PHYSICAL REVIEW B 92, 165309 (2015)

Breaking time-reversal symmetry at the topological insulator surface by metal-organic

coordination networks

M. M. Otrokov,1,2,3 E. V. Chulkov,1,4,3 and A. Arnau1,4

1
Donostia International Physics Center (DIPC), 20018 San Sebastián/Donostia, Spain
2
Tomsk State University, 634050 Tomsk, Russia
3
Saint Petersburg State University, 198504 Saint Petersburg, Russia
4
Departamento de Fı́sica de Materiales UPV/EHU, Centro de Fı́sica de Materiales CFM-MPC and Centro Mixto CSIC-UPV/EHU,
20080 San Sebastián/Donostia, Spain
(Received 5 June 2015; revised manuscript received 31 August 2015; published 12 October 2015)

We propose a way to break the time-reversal symmetry at the surface of a three-dimensional topological
insulator that combines features of both surface magnetic doping and magnetic proximity effect. Based on the
possibility of organizing an ordered array of local magnetic moments by inserting them into a two-dimensional
matrix of organic ligands, we study the magnetic coupling and electronic structure of such metal-organic
coordination networks on a topological insulator surface from first principles. In this way, we find that both Co
and Cr centers, linked by the tetracyanoethylenelike organic ligand, are coupled ferromagnetically and, depending
on the distance to the topological insulator substrate, can yield a magnetic proximity effect. This latter leads to
the Dirac point gap opening indicative of the time-reversal symmetry breaking.

DOI: 10.1103/PhysRevB.92.165309 PACS number(s): [Link], [Link], [Link], [Link]

I. INTRODUCTION by bringing TI in contact with (an) a (A)FM compound. For

example, the proximity of the AFM insulator MnSe to Bi2 Se3
Three-dimensional topological insulators (TIs), a novel
induces the gap of ∼8.5 meV at the DP [26]. However, such
class of materials in which an insulating bulk necessarily
an approach may lead to the appearance of undesirable trivial
coexists with a metallic surface, have been attracting a great
states [24,26,29] inside the TI bulk band gap which are harmful
deal of attention for several years [1–4]. As a consequence of
for the topological transport.
the strong spin-orbit coupling, the band gap in TIs gets inverted
As far as the surface doping by the magnetic atoms is
giving rise to a special type of surface states that have linear
concerned, the issue of the DP gap opening proves to be
dispersion characteristic of Dirac fermions. The uniqueness of
controversial so far. On the one hand, ab initio calculations
these Dirac states lies in that the electron’s spin is locked
performed for ordered arrays of Co [34] and Cr [35] adatoms
perpendicular to its momentum, forming a surface state’s
at the Bi2 Se3 surface predict FM ordering, out-of-plane mag-
spin structure which protects the electrons from the elastic
backscattering on defects or due to disorder [5–9]. This prop- netization, and, therefore, the DP splitting. This is in agreement
erty, provided by the time-reversal symmetry, leads to a nearly with angle-resolved photoemission spectroscopy (ARPES)
dissipationless current whereby TIs possess an enormous po- measurements of magnetically doped bismuth chalcogenide
tential for applications in spintronics and quantum computing. surfaces exhibiting a feature near the DP which resembles a
To date, the research trend of TIs has developed into a stan- gap [36,37]. On the other hand, magnetic measurements found
dalone field giving rise to the subfields of Weyl [10] and three- no evidence of the long-range FM order in the systems of Fe
dimensional Dirac [11] semimetals, while similar physics has and Co adatoms at the Bi2 Te3 [38] and Bi2 Se3 [39–41] surfaces
also been found in graphene-based systems [12,13]. (the coverage in the latter case was reaching 0.9 monolayer).
Although it is time-reversal symmetry what topologically Accordingly, several ARPES studies report the absence of the
protects the electrons from backscattering, an interesting DP gap opening in such systems [40–45]. The suppression
consequence arises upon its breaking. The latter can be realized of the long-range FM order may stem from the nonuniform
by adding magnetic functionality to TI, i.e., either by surface distribution of magnetic adsorbates on the TI surface, that tend
[14–16] or bulk [17–22] doping with magnetic atoms or to form clusters when their coverage is around 0.1 monolayer
bringing the TI in contact with (an) a (anti)ferromagnetic or higher [39,40,44,46]. This situation may be partly overcome
[(A)FM] material [23–29]. In the presence of FM order with by annealing, as it triggers the diffusion of the adsorbates
an out-of-plane magnetization the TI energy band structure inside the TI bulk, where they substitute Bi atoms [44,47,48].
becomes fully gapped due to the splitting of the Dirac point It was predicted theoretically, that such an alloying favors the
(DP). In such a case, the quantum anomalous Hall effect is long-range FM order and out-of-plane magnetization that leads
expected to appear [30], which might establish a ground for to the DP gap opening in Bi1.8 Mn0.2 Te3 [49,50]. Nevertheless,
the realization of the fault-tolerant electronic devices. a recent ARPES experiment [44] on Fe at Bi2 Se3 doesn’t
The strategy of bulk doping has already yielded fruits support this result, but the amount of the deposited Fe was
and quantum anomalous Hall effect was observed in twice as small as that of Mn in [49,50].
Crx (Bi1−y Sby )2−x Te3 [31,32] and V0.11 (Bi0.29 Sb0.71 )1.89 Te3 Here we propose a way to avoid the above described
[33] magnetic TI thin films, although at extremely low problems of the adatoms clustering and inhomogeneous
temperatures of 30 and 130 mK, respectively. The drawback of distribution aiming at meeting the conditions for the time-
the low operational temperatures can in principle be overcome reversal symmetry breaking via the surface magnetic doping.

