Accepted Manuscript

DFT study of Sb and Pb layers on the Bi(111) surface

I.N. Yakovkin, N.V. Petrova

PII: S0169-4332(18)30838-9
DOI: https://doi.org/10.1016/j.apsusc.2018.03.152
Reference: APSUSC 38900

To appear in: Applied Surface Science

Received Date: 26 November 2017

Revised Date: 13 March 2018
Accepted Date: 20 March 2018

Please cite this article as: I.N. Yakovkin, N.V. Petrova, DFT study of Sb and Pb layers on the Bi(111) surface,
Applied Surface Science (2018), doi: https://doi.org/10.1016/j.apsusc.2018.03.152

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 DFT study of Sb and Pb layers on the Bi(111) surface

I.N. Yakovkin* and N.V. Petrova

Institute of Physics of National Academy of Sciences of Ukraine, Prospect Nauki 46, Kiev, 03028,
Ukraine

The electronic structures of Sb and Pb-covered Bi(111) are studied by means of relativistic DFT
calculations. The Bi bilayer built of Bi(111) atomic planes is found to be semiconducting, with the
indirect band gap of 0.51 eV. It is suggested therefore that the closing of the gap, leading to
semimetallic properties of slabs built from Bi bilayers as well as of a bulk Bi crystal, stems from the
interaction between Bi bilayers and not just from the surface states. One monolayer of adsorbed Sb
or Pb leads to dramatic redistribution of electronic densities in the surface region and related
metallization of the Bi(111) surface, with a high density of states at Fermi level. Adsorbed Sb and
Pb bilayers, in contrast, do not destroy the electronic distribution pertinent to the layered Bi crystal.
However, while under Sb bilayer the Bi(111) film again becomes semimetallic, the surface with
adsorbed Pb bilayer remains metallic. This difference in behavior can be explained by a significant
charge transfer, that is, electronic donation from Pb bilayer to the substrate, which is absent for Sb
bilayer. The adsorption of Sb or Pb on one face of the Bi(111) film destroys the inversion symmetry
of the system and leads to the appearance of Rashba splitting of the bands. For a clean Bi(111) film,
the spin-splitting is absent, which means that the existence of the surface itself cannot cause the
required break of the inversion symmetry.

Keywords: Layered structures; Bi(111) surface; Density functional calculations; Charge transfer

PACS: 68.35.B; 68.35.Rh; 73.20.-r

* Corresponding author. Email: yakov@iop.kiev.ua

 1. Introduction
A low density of states (DOS) at Fermi level of the Bi crystal stems from the coupling of Bi
atoms, having the 6s2p3 configuration of valent electrons, which results in even number of electrons
per unit cell. This explanation of the semimetallic property of Bi, first suggested by Jones [1]), is
consistent with the formation of the A7 rhombohedral structure with two atoms per unit cell,
pertinent also to other group V elements. The A7 structure can be presented as Bi bilayers stacking
along the [111] direction, so that the (111) surface corresponds to a natural split of the crystal by the
cutting plane between the bilayers.
In 1993, Hoffman et al. [2] performed field- and temperature-dependent magnetotransport
measurements on Bi layers and suggested that quantum confinement should convert Bi from a
semimetal to a semiconductor at a critical thickness on the order of 300 Å. The discovered
semimetal-to-semiconductor transition in bismuth thin films, however, later was questioned [3].
Specifically, it was argued that the existing experimental data are not sufficient to establish the
picture that the energy overlap of the conduction and valence bands is replaced by an energy gap in
thin films. Nonetheless, the variations of metallicity depending on the film thickness of Bi films
initiated further studies of the electronic structure of the Bi surfaces and films by photoemission and
first-principles calculations [4-8].
Peculiarities of the electronic structure of Bi films appeared to be in line with predictions of
newly developed theory of insulating state, in particular, of existence of so-called topological
insulators (for review, see, e.g. [9-12]). In contrast to ordinary insulators or semiconductors, the
topological insulators have the band gap in the bulk band structure, while the topologically
protected surface bands crossing EF provide a surface metallicity of the films. Then, Murakami [13]
predicted that two-dimensional bismuth (actually, Bi ribbons, cut from Bi(111) bilayer [13,14]) will
show the quantum spin-Hall effect, and this finding initiated a great interest to Bi films and
numerous studies of electronic structures of Bi surfaces and adsorbed layers, including also
theoretical calculations for free Bi layers [15-25]. To date, it is well established that the spin-orbit
interaction plays an important role in the formation of the band structure of heavy Bi and can
explain the shape of the surface bands in vicinity of EF [4-8, 15-18]. Then, the currently widely
accepted view is that Bi(111) films built of several bilayers are semiconductors in the bulk while
with metallic surface [15-20], so that the metallicity of adsorbed layers, observed in a number of
experiments, stems from the surface bands only.
The inversion symmetry of the bulk Bi, together with the time-reversal symmetry, leads to the
Kramers' degeneracy of the bands, that is, the spin-orbit interaction does not lift the degeneracy by
spin and thus every band contains two states with opposite spins. In contrast, it is widely believed
that a surface a priori has a different symmetry because of the dimensionality issue [26-28], which

