographene
these quantities are also given for diamond.
LDA GGA LDA GGA LDA GGA
The calculated band gap for monolayer fluorographene
is in good agreement with previously published results Egap 2.960 3.089 3.951 4.040 5.618 5.572
when using GGA calculations. [42] Although the com- Ef /atom -1.057 -0.944 -0.722 -0.593 -0.011 0.132
puted band gap value for fluorographene is close to ex-
perimental measured values [14], this should be seen as The band structure of bilayer fluorographene is dis-
a coincidence. LDA and GGA calculations are known to played in Fig. 4 together with a diagram of the density
largely underestimate the value of the band gap. The cal- of states. The depicted band structure is seen to be qual-
culated band gaps are in fact two times lower than more itatively similar to the one of monolayer fluorographene
accurate results of many-electron GW calculations. [23] [22] with the size of the band gap as the only obvious
This apparent discrepancy is attributed to the presence difference. We also calculated the effective masses of the
of a considerable amount of defects in the experimental charge carriers around the Γ-point in order to find other
samples which induce midgap states (similar to defected differences or similarities between the two materials.
graphane [43]). The obtained effective masses of electrons, and heavy
The band gap of bilayer fluorographene is found to be and light holes for both studied materials, can be found
larger than the one of monolayer fluorographene by ap- in Table IV. It should be noted that these masses were
proximately 1 eV. This is different from the case of hy- calculated within the DFT formalism with usage of the
drogenated graphene where monolayer graphane is found LDA for the exchange-correlation functional which has
to have a slightly larger band gap than bilayer graphane. been shown to give reasonable results. [47]
[31] In fact, within LDA and GGA calculations, graphane The effective mass of charge carriers in crystalline ma-
has a larger band gap than monolayer fluorographene terials usually depends on the direction in reciprocal
[44, 45] but this observation does not apply to bilayer space. Therefore we have chosen two common directions
compounds where bilayer fluorographene surpasses bi- for the hexagonal lattice at the Γ-point, namely: Γ → K
layer graphane in the size of the energy gap. Although and Γ → M . The results for these two directions were
our calculations are not accurate enough to provide the found to be indistinguishable and so we can conclude
real band gap, it is probable that this difference in the that the effective masses at the Γ-point are isotropic.
size of the band gap between monolayer and bilayer fluo- The direction independence for the effective masses that
rographene is qualitatively correct. This follows from the we observe contradicts previous results in which the ef-
fact that LDA and GGA usually produce correct trends fective masses of monolayer fluorographene were found
in the variation of the band gap among similar systems. to be highly anisotropic. [48] Our statement about the
 6

15 ference in its values. We therefore conclude that both

materials have similar electronic properties apart from a
10 difference in the band gap of about 1 eV.

5
TABLE IV: Effective masses of holes and electrons (in units
Energy (eV)

0 of the electron mass) and the 2D Young’s modulus, E, along

the cartesian axes. E is expressed in N m−1 .
-5 fluorographene bilayer
fluorographene
-10
m 0.48 0.50
-15 mhh 1.13 1.10
mlh 0.41 0.37
Γ K M Γ
Ex 195 284
Ey 197 293
FIG. 4: The electronic band structure and density of states
of bilayer fluorographene. The energies are relative to the
Fermi level (EF =0). In addition to the electronic properties we calculated
the (2D) Young’s modulus, E, for monolayer and bi-
layer fluorographene which are also included in Table
isotropic character of the effective masses is supported IV. We followed the same approach as applied before in
by a direct plot of the energy value map around the Γ- Ref. 22. The 2D Young’s modulus of graphene is found
point. In Fig. 5 we show a picture of the highest valence to be 307 N m−1 shifted from the experimental value,
band of monolayer fluorographene. The isotropic char- Eexp = 340 ± 50N m−1 , [49] and other theoretical values.
acter of this band is clearly visible close to the Γ-point. [34] The 2D Young’s modulus of fluorographene is found
Farther away from the Γ-point an anisotropy of the sur- to be 1/3 smaller in comparison to intrinsic graphene,
face map is visible which can be attributed to fourth and whereas the obtained moduli for bilayer fluorographene
higher order effects. However, these higher order effects reach almost the values of graphene, making these mate-
do not induce anisotropy in the effective mass which is rials very strong. The values unveil the isotropic charac-
a second order effect. Similar results are found for the ter of the Young’s modulus for both compounts.
light hole and the electrons.

IV. CONCLUSIONS
Energy levels (eV)
0
As an extension to previous work [22, 31] we studied
-0.05 the potentially interesting case of bilayer fluorographene.
We demonstrated that fluorination of bilayer graphene
-0.1
results in more stable structures than hydrogenation.
-0.15 This can be clearly observed by a comparison of the for-
mation energies of the final structures [20] and is accen-
-0.2
tuated by the fact that the formation energy of partially
-0.25 fluorinated bilayer graphane is always negative in distinct
contrast to partially hydrogenated bilayer graphene. The
-0.3
creation of interlayer chemical bonds occurs at higher
-0.35 amounts of fluorination as compared to hydrogenation.
The calculated band gap of bilayer fluorographene
-0.4
shows a 30% increase over the one of bilayer graphane,
-0.45 and we also observed quantitatively significant differences
Γ
between monolayer and bilayer fluorographene. From the
FIG. 5: Energy levels of the highest valence band of mono-
value of the Young’s modulus, we can conclude that bi-
layer fluorographene in reciprocal space. The displayed region layer fluorographene is substantially stronger than mono-
is a squared portition of the Brioullin zone with a side length layer fluorographene and is almost as strong as graphene.
0.22 of the Γ-M distance. The Γ-point is taken as the origin
and the x-axis directed towards the M -point. Contour lines
are displayed for a better notion of the symmetry. Acknowledgments

When we compare the effective masses of monolayer This work is supported by the ESF - Eurocores pro-
and bilayer fluorographene, we observe only a small dif- gram EuroGRAPHENE (project CONERAN) and the
 7

Flemish Science Foundation (FWO-Vl).

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