1098-0121/2015/92(16)/165309(9) 165309-1 ©2015 American Physical Society

M. M. OTROKOV, E. V. CHULKOV, AND A. ARNAU PHYSICAL REVIEW B 92, 165309 (2015)

Namely, to achieve the long-range FM order in the system of

adatoms at the TI surface one has to organize their ordered
arrays [14,34,35] and prevent them from diffusion [44,47] or Co
intercalation inside the bulk or the van der Waals gaps [34,51–
54]. Lately, a type of system which may provide these condi- b
tions were successfully grown on metallic substrates—self-
assembled metal-organic coordination networks (MOCNs)
[55–64]. In such experiments, strong electron acceptors Si
like tetracyanoethylene (TCNE, C6 H4 ), tetracyanobenzene
(TCNB, C10 H2 N4 ), and tetracyanoquinodimethane (TCNQ, N C
C12 H4 N4 ) are the most frequently used molecules. Their
networks represent themselves the two-dimensional hosts
where the metallic centers carrying magnetic moment can a
reside. Therefore, one is able to organize an ordered array of
magnetic adatoms thus suppressing their clustering. The latter FIG. 1. (Color online) Unit cell of the unsupported Co-TC(Si)NE
is provided by the strong chemical bonding to the cyano groups monolayer constrained to the parameters of the Sb2 Se2 Te/Bi2 Se3
of the organic ligands which prevents adatoms from diffusion heterostructure. We assume, for clarity, that a (b) is perpendicular
on the surface or below it. Importantly, the local spins of the (parallel) to the Si-Si bond.
metallic centers don’t quench upon contact with the substrate
and the FM exchange interactions mediated by the organic
ligands have been shown to exist in Fe- and Ni-based MOCNs exchange-correlation potential in the Perdew-Burke-Ernzerhof
deposited on the noble metal surfaces [58,60,64]. version [79] was employed. All calculations were performed
Hitherto, the [organic molecules]/TIs interfaces were or- using a model of repeating slabs separated by a vacuum gap
ganized only in order to tune the transport properties of TI of a minimum of 10 Å; the energy cutoff for the plane-wave
surfaces [65–68]. A well-ordered purely organic layer has also expansion was set to 400 eV.
been reported to form on graphene [69]. However, in the recent The MOCNs considered in this study consisted of Co or
work [70] the formation of the well-defined networks of Co Cr metallic centers connected by modified TCNE molecules
and Cu phthalocyanine at the Bi2 Te3 TI surface have been in which two central carbon atoms were replaced by two
reported. Unfortunately, although one of the systems under silicon atoms (Fig. 1). Below, this “synthetic” molecule will
consideration contained Co atoms, its magnetic properties be referred to as TC(Si)NE. Such a replacement of the TCNE
were out of the work [70] scope. central carbon pair by that of silicon was made in order to
Conceptually, the deposition of the MOCNs at TIs surfaces achieve better lattice matching with the underlying TI, since
can be considered as a “hybrid method” to break the time- the one provided by TCNE was rather large. The reasonable
reversal symmetry as it bears features of both surface magnetic matching is crucial for our ability to study the system using
doping and magnetic proximity effect simultaneously. The a first-principles method. Otherwise one has to consider an
former because the magnetic atoms are located at the surface, incommensurate interface, modeling which will require a very
the latter due to the presence of well-defined interface between large in-plane cell. The latter, in combination with a big
magnetic and nonmagnetic systems. The important question thickness of the slab [at least six quintuple layers (QLs)]
to be answered in this context is whether this kind of system and spin-orbit coupling, needed for correct description of
can produce the proximity effect which is strong enough to the TI surface band structure, makes the density functional
break the time-reversal symmetry at TI surface. Here we theory study of MOCN/TI with an incommensurate interface
study the general characteristic features of the MOCN/TI practically impossible. We stress that TC(Si)NE is used as
systems as exemplified by a representative organic ligand (an a representative organic ligand. Apart from TCNE, it bears
artificial TCNE analog) linking together Co or Cr magnetic common features with such other molecules as, e.g., TCNB
centers on the surface of the Bi2 Se3 -based heterostructure and TCNQ. First, all these molecules are strong electron
[71]. We explore possible adsorption geometries, magnetic acceptors which is provided by the presence of four peripheral
properties and electronic structure of such MOCNs/TI. The cyano groups. Second, they are planar and have rectangular
consequences of an incommensurate growth of MOCN/TI are shape. We have artificially designed TC(Si)NE using TCNE
also discussed. We believe that the results obtained reflect as a “parent” molecule since it is the smallest one among those
general characteristic features of the TCNE-, TCNB-, and mentioned. The small size of TC(Si)NE and its reasonable
TCNQ-based MOCNs deposited on top of tetradymite-type matching to Bi2 Se3√ allow us to choose relatively small
TIs [8,72–74]. The main conclusion of this study is that the in-plane cell—(2 × 3)a0 , where a0 is the Bi2 Se3 in-plane
time-reversal symmetry can indeed be broken by the deposition lattice parameter. Such a MOCN/TI system (∼180 atoms) is
of a MOCN on top of the TI surface. computationally affordable for the first-principles method.
In fact, the substrate was chosen to be not Bi2 Se3 , but the
Sb2 Se2 Te/Bi2 Se3 (SST/BS) heterostructure [71], consisting of
II. METHOD AND MODEL DESCRIPTION
a single Sb2 Se2 Te QL block on top of the Bi2 Se3 substrate.
The calculations were carried out using the projector This complex system had been preferred to the simple Bi2 Se3
augmented-wave method [75] as implemented in the VASP due to the fact that deposition of the Co(Cr)-TC(Si)NE on
code [76–78]. The generalized gradient approximation to the top of Bi2 Se3 leads to a significant potential bending as a