2
leads to an absence of the inversion symmetry of the surface and therefore to the Rashba splitting of
the surface bands [6,21-25]. For instance, Koroteev et al. [6], from performed relativistic DFT
calculations, found a pronounced Rashba splitting of the surface bands for Bi(111) films, thus
seemingly supporting the concept of the braking inversion symmetry at the surface.
Properties of surfaces can be substantially modified by deposition of various adsorbates (so-
called functionalization). In this regard, it is very perspective to study the electronic structure of the
Bi(111) modified by group IV and other group V elements (e.g., by forming Sb-Bi alloys [29]).
Macroscopic magnetotransport measurements at Bi films grown epitaxially on Si(111) substrates
performed by Lükermann et al. [30] revealed two characteristic regimes, assigned to
magnetotransport by surface and bulk states, respectively. Then, it was found that deposition of Pb
monolayer led to an increase of conductivity of the Bi film, while several monolayers of Sb did not
noticeably influence surface properties [31]. In absence of first-principles calculations, the changes
of the surface electronic structure were attributed to possible charge transfer between the layers and
Bi(111) surface states.
In the present paper we perform a relativistic DFT study of the electronic structure of free
Bi(111) films, modified by adsorption of Sb and Pb layers, with the focus on the issue of the role of
spin-orbit interaction, metallicity of the surface and interior of the films, and Rashba splitting of the
bands.

2. Methods
The relativistic DFT calculations (with account for spin-orbit interaction) were performed using
the plane-wave expansion of the wave function with Goedecker-Teter-Hutter (GTH) LDA
functional [32] and Hartwigsen-Goedecker-Hutter (HGH) [33] norm-conserving pseudopotentials,
as implemented in the ABINIT [34] package. The periodicity along the surface normal was
maintained using the repeated-slab model, with the vacuum gap about 12 Å. The 6×6×1 k-points
lattice and 16 Ha energy cutoff provided the 10-4 Ha convergence. The standard Broyden structural
optimization of atomic positions was performed until the forces became less than 1×10 -3 Ha/Bohr.
After a optimization of the Bi(111) slab, Sb and Pb layers were deposited on one side of the slab,
and positions of all atoms were optimized again to obtain equilibrated configurations of the
adsorption systems. In the course of the structural optimization, the calculations were performed in
the semirelativistic approximation (i.e. without spin-orbit coupling).

