Computational Materials Science 144 (2018) 154–160

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Computational Materials Science

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

New predicted ground state and high pressure phases of TcB3 and TcB4:
First-principles
Chun Ying a, Tianhui Liu b, Lin Lin a,c, Erjun Zhao a,c,⇑, Qingyu Hou a
a
College of Sciences, Inner Mongolia University of Technology, Hohhot 010051, China
b
Electronic Information Products Supervision Inspection, Institute of Jilin Province, Changchun 130012, China
c
Inner Mongolia Key Laboratory of Theoretical Chemistry Simulation, Inner Mongolia University of Technology, Hohhot 010051, China

a r t i c l e i n f o a b s t r a c t

Article history: The energetically favorite crystal structures at special composition for Tc-B system are studied systemat-
Received 17 October 2017 ically based on the density functional theory combined with the particle-swarm optimization (PSO)
Received in revised form 12 December 2017 method. The experimentally obtained structure hP6-TcB2 is in excellent agreement with the predicted
Accepted 13 December 2017
one. Moreover, a new ground state phase hP4-TcB3 (P-6m2, No. 187) is predicted for stoichiometric ratio
as 1:3 (TcB3) for the first time. For TcB4, the predicted favorite hP10-TcB4 (P63/mmc, No. 194) is meta-
stable at 0 GPa and becomes the absolutely stable phase at 100 GPa. The hP6-TcB2 exhibits the highest
Keywords:
shear modulus of 269 GPa, and smallest Poisson’s ratio of 0.188, followed by hP10-TcB4 (239 GPa and
First-principles
Technetium borides
0.200), and then hP4-TcB3 (237 GPa and 0.209). Those are comparable to the experimental data (267
Particle-swarm optimization GPa and 0.15) of ReB2. The calculated convex hull and phonon dispersions indicate that all the newly pre-
Convex hull dicted structures for Tc-B system are thermodynamically and dynamically stable. The computed DOS
Mechanical properties illustrates the metallic nature of considered compounds. Moreover, the high hardness about 39.4, 32.4,
and 30.7 GPa are estimated to the most stable hP6-TcB2, hP10-TcB4, and hP4-TcB3, respectively, indicat-
ing these might be the candidates for hard or ultra-incompressible materials.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction
The search for transition-metal borides with properties that
rival those of diamond continues to be an exciting and active area
of research [1,2]. The experimentally obtained transition-metal
borides, such as ReB2 [3], OsB2 [4,5], and novel highest boron com-
pounds WB4 [6,7], CrB4 [8], MnB4 [9–11], and FeB4 [12,13] have
outstanding properties and perform very important roles for both
fundamental and technological fields. For example, the well-
known transition-metal diboride ReB2 have been synthesized suc-
cessfully at ambient pressure and exhibited an average hardness of
48 GPa under an applied load of 0.49 N [3]. The technetium is iso-
valent with rhenium and also can form boron-rich borides, which
can reduce the weight and cost of materials and also increase cova-
lent bonding [14,15]. Several compounds of Tc-B system that exist
only oC16-Tc3B (Cmcm, No. 63), hP20-Tc7B3 (P63/mmc, No. 186)
and hP6-TcB2 (P63/mmc, No. 194) have been identified experimen-
tally [16]. Among them, TcB2 was indexed as of hexagonal symme-
⇑ Corresponding author at: College of Sciences, Inner Mongolia Key Laboratory of
Theoretical Chemistry Simulation, Inner Mongolia University of Technology,
Hohhot 010051, China.
E-mail address: ejzhao@imut.edu.cn (E. Zhao).
try with a = 2.892, c = 7.453 Å, and structurally similar to ReB2 [16].
TcB2 in hP6-ReB2 (P63/mmc, No. 194) type structure was not only
energetically more favorable than other structures [14,15], but also
exhibited high shear modulus of 260 GPa [17] and high hardness of
37 GPa [15]. For TcB, a new phase oC8-TcB (Cmcm, No. 63) was pre-
dicted with a = 3.308, b = 8.818, and c = 3.008 Å by using particle
swarm optimization (PSO) algorithm [17]. However, the mechani-
cally and dynamically stable oC8-TcB is not a ground state struc-
ture for TcB at ambient conditions, because it lies above the
convex hull of Tc-B system [17]. Although Zhang et al. [18] have
investigated the structural and physical properties of TcB and
found that the hP4-TcB (P-3m1, No. 164) is energetically much
superior to oC8-TcB, oC16-TcB predicted in this work is more
stable than the previously proposed oC8-TcB and hP4-TcB. TcB3
in different structures have been investigated by using the density
functional theory within the GGA, and the calculated results indi-
cated the hP4-TcB3 (P63/mmc, No. 194) has high shear modulus
of 240 GPa and high hardness of 33.1 GPa [19]. For TcB4, the pre-
dicted hardness reached about 40 GPa for TcB4 in hP20-WB4
(P63/mmc, No. 194) type structure, implying that it is a potential
superhard material [20]. Further calculations indicated that the
potential ground state for TcB4 should be hP10-MoB4 (P63/mmc,
No. 194) type structure by using the Particle Swarm Optimization