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BREAKING TIME-REVERSAL SYMMETRY AT THE TOPOLOGICAL . . . PHYSICAL REVIEW B 92, 165309 (2015)

result of which the DP falls into the continuum of the valence TABLE I. Equilibrium lattice parameters a and b (in Å) of the
band states thus acquiring a resonance character. In contrast, free-standing Co- and Cr-TC(Si)NE, the local spin moments of the
SST/BS doesn’t suffer from this drawback, since its DP is metallic centers (in μB ), and the lattice parameters’ mismatches
√ 
originally located close to the conduction band minimum [71]. (in %) with the SST/BS substrate. For SST/BS, a = a0 3 = 7.12 Å
As in the case of Bi2 Se3 , SST/BS provides a reasonable lattice and b = 2a0 = 8.22 Å, where a0 = 4.11 Å is the Bi2 Se3 parameter.
matching to both the Co- and Cr-TC(Si)NE MOCNs.
All structural optimizations were performed within the a (Å) b (Å) a (%) b (%) m (μB )
scalar-relativistic approach using a conjugate-gradient algo- Co 7.65 8.29 7.44 0.85 2.10
rithm and a force tolerance criterion for convergence of Cr 7.64 8.46 7.30 2.92 3.63
0.05 eV/Å. In the first step, the in-plane lattice parameters
and the atomic coordinates of the free-standing MOCNs were
optimized to determine their equilibrium structure. After that,
the lattice parameters were constrained to those of SST/BS to bend [63,84]. According to the results of a recent theoretical
and the atomic coordinates were relaxed accordingly. The study [64], there is a significant charge transfer (between 1
equilibrium adsorption geometry, i.e., the MOCN’s xy position and 2 e− ) from the Ni and Mn atoms to the TCNQ lowest
with respect to the substrate and the distance to it, were then unoccupied molecular orbital (LUMO). This could enable the
determined. For that purpose, only the SST QL block was bending of the cyano groups thus facilitating a complete or
used to model the substrate. In order to account for the van partial accommodation of the mismatch. Interestingly, both
der Waals interactions we made use of DFT-D2 approach Co and Cr atoms feature significant local magnetic moments
proposed by Grimme [80]. Once the adsorption geometry was (Table I) and, therefore, their respective MOCNs are good
established, the magnetic order was investigated by means candidates for the deposition on the TI substrate aiming at the
of the scalar-relativistic total-energy calculations performed opening of the DP, provided they order ferromagnetically and
for the FM phase and three different AFM phases (horizontal show out-of-plane magnetization.
and vertical stripes, as well as a checkerboard phase). This The compression of the MOCNs to the lattice parameters
was done using (2 × 2) surface supercells with four metal of the substrate is expected to affect their structural properties.
atoms, that allow treating all these spin structures on equal Indeed, we found that when constrained to the SST/BS lattice,
footing. Finally, as soon as the FM order at T = 0 is confirmed both Co- and Cr-TC(Si)NE change their internal atomic
for the particular MOCN system, the surface electronic structure in such a way that Si–Si–C connection somewhat
structure calculations of the MOCN-on-TI heterostructure decreases its angle. As a result, the a > b relation takes place
with the spin-orbit coupling included by the second variation (as opposite to the equilibrium case, see Table I), and the
method [81] were performed. Symmetric slabs composed of energy gain with respect to the constrained a < b case is equal