3
 3. Results
3.1. Free Bi(111) layers
The top view on the Bi(111) surface might incline one to conclude that the surface has a
honeycomb structure, like graphene, or, rather, a corrugated honeycomb structure pertinent to heavy
IV-group monolayers – stanene and plumbene [35-37]. To reveal the equilibrated structure, we have
performed the structural optimization of a free Bi monolayer starting from a slightly corrugated
honeycomb structure. Similarly to plumbene, the Bi monolayer reconstructs with the formation of a
strongly buckled structure (Fig. 1), thus forming a bilayer. The lattice period of the equilibrated
Bi(111) bilayer is found to be of 4.19 Å, while the distance between the hexagonal layers, which
characterizes the degree of buckling, is of 1.70 Å. This value of buckling is close to the distance
between the Bi layers forming bilayers in the bulk Bi. The Bi(111) bilayer with optimized lattice
period is found to be a semiconductor with an indirect band gap of 0.51 eV.

a = 4.19 A
Bi(111) bilayer
2

1
E (eV)

-1

-2 M
K

-3
M  K

Fig. 1. The relativistic band structure of a free Bi bilayer with LDA-optimized lattice period a = 3.19 Å.
The grey rectangle indicates the indirect band gap.

The (111) surface quite naturally terminates the hexagonal structure of Bi crystal, and the
model slab built from 3 bilayers can well reproduce the Bi(111) surface and, to a certain degree, the
truncated bulk Bi structure [6-8]. However, the optimized lattice period for the 3-BL slab was found
to be of 4.306 Å, which is significantly less than the period estimated for bulk Bi, a = 4.492 Å,
which is close to the 4.533 Å experimental value. Consequently, the 3-bilayer slab seems incapable
to reproduce all important features of the surface and bulk-projected band structures of Bi(111).
In the most of the experiments, the Bi(111) films were grown on Si(111) surface in which case
the Bi(111) film becomes well-ordered and adopt a proper allotrope structure only beyond about 6
bilayers [8]. Then the Bi(111) films display the characteristic band structure which does not
essentially change for greater thicknesses, as observed in ARPES experiments [7,8].

4
 The band structure and density of states (DOS), calculated for the Bi(111) 6-bilayer film in the
full-relativistic approximation (i.e. with account for the spin-orbit coupling) are shown in Fig. 2.
There is a drastic difference between the electronic structures of a free Bi(111) bilayer and of the 6-
bilayer film. Specifically, while the 6-bilayer film is metallic, the free bilayer is a semiconductor.
Hence, the metallicity of Bi stems from the interaction between bilayers. Consequently, it cannot be
of the van der Waals type, since the interaction is strong enough to cause dramatic transformations
of the band structure from semiconducting for a free Bi(111) bilayer to metallic for the Bi(111) slab.

Bi(111) 6-BL relativistic Bi(111) 6-BL a=4.50

relativistic
1.0 a = 4.50 A 20

0.5 16

DOS (states/eV)
E (eV)

0.0 12

-0.5 8

-1.0 4

0
-1.5
-6 -4 -2 0 2
M  K E (eV)

Fig. 2. The band structure and DOS, calculated for the 6- bilayer Bi(111) film in full-relativistic
approximation. The bands with strong surface weights are marked by thick red lines.

It should be noted that the calculated band structure of the 6-bilayer Bi(111) slab is consistent
with similar results in Ref. [7]. In particular, in agreement with [7], it is found that the surface bands
(marked by thick red solid lines in Fig. 2) loose their surface weights about a halfway from  to M,
which does not agree well with estimates in recent calculations [22]. We underscore that all the
bands are doubly degenerated, so the Rashba-type spin-splitting for pristine Bi(111) slabs is absent,
which, obviously, is a result of Kramers' degeneracy because of retained inversion symmetry.