https://doi.org/10.1016/j.commatsci.2017.12.023
0927-0256/Ó 2017 Elsevier B.V. All rights reserved.
 C. Ying et al. / Computational Materials Science 144 (2018) 154–160 155

code [21]. It is well known that crystal structures are the key for
understanding of mechanical properties of materials. Theoretical
studies have often been employed to identify new compounds
prior to their realization [22–24]. Recently developed structure
prediction codes have opened a way to uncover the crystal struc-
ture of new compounds at given conditions [25–27]. Up to date,
there is no more report discussed systematically for Tc-B system
theoretically or experimentally, especially for the boron rich side.
A driving force behind this work is to search the ground state
structures of new compounds with excellent mechanical and elec-
tronic properties in the binary Tc-B system by using the Crystal
structure AnaLYsis by Particle Swarm Optimization (CALYPSO)
code [28] combined with the first-principles based on the density
functional theory (DFT). The most stable phases for TcB, TcB2,
TcB3, and TcB4 are predicted at the ambient conditions. Meanwhile,
the relative stability of these technetium borides with different
compositions is explored also at ambient and high pressure condi-
tions. These findings may lead to a new discovery of technetium
borides, especially on the boron-rich side of phase diagram, pro-
ducing a significantly expanded family of the Tc-B system with
unique and novel properties.
2. Computational details
The variable-cell structure predictions are performed for Tc-B
system (at Tc:B ratios of 1:1, 1:2, 1:3, and 1:4) at 0 GPa with sim-
ulation cells containing 1–4 formula units (f.u.) with population
size being 30 and generations being 50 as implemented in the
CALYPSO code [28]. The further geometry optimization based on
predicted phase in Tc-B system is carried out by using density
functional theory with projector augmented wave (PAW) [29] as
implemented in the VASP code [30]. The exchange-correlation
potentials is treated by the local density approximation (LDA)
[31]. The plane wave cut-off energy is chosen to be 600 V. The Bril-
louin zone sampling is carried out using Monkhorst-Pack k point
meshes [32]. The structures are relaxed with respect to both lattice
parameters and atomic position. The structural relaxations are per-
formed until the difference in the total energy and the residual
forces are less than 1.0
106 eV and 1.0
103 eV/Å, respec-
tively. Formation enthalpy is calculated from 4H = E(TcxBy)  xE(-
solid Tc)  yE(solid B), where the hex-Tc and a-B are adopted for
the corresponding ground states of elements (technetium and
boron). The elastic stiffness constants are calculated by using
stress-strain method, and bulk modulus (B), shear modulus (G)
and Young’s modulus (E) are calculated from Viogt-Reuss-Hill
approximation [33–35].
3. Results and discussion
By using the evolutionary methodology of the crystal structure
prediction, the most stable phases are predicted for technetium
borides with different compositions. Their formation enthalpies,
equilibrium lattice parameters, elastic constants, bulk modulus,
shear modulus, Young’s modulus, Poisson’s ratio, and Debye tem-
perature for Tc-B system are listed in Tables 1 and 2. Other meta-
stable phases are listed in Tables S1 and S2 (see in Supplementary
Materials). The formation enthalpies are calculated to illustrate the