Co(Cr)−TC(Si)NE/[Sb2 Se2 Te]1QL /[Bi2 Se3 ]6QL in the (2 × to 0.033 and 0.514 eV per unit cell (31 atom) for Co- and
√
3) in-plane geometry were used. Formally, this can be Cr-TC(Si)NE, respectively. Since for Co-TC(Si)NE this gain
considered as a Co(Cr) coverage of 0.25 monolayer. In all is marginal, the next step, i.e., determination of the adsorption
calculations (including those with the duplicated cells) a geometry, was performed for both a > b and a < b cases. This
-centered k-point grid of 4 × 5 × 1 was used to sample the was done for Cr-TC(Si)NE as well.
two-dimensional Brillouin zone. To investigate the adsorption geometry, i.e., the xy position
According to a recent study by Faraggi et al. [64], the elec- of the MOCN with respect to the substrate and the adsorption
tronic and magnetic structure of the 3d transition metal atoms height, we performed static total-energy calculations for 15
based MOCNs is very sensitive to the specific 3d manyfold different distances between the substrate and MOCN. At
occupation that may give rise to delocalized or localized spin that, we explored four different registries of the metallic
densities depending on the existence of hybridizations between center with respect to the substrate—top, bridge, fcc, and hcp
3d states and molecular orbitals. Therefore, in the present work hollows. For both MOCNs, the calculations were performed
the 3d states of Co or Cr were treated within the GGA+U for the previously determined structures with a both larger
approach [82] and Dudarev’s scheme [83]. The U -J value of and smaller than b. Note that the MOCNs were kept planar
4 eV was used for both Co and Cr in all calculations. during these calculations. It appeared that the a > b case
is again more favorable than the a < b one. Indeed, the
min
Ea<b − Ea>bmin
value, i.e., the energy difference of the two more
III. RESULTS AND DISCUSSION
favorable structures of these situations, amounted to 0.85 eV
Table I reports the equilibrium lattice parameters of the [0.83 eV] for Co-TC(Si)NE [Cr-TC(Si)NE]. Figure 2, showing
unsupported Co- and Cr-TC(Si)NE as well as their mismatches the curves for the a > b case, summarizes the results of these
to those of the SST/BS substrate. It is seen that Co-TC(Si)NE’s calculations. One can see that once placed above SST, both Co-
b parameter matches quite well to that of SST/BS since and Cr-TC(Si)NE strongly prefer the top structure in which
b = 0.85%, while the a parameter of the MOCN is 7.44% the metallic center resides right above one of the topmost
greater than the respective substrate parameter. The matching layer Se atoms. The equilibrium adsorption heights for planar
of the Cr-TC(Si)NE is qualitatively the same but slightly worse MOCNs amount to ∼2.85 Å and ∼2.90 Å for Co- and Cr-based
quantitatively. The mismatch obtained can to some extent be systems, respectively. Since the metal centers are located in top
accommodated with the bending of the MOCN units. Indeed, positions, these values correspond to the Co-Se and Cr-Se bond
the conformational freedom of the organic acceptor increases length, i.e., there is chemical bonding between metallic centers
upon the uptake of electrons and the cyano groups are then able and Se atom. As far as the bridge, hcp, and fcc configurations

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M. M. OTROKOV, E. V. CHULKOV, AND A. ARNAU PHYSICAL REVIEW B 92, 165309 (2015)

-158 A FM checkerb. A FM stripe-I

bridge
-159 fcc
hcp
top A FM stripe-II FM
-160
Co
-161 Cr
160 Co
E (eV)