5
 3.2. Sb layers on Bi(111)
Similarly to Bi, a flat honeycomb structure is unfavorable for the Sb monolayer, so that the
optimization results in substantial buckling, which, again, can be better characterized as the
formation of a hexagonal Sb bilayer. The lattice period of the Sb bilayer is of 4.06 Å and the
buckling is of the surface is 1.6 Å, close to the values for Bi bilayer. The indirect band gap,
estimated within LDA and full relativistic approximation, is of 1.02 eV, with the top of the valence
band at  and the bottom of the conduction band near a middle of the  – M line (Fig. 3 a-b). The
optical (vertical) gap at  is of 1.33 eV.
It is instructive to learn how different can be the electronic structure of Sb monolayer
containing one atom in unit cell. Such monolayer can be built formally as the 1/2 of the bilayer,
with the same period of the hexagonal lattice. The semirelativistic band structure and DOS for the
monolayer Sb are shown in Fig. 3 c-d. The Sb monolayer is definitely metallic, showing a
picturesque peak at EF in DOS, despite the increased (with respect to a bulk Sb) distances between
Sb atoms.
Sb bilayer Sb bilayer
2 6
(a) (b)
1
DOS (states/eV)

4
E (eV)

0
2
-1

-2 0
-3 -2 -1 0 1 2
-3
M  K E (eV)

Sb monolayer Sb monolayer
2 6
(c) (d)
1
DOS (states/eV)

4
E (eV)

2
-1

-2 0

-3 -3 -2 -1 0 1 2
M  K E (eV)

Fig. 3. The band structures (a,c) and DOS (b,d) for free Sb(111) layers.

6
 On the Bi(111) surface, the Sb monolayer (with the coverage  = 1.0) readily forms the
structure with Sb atoms situated in the sites that could be occupied by the next Bi monolayer of a
growing Bi crystal. This layered system is strongly metallic, as is evident from a number of bands
crossing EF and the peak in DOS at EF (Fig. 4 a,b). The deposited Sb bilayer, in contrast, does not
substantially transform the electronic structure of the pristine Bi(111) surface (Fig. 4 c,d), so that
the band structure and DOS remain typical for semimetals, with a low density of states at E F.

a = 4.50 A
Sb monolayer on Bi(111) relativistic Sb monolayer on Bi(111) a=4.50
relativistic
0.5 20
(a) (b)
16

DOS (states/eV)
0.0
E (eV)

12

8
-0.5
4

0
-1.0 -6 -4 -2 0 2
M  K E (eV)
a = 4.50 A
Sb bilayer on Bi(111) relativistic Sb bilayer on Bi(111) a=4.50
relativistic
0.5 20
(c) (d)
16
DOS (states/eV)

0.0
E (eV)

12

8
-0.5
4

0
-1.0 -6 -4 -2 0 2
M  K E (eV)

Fig. 4. Relativistic band structures and DOS for Sb monolayer (a,b) and bilayer (c,d) on the Bi(111) 6-bilayer slab.
The bands with strong weights in Sb layers are marked by thick red lines. Blue dashed lines mark the bands with
strong weights on the bottom surface.

The surface bands, marked by thick red solid lines in Fig. 4, denote the states with substantial
weights in Sb layers. For the bilayer Sb on Bi(111), the bands, located within the bilayer, resemble
the surface bands of pristine Bi(111) (c.f. Fig. 2). It should be noted also that the surface states of
the bottom (non-covered) face of the slab (marked by dash blue lines) remain essentially the same
as estimated for pristine slab. In spite of an apparent similarity, there is a quite important difference
between the relativistic band structures of clean Bi(111) slabs and slabs with one face covered by

7
Sb. Namely, in contrast to clean slabs, the bands of Sb-covered slabs undergo Rashba-type splitting,
which becomes possible due to absence of the inversion symmetry in the latter case.
From comparison of Figs. 4a and 4c it is evident that the band structures for Sb monolayer and
bilayer on Bi(111) are similar, but the numbers of the bands crossing Fermi level are different. For
the adsorbed Sb bilayer, some bands, inherent for Sb monolayer on Bi(111), are partly removed
from vicinity of the Fermi level, which leads to a substantial decrease of DOS at EF, thus restoring
semimetal properties of the Bi(111) surface.
The dramatic changes of the electronic structure of the Bi(111) surface from semimetallic to
strongly metallic, induced by a single Sb hexagonal monolayer, and then the backward
transformation to the semimetal for adsorbed Sb bilayer may indicate a significant redistribution of
electrons in the model system and related relaxation of atomic layers. The charge distribution in
layered systems can be characterized with the help of plane-integrated one-dimensional electronic
densities along the normal to the surface, such as shown in Fig. 5 for a clean 6-bilayer Bi(111) and
the film covered either with Sb monolayer or Sb bilayer.