relative stability of predicted structures over the entire range from
0 to 140 GPa. The negative formation enthalpy indicates that all of
these compounds are thermodynamically stable and synthesizable
under the ambient conditions.
3.1. Crystal structure and thermodynamic properties of Tc-B system
For TcB, the energetically most favorable phase oC16-TcB
(Cmcm, No. 63) is uncovered with a = 2.897, b = 18.621, and c = 2.
930 Å, which contains eight TcB f.u. in one unit cell. The Tc atoms
are located at site 4c (0, y1, 1/4) and 8e (1/2, y2, 1/4) (y1 = 0.7989,
0.4293 and y2 = 0.2989, 0.9293), while the B atoms are occupied
at site 4c (0, y1, 1/4) and 8e (1/2, y2, 1/4) (y1 = 0.0269, 0.6603 and
y2 = 0.8397, 0.4731). In Fig. 1(a) for oC16-TcB, the Wyckoff position
of 4c is fully occupied by Tc (or B), while 50% of 8e site is occupied
orderly. At 0 GPa, the calculated formation enthalpy (0.709 eV) for
oC16-TcB is energetically more superior than the previously pro-
posed oC8-TcB [17] and hP4-TcB [18] with our calculated formation
enthalpies of 0.656 eV and 0.684 eV, respectively. This demon-
strates that the predicted oC16-TcB is a new stable phase.
In order to investigate structural stability, we give the forma-
tion enthalpy-pressure relationship. Among all the selected tech-
netium borides under the considered pressure range from 0 to
140 GPa, the pressure induced phase transition occurs only in
TcB group, as seen in Fig. 2. It is clear to observe that oC16-TcB is
the most stable one under the pressures from 0 to 50 GPa. The
oP8-TcB (Pmcn, No. 62) becomes the most stable under pressures
from 50 to 140 GPa.
From a structural point of view for oC16-TcB, seen in Fig. 1(a),
there exist two different types of layers: the first one is constructed
by a wrinkled B1-B1 (1.774 Å) layer connected the two plane Tc lay-
ers, and the second is two parallel wrinkled Tc-B2 layers sand-
wiched between the type one. In the first type, the distance of
Tc-B1 is about 2.216 Å. In the second type, the distance of Tc-B2
bond is about 2.196 Å. However, both Tc and B forms wrinkled lay-
ers apart from 2.302 Å along the c-axis for oP8-TcB (Fig. 1b). The B-
B distance in oP8-TcB is about 1.775 Å, which is slightly larger than
that of B1-B1 (1.774 Å) in oC16-TcB. The shortened Tc-B and B1-B1
distances in the oC16-TcB might be the reason for the lower energy
of oC16-TcB at 0 GPa. Furthermore, the coordination number of B2
(at 8e sites) in oC16-TcB changes from seven to eight in oP8-TcB.
Meanwhile, the coordination number of Tc atoms changes from
eight in oC16-TcB to thirteen in oP8-TcB. This suggests that the
coordination numbers of Tc and B increase with the increase of
pressure, which is typical behavior in a phase transformation

Table 1
Calculated lattice parameters (Å) and elastic constants Cij (GPa) for TcBX in most stable structures.

a b c C11 C22 C33 C44 C55 C66 C12 C13 C14 C15 C23
oC16-TcB 2.897 18.621 2.930 585 532 695 196 257 188 248 209 234
hP6-TcB2 2.864 7.394 624 1021 270 173 132
2.892a 7.453a 627b 1022b 271b 175b 132b
2.877c 7.421c 595c 937c 251c 142c 96c
hP4-TcB3 2.871 4.535 566 895 243 210 146 180
hP10-TcB4 2.890 10.682 583 1013 204 134 126
2.932d 10.787d 532d 912d 194d 115c 117d
a
Ref. [16], EXP.
b
Ref. [14], LDA, DFT.
c
Ref. [15], GGA, DFT.
d
Ref. [21], DFT.
156 C. Ying et al. / Computational Materials Science 144 (2018) 154–160