E (meV)
-162 120 Cr
80
-163 40
0
-164 checkerboard stripe-I stripe-II FM

-165 FIG. 3. (Color online) Total energies of the three AFM spin
structures (shown above), the checkerboard, stripe-I, and stripe-II,
with respect to the energy of the FM one. Energies are in meV per
-166
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 two local moments. The lines are guides to the eyes.

z (Å)
FIG. 2. (Color online) Total energy of the Co- (solid circles) and
Cr-TC(Si)NE/SST (open circles) as a function of the adsorption MOCN. The realization of these scenarios depends on how
distance for different MOCNs’ registries with respect to the SST much energy gains the resultant system from the interface
substrate (color lines). The a > b case is shown. formation. Let us illustrate these two cases by the examples
of Co- and Cr-TC(Si)NE. As it can be seen from Table I,
the Co-TC(Si)NE MOCN matches SST/BS somewhat better
are concerned, the MOCNs would appear to be physisorbed at than the Cr-TC(Si)NE one. In the former, the top registry
roughly 3.4 Å above SST. is so favorable (see above), that the energy gain due to the
We then found that in the described top geometry the chemical bonding to the substrate (0.375 eV) turns out to
metallic centers tend to get closer to the substrate. Therefore, be comparable to the energy loss of 0.38 eV due to the
they were allowed to relax downwards until the forces acting constraining of the free-standing Co-TC(Si)NE to the SST/BS
on them were less than 0.05 eV/Å. As a result, the Co- parameters. Therefore, in principle, one cannot exclude the
Se (Cr-Se) bond length was reduced to 2.75 Å (2.79 Å). possibility of the commensurate interface formation in the case
Further relaxations of the TC(Si)NE atoms revealed that it is of particular MOCN and TI. Concerning the Cr-TC(Si)NE
extremely difficult to diminish the forces somewhat noticeably. case, the worse matching leads to the higher cost of the
Therefore, the organic ligands were kept fixed in both cases. commensurability (0.607 eV). Therefore, the energy gain of
However, such an incomplete relaxation is not expected to the chemisorbed top case of 0.317 eV is far from being enough
affect the results and conclusions of the present work by two to make the commensurate growth favorable and formation of
reasons. First, the adsorption registry (top) is not expected the incommensurate interface is expected in such cases.
to change since it is by far more favorable than the other Figure 3 shows the calculated energies of the different
adsorption geometries. Indeed, in the Co-MOCN (Cr-MOCN) collinear magnetic structures for the above described bent
case the chemisorbed top registry is 0.375 eV (0.317 eV) more geometries of Co- and Cr-TC(Si)NE/SST. The energy of the
favorable than the bridge registry, which has the lowest energy FM state is taken as zero in both cases. It is seen that both
among the three physisorbed cases—bridge, fcc, and hcp ones. systems feature a FM ground state and that ferromagnetism
Second, the organic ligand atoms don’t play a significant role in proves to be energetically much more stable in the Cr-based
the magnetic proximity effect. Therefore, their displacements MOCN. Thus, in the MOCN/TI systems, there exists an
will not affect the magnetic proximity effect qualitatively. As essential possibility to realize the magnetically ordered state:
far as the quantitative side is concerned, we recall that the magnetic moments of the Co and Cr centers aren’t quenched
purpose of our study is not to propose certain system, but rather (2.08 and 3.35μB , respectively) and there is an exchange
explore and extract the general features of the FM MOCNs on interaction between them.
top of TIs. Therefore we further study the MOCNs/TI in such Next, we proceed with a detailed analysis of the calculated
a “metastable” geometry. Additionally, we treat the adsorption projected densities of states (PDOS) onto different 3d metal
distance as a parameter, varying it in the physically meaningful atoms orbitals, p orbitals of the cyano groups (CN− ), and
range. pz orbital of the Se atom located directly below the metallic
It is appropriate here to discuss in more detail the mismatch center. This analysis permits us to gain information about
between the lattice constants of the free-standing MOCNs and (i) the metallic/insulating character of the system and the
the TI substrate. As is shown below, there are two possible localization of magnetic moments, (ii) the relevant in-plane
scenarios when a MOCN and TI are brought in contact, and out-of-plane hybridizations between metal atoms and
namely, an incommensurate and commensurate growth of a organic ligands, and (iii) the out-of-plane hybridizations

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1.0 (a) (b) 1.0

Co dxy Cr dxy
Co dx2 −y2 Cr dx2 −y2
0.5 0.5

0.0 0.0

-0.5 -0.5
CN− px CN− px
PDOS (states/eV atom spin)