Bi(111) (6-bilayer) Sb monolayer on Bi(111) Sb bilayer on Bi(111)

160 160 160
(a) (b) (c)
Electronic density

Electronic density

120 120 Electronic density 120

80 80 80

40 40 40

0 0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
z coord. (reduced) z coord. (reduced) z coord. (reduced)

Fig. 5. Plane-integrated one-dimensional electronic densities along the normal to the surface for a
clean 6-bilayer Bi(111) (a) and the film covered either with Sb monolayer (b) or Sb bilayer (c).

From Fig. 5b it can be concluded that a single adsorbed Sb monolayer causes not only
metallization, but also a dramatic redistribution of electronic density in the substrate Bi(111) film.
In fact, only the bottom bilayer remains essentially unperturbed, while not only the interface but
even the next-to-interface layer relaxes dramatically, so that the film hardly could be characterized
as built of well formed bilayers, as does the Bi(111) substrate. In this situation, it is difficult to
estimate the charge transfer between the Sb layer and the substrate, since their electronic densities
are strongly mixed.
With adding another Sb monolayer, thus forming the Sb bilayer, the electronic density of the
Bi(111) substrate restores the 6-peak outlook which corresponds to the essentially restored 6-bilayer
structure of the substrate, and there appears the 7th peak related to the electronic density in Sb

8
bilayer (Fig. 5c). Now the layered structure of the Sb/Bi(111) is well pronounced, which allows one
to estimate the charges in the bilayers by integration over the corresponding ranges of z coordinate.
The integration of the electronic density over the range right to the vertical dashed line, which
separates the Sb peak from the substrate peaks (Fig. 5c) gives the electronic charge of 9.95 e, which
can be compared with 10.00 e for valent electrons of two Sb atoms in the cell. Hence, the charge
transfer from Sb bilayer to Bi(111) substrate is negligible.

3.3. Pb layers on Bi(111)

The presence of Pb monolayer on the Bi(111) surface (with the coverage  = 1.0), similarly to
Sb monolayer, leads to dramatic transformations of the electronic structure and strong relaxation of
the substrate. In particular, the system becomes strongly metallic (Fig. 6 a,b) despite an even
number of the valent electrons per unit cell (recall that Pb has 4 valent electrons while Sb has 5).
a = 4.50 A
Pb monolayer on Bi(111) relativistic Pb monolayer on Bi(111) a=4.50
relativistic
0.5 20
(a) (b)
16
DOS (states/eV)

0.0
E (eV)

12

8
-0.5
4

0
-1.0 -6 -4 -2 0 2
M  K E (eV)
a = 4.50 A
Pb bilayer on Bi(111) relativistic Pb bilayer on Bi(111) a=4.50
relativistic
0.5 20
(c) (d)
16
DOS (states/eV)

0.0
E (eV)

12

8
-0.5
4

0
-1.0 -6 -4 -2 0 2
M  K E (eV)

Fig. 6. The band structures and DOS for Pb monolayer (a,b) and bilayer (c,d) on the Bi(111) 6-bilayer slab.
The bands with strong weights on Sb layers are marked by thick red lines. Blue dashed lines mark the bands
with strong weights on the bottom surface.