CN− py CN− py
-1.0 -1.0
1.0 (c) (d) 1.0
Co dyz Cr dyz
0.5 Co dxz Cr dxz 0.5

0.0 0.0

-0.5 -0.5
CN− pz CN− pz
-1.0 -1.0
1.0 (e) (f) 1.0
Co d3z 2 −r2 Cr d3z 2 −r2
0.5 0.5

0.0 0.0

-0.5 -0.5

Se pz Se pz
-1.0 -1.0
-8 -6 -4 -2 0 2 4 -8 -6 -4 -2 0 2 4
E − EF (eV) E − EF (eV)

FIG. 4. (Color online) PDOS onto different atomic orbitals of Co- (a),(c),(e) and Cr-TC(Si)NE/SST (b),(d),(f) in FM state. Majority PDOS
are plotted as positive values, while minority as negative ones. The vertical dotted line indicates the Fermi energy.

between metal atoms and the underlaying substrate. The Fermi energy is located much closer to 3d states which have
corresponding PDOS are presented in Fig. 4. mainly dxz and dyz (dx 2 −y 2 ) character in Co-MOCN (Cr-
First, we focus on the global information extracted from MOCN), corresponding to out-of-plane angular momentum
a simple examination of peak positions and its location states with |m| = 1 (m = +2) [85,86]. Thus there is a certain
with respect to the Fermi level. We see that both Co- and tendency to an out-of-plane magnetization in both Co- and
Cr-TC(Si)NE/SST are metallic since the Fermi level, EF , Cr-TC(Si)NE which is crucial for the DP gap opening at TI
crosses the dxz and dyz projections of both spin subsystems surface [30] (we recall that the in-plane magnetization leads
in the former case [Fig. 4(c)] and the spin-down dx 2 −y 2 as well to the shift of the DP out of the  point; see, e.g., Ref. [50]).
as spin-up dxz and dyz states in the latter case [Figs. 4(b) and Second, we explore the different hybridizations between
4(d)]. Concerning the 3d metal atom orbital occupations that the atomic orbitals based on the symmetry considerations of
determine the corresponding magnetic moments, we observe the orbitals involved. We find the following. (i) The in-plane
that the majority spin states of Co are almost fully occupied, orbitals dxy and dx 2 −y 2 in both Co and Cr cases hybridize
while the minority d3z2 −r 2 [Fig. 4(e)] and, to a large extent, with the px and py states of the CN− , both below and above
dxy [Fig. 4(a)] are empty giving rise to a S = 1 local moment the Fermi level [Figs. 4(a) and 4(b)]. Concentrating on the
(2.08μB as calculated within Wigner-Seitz sphere). In the Cr occupied states only, for Co-TC(Si)NE the orbital overlaps are
case there are, roughly, four fully occupied majority orbitals manifested in the appearance of the hybrid dx 2 −y 2 − py peaks
[dx 2 −y 2 , dxz , dyz , and d3z2 −r 2 ; see Figs. 4(b), 4(d), and 4(f)] at −2.9 and −1.1 eV of the spin-up and spin-down channels,
and partially occupied minority dx 2 −y 2 orbital [Fig. 4(b)] respectively [Fig. 4(a)], while for Cr-TC(Si)NE they appear at
which leads to a localized spin moment somewhat larger than −2.83 eV and EF [Fig. 4(b)]. The hybridization with the dxy
S = 3/2 [3.35 μB ; the contribution of the occupied spin-up states appears mostly below −6 eV, except for Co-TC(Si)NE,
dxy state cancels by that of its spin-down counterpart; see which features a hybrid spin-up dxy − px peak at −1.1 eV. (ii)
Fig. 4(b)]. Furthermore, in the Co- and the Cr-based systems, The CN− − pz states hybridize with dxz and dyz [Figs. 4(c)
there are unpaired electrons in the dxy and dx 2 −y 2 orbitals and 4(d)]. Near the Fermi level these hybrid states form a
[Figs. 4(a) and 4(b)], respectively, what leaves out-of-plane so-called LUMO. As a result of these Co- and Cr-TC(Si)NE
(|m| = 2) orbital angular moment components. Besides, the hybridizations, the LUMO becomes partially occupied and

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M. M. OTROKOV, E. V. CHULKOV, AND A. ARNAU PHYSICAL REVIEW B 92, 165309 (2015)

0.4 0.4
(a) (b)
0.3 0.3
M

0.2 0.2
K
E − EF (eV)
Γ M
0.1 0.1
Y
0.0 0.0 K
Γ X

-0.1 -0.1

-0.2 -0.2

-0.3 -0.3

-0.4 -0.4
K Γ M X Γ Y
0.4 -0.26 0.4 -0.27
Co-MOCN Cr-MOCN
0.3 2 meV
SST 0.3 -0.28 SST
-0.27
-0.29
4.5 meV
0.2 0.2
-0.3
-0.28
0.1 Γ
0.1 Γ
E − EF (eV)

0.0 0.0
-0.1 (c) -0.1 (d)
-0.2 -0.2
-0.3 -0.3
-0.4 -0.4
-0.5 -0.5
-0.6 -0.6
-0.7 -0.7
X Γ Y X Γ Y
√
FIG. 5. (Color online) (a),(b) Surface band structure of SST/BS calculated in (1 × 1) and (2 × 3) in-plane supercells. (c), (d) Surface
band structure of the Co- and Cr-TC(Si)NE networks placed on top of SST/BS. Purple-shaded areas correspond to the bulk band structure
projected onto the surface Brillouin zone. The size of red and blue circles in panels (c),(d) reflects the weight of the state in the (Co,Cr)-MOCN
and in the SST QL, respectively. The insets show the magnified views of the split DPs.

acquires spin polarization with the same (opposite) sign as that closer to the substrate, such that the Co-Se bond length is
of the metallic Co (Cr) center, a prerequisite for FM coupling, reduced to 2.5 Å (instead of 2.75 Å) increases the mentioned
as was recently shown in Ref. [64]. induced moments roughly twice. Contrary to a Co center, the
Finally, we consider the interaction of the metallic centers Cr one induces a notably larger moment of −0.03μB in the Se
with the SST substrate. It is seen in Figs. 4(e) and 4(f) p states, and upon pushing Cr-TC(Si)NE closer to the substrate
that the d3z2 −r 2 states hybridize with the pz states of the it increases up to almost −0.05μB (the Cr-Se bond length being
underlying Se atom. Although it is difficult to spot the common equal to 2.5 Å). We note that the Se p-states magnetic moment
p − d features, it is clear that the Se-pz states are strongly induced by Cr-TC(Si)NE is comparable to that induced at Bi
modified, as compared to those of the clean SST surface, atom, lying in the second atomic layer from the Bi2 Se3 /MnSe
where the spin-up and spin-down states are of identical shape. interface, by Mn atom lying at the interface [26]. Thus, at
As for the Se-px and py states, they do not appear to be least in the Cr-TC(Si)NE/SST case, there is clear magnetic
affected by the proximity of the MOCN (not shown). However, proximity effect, which is crucial for the gap opening at the
despite such a strong modification of the pz states, in the Co three-dimensional TI surface [26].
case there is almost no induced magnetization in the Se p Let us now discuss the electronic band structure of the
states: the calculated moment amounts to  − 0.01μB (within systems when the Co- and Cr-TC(Si)NE networks are placed
the Wigner-Seitz sphere). Bringing Co-TC(Si)NE somewhat on the complete SST/BS substrate. The calculations are