9
 However, in contrast to Sb, the formation of Pb bilayer does not restore a semimetallic
electronic structure of Bi and the surface remains strongly metallic, as is seen from a significant
number of bands crossing EF thus giving a substantial DOS at EF (Fig. 6 c,d). The spin-orbit
coupling initiates a strong splitting of the bands, as could be expected for heavy Pb and Bi. Hence,
as well as Sb bilayer, the Pb bilayer on Bi(111) leads to the absence of the inversion symmetry and
therefore to Rashba splitting of the bands, which, is well pronounced for all k except  and M
points.
The plane-integrated electronic densities for the Pb monolayer and bilayer on the 6-bilayer
Bi(111) slab are shown in Fig. 7. At the first glance, the plots of the electronic densities for Pb
adlayers on Bi(111) are similar to those for Sb/Bi(111) (c.f. Fig. 5). Indeed, the Pb monolayer
strongly affects the distribution of electrons at the Bi (111) surface, and so does the Sb monolayer,
then, the Pb bilayer restores the peaked structure of the surface, also similarly to Sb bilayer. There is
a very important difference, however, between the electronic distributions for adsorbed Pb and Sb
bilayers. In particular, it is found that the peak of the linear electronic density for Pb bilayer is
noticeably lower than the peaks related to the Bi(111) bilayers not only because of 4 valent
electrons in Pb atom while 5 in Bi atom, but also due to significant electronic charge transfer from
Pb bilayer to the substrate, essentially absent in the case of Sb. Thus, the integral of electronic
density over the Pb bilayer (right to the dashed line in Fig. 7) gives 6.44 e (to be compared with
8.00 e for valent electrons of two Pb atoms in the cell), which gives the 1.56 e charge transfer from
Pb bilayer to the substrate.

Pb monolayer on Bi(111) Pb bilayer on Bi(111)

160 160
Electronic density

Electronic density

120 120

80 80

40 40

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
z coord. (reduced) z coord. (reduced)

Fig. 7. Plane-integrated one-dimensional electronic densities along the normal to the

surface for Pb monolayer and bilayer on the 6-bilayer Bi(111) film.

Hence, the relatively strong metallicity of the Bi(111) surface effected by Pb bilayer can be
explained by the charge donation, that is, the adsorbed Pb bilayer serves as a donor thus providing a

10
substantial number of electrons in vicinity of E F, which can be predicted to provide a certain
conductivity of the surface.

4. Conclusion
The Bi bilayer built of Bi(111) atomic planes is found to be semiconducting, with the indirect
band gap of 0.51 eV. This finding suggests that the closing of the gap, leading to semimetallic
properties of slabs built from Bi bilayers as well as of a bulk Bi crystal, stems from the interaction
between Bi bilayers and not only from the surface states.
The adsorption of a single Sb or Pb monolayer leads to dramatic redistributions of electronic
densities in the net near-surface region. The second monolayer (and thus forming bilayer) of Sb or
Pb restores the electronic distribution pertinent to the layered Bi crystal. One monolayer of
adsorbed hydrogen, Sb, or Pb leads to metallization of the surface, with a high density of states at
Fermi level, which implies a substantial mobility of the electrons and significant electric conduction.
Two monolayers of Sb and Pb, forming bilayers, behave differently. While the adsorption of Sb
bilayer restores semimetallic properties of the Bi(111) surface, Pb bilayer still keeps the surface
metallic. This difference can be explained by a significant charge transfer, that is, electronic
donation, in the case of Pb, which is absent for the adsorbed Sb bilayer.
The adsorption of Sb or Pb on one face of the Bi(111) film destroys the inversion symmetry of
the system and leads to the appearance of Rashba splitting of the bands. For a clean Bi(111) film,
the Rashba splitting is absent, which means that the existence of the surface itself cannot cause the
break of symmetry required for the spin-splitting of the bands.

11
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13
► Metallic state of Bi films stems from the interaction between Bi bilayers and not just from the
surface states.
► One monolayer of adsorbed Sb or Pb leads to metallization of the Bi(111) surface.
► Adsorbed Sb and Pb bilayers do not destroy the electronic distribution pertinent to the layered
Bi crystal.
► The Bi(111) film covered with Sb bilayer is semimetallic, while the film with adsorbed Pb
bilayer is metallic.
► For a clean Bi(111) film, the spin-splitting is absent, because the existence of the surface itself
cannot cause the required break of inversion symmetry.

14