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performed with spin-orbit coupling included. The SST/BS BS bulk band gap. This means that wide band gap TIs [88] with
surface band structure is shown in Fig. 5(a). Its characteristic the DP lying in the midgap or close to the conduction band
feature is the DP lying close to the conduction band minimum minimum are suitable candidates for deposition of MOCNs
[71] in contrast to the BS surface band structure showing the aiming at a controlled modification of its electronic properties
DP in the vicinity of the valence band maximum [74]. Fig- close to the Fermi level. The former could be obtained by a
ure 5(b) shows essentially
√ the same SST/BS band structure but variation of bulk atomic composition [89,90], while the latter
calculated in (2 × 3) surface supercell, which is manifested by constructing heterostructures [71,91,92] like the one used
in the folded surface bands near the X and Y points below in the present work.
the Fermi level. Then the band structures of the SST/BS with Finally, it should be noted that the MOCN deposition results
the MOCNs on top were calculated. It turned out that in the in a significant electron doping of the TI band structure (Fig. 5).
equilibrium geometry with metallic centers residing at 2.75– Although the Fermi level position can be tuned into the bulk
2.79 Å above the substrate neither Co- nor Cr-based network band gap by electrical gating, the use of p-doped TIs (e.g.,
produces the splitting of the DP larger than 1 meV (not shown). Sb2 Te3 [72]) as substrates for MOCNs deposition can help in
To see whether the violation of time-reversal symmetry using decreasing the magnitude of the gate bias voltage required to
the MOCN is ultimately feasible, the metal-organic overlayers access the Dirac state and the induced DP gap in particular.
were brought closer to the SST/BS substrate since it enhances
the magnetic proximity effect, as it has already been discussed
IV. CONCLUSIONS
above. Figures 5(c) and 5(d) show the surface band structure
of the Co- and Cr-TC(Si)NE networks both located at 2.5 Å The surface electronic structure of metal-organic coordi-
above SST/BS. One can clearly see the splitting of the DP in nation networks on top of a topological insulator surface has
both cases, with the gap sizes of 2 and 4.5 meV in Co- and been studied using first-principles calculations. An analog of
Cr-based systems, respectively. However, in neither case there the tetracyanoethylene molecule with a central carbon pair
is a global gap in the surface band structure, because the DP substituted by a silicon one has been chosen as an organic
gaps are spanned by the trivial bands which appear inside the ligand, representative of the flat, strong acceptor molecules
BS fundamental band gap at larger k.  These bands stem from characterized by the presence of the peripherally located cyano
the MOCN but also have a contribution from the substrate groups. Being used as a part of the metal-organic network with
atoms due to the hybridization. It should also be noted that in 3d atoms acting as magnetic centers, it provides reasonable lat-
the Cr case the DP splitting is of the same order of magnitude tice matching to the topological insulators of the Bi2 Se3 family,
as that brought about by the BS proximity to the compound thus enabling an efficient ab initio study of such a complex
AFM semiconductor MnSe [26]. This is despite the fact that system. Thus we have been able to elicit general features,
the effective concentration of the Cr atoms at the MOCN/SST characteristic of a MOCN-on-TI, when a metal-organic coor-
interface is four times smaller than that of Mn atoms at the dination network is based on a flat, strong acceptor molecule
Bi2 Se3 /MnSe one. (TCNE, TCNB, TCNQ, etc.), while a topological insulator
The spectra shown in Fig. 5 are obtained under the belongs to the tetradymite family (Sb2−x Bix Te3−y Sey ). The
assumption of commensurate growth of the MOCNs on top of most important of these features are as follows. The deposition
SST/BS. Let us now briefly discuss possible consequences of of a metal-organic coordination network on top of a topological
the incommensurate growth illustrated by an example of our insulator surface doesn’t lead to a quenching of the 3d atom
model Cr-TC(Si)NE/SST/BS system. In this case, different local magnetic moments (at least in the Co and Cr cases) and
Cr centers will have different atomic environment, i.e., the there is a significant exchange interaction between them. Thus
MOCN will not always be in the top registry, but there rather there exists a possibility for the realization of the magnetically
will be a continuous change of the registries. However, not ordered state in such systems. In the regions where the mag-
all of them produce the magnetic proximity effect. Thus one netic centers are chemically bound to the topological insulator
can expect that in the case of the incommensurate growth surface, the magnetic proximity effect can be achieved. Finally,
the Dirac state will only be gapped in those regions, where and most importantly, it has been shown that the deposition
this effect exists. In the case of Cr-TC(Si)NE/SST/BS it takes of the ferromagnetic metal-organic coordination networks can
place when the MOCN is in the top registry or nearly. As for indeed provide all the conditions for time-reversal symmetry
the regions where the Cr atoms fall into or close to the bridge, breaking at the topological insulator surface.
fcc, and hcp sites, there was no magnetic proximity effect
found and therefore no gap opening is expected. Due to the
ACKNOWLEDGMENTS
rectangular symmetry of the FM MOCNs under consideration
they could create quasi-one-dimensional regions (stripes) of We acknowledge the support by the Basque Departamento
the gapped Dirac state at the TI surface. This is somewhat de Educacion, UPV/EHU (Grant No. IT-756-13), Spanish
similar to the spatially dependent DP gap opening in the case Ministerio de Economia y Competitividad (MINECO Grant
of Crx (Bi0.1 Sb0.9 )2−x Te3 stemming from the inhomogeneous No. FIS2013-48286-C2-2-P), and Tomsk State University
distribution of Cr dopants [87]. Academic D.I. Mendeleev Fund Program in 2015 (Research
In Figs. 5(c) and 5(d) it can also be seen that the Dirac states Grant No. 8.1.05.2015). Partial support by the Saint Peters-
are subject to a significant downward shift due to the potential burg State University Project No. 11.50.202.2015 is also
bending produced by the deposition of the MOCN. Indeed, acknowledged. The calculations were performed in Donostia
the shift of the split DP due to the deposition of Co-(Cr-)based International Physics Center as well as on the SKIF-Cyberia
MOCN amounts to ∼203 (220) meV, roughly the 2/3 of the supercomputer of Tomsk State University.

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