Table 2
Calculated formation enthalpy per formula unit DH (eV), cell volume per formula unit V0 (Å3), bulk modulus B (GPa), shear modulus G (GPa), Young’s modulus E (GPa), Poisson’s
ratio m, Debye temperature HD (K), Vickers hardness HV (GPa), universal anisotropic factor AU, and shear anisotropic factors A1, A2, and A3 for TcBX with most stable structures.

DH V0 B G E m HD B/G HV AU A1 A2 A3
oC16-TcB 0.709 19.76 353 200 504 0.262 721 1.77 20.8 0.967 0.909 1.354 1.211
hP6-TcB2 1.398 26.27 343 269 640 0.188 951 1.35 39.3 0.256 0.782 1.198
26.69a 345a 299a 728a 0.22a
26.68b 306b 260b 608b 0.17b 37b
hP4-TcB3 1.422 32.39 329 237 574 0.209 977 1.39 30.7 0.174 0.883 1.157
hP10-TcB4 1.317 38.65 319 239 574 0.200 1027 1.33 32.4 0.361 0.606 0.909
0.175c 40.15c 282c
a
Ref. [14], LDA, DFT.
b
Ref. [15], GGA, DFT.
c
Ref. [21], DFT.

Fig. 1. Crystal structures and the nearest coordination numbers of the most stable new structures in Tc-B system: (a) oC16-TcB, (b) oP8-TcB, (c) hP4-TcB3, and (d) hP8-TcB3
structure. The large and small spheres represent technetium and boron atoms, respectively.

under high pressure [36]. For oC16-TcB, the net charges of 0.48 and
0.30 for two type Tc atoms (and of 0.38, 0.40 for two type B
atoms) change to be 0.57 and 0.38 (0.47 and 0.48 for B atoms)
under the pressures from 0 to 100 GPa. For oP8-TcB, the charges of
Tc (and B) atoms also change from 0.45 (and 0.45) to 0.55 (and
0.55) with the pressures from 0 to 100 GPa, indicating an increase
in ionicity. The above discussions are consistent with that one
could expect an increase in the coordination number and the loss
of covalency with an increase in pressure [37].
For TcB2, the predicted hP6-TcB2 (P63/mmc, No. 194), which is
indeed experimental crystal structure, is the most stable phase.
The calculated lattice parameters a = 2.864 Å, and c = 7.394 Å are
in good agreement with the data from experimental and previous
theoretical studies within 0.98% (Table 1). This means that pre-
dicted results of this work is reliable and reasonable.
For the boron rich side, a new energetically favorite phase hP4-
TcB3 (P-6m2, No. 187) is uncovered successfully with a = 2.871, and
c = 4.535 Å for technetium triborides for the first time. The hP4-
TcB3 contains one TcB3 f.u. in one unit cell with the Tc atom at site
1d (1/3, 2/3, 0.5), and the three type B atoms at 1c (1/3, 2/3, 0), 2i
(2/3, 1/3, 0.18), and 2i (2/3, 1/3, 0.82), respectively. The hP4-TcB3 is
characterized by intriguing B-Tc-B sandwiches stacking order
 C. Ying et al. / Computational Materials Science 144 (2018) 154–160
Fig. 2. Calculated formation enthalpy–pressure diagrams for TcB in different
structures.
along the c-axis (Fig. 1c). Each Tc atom, located at the center of the
hexagonal prism, is coordinated by eight B atoms. The boron atoms
between the plane hexagonal Tc layers form a wrinkled graphite-
like layer, and each boron is replaced by a pair of vertical boron
dimers (1.632 Å) for a half of the boron atoms. B1 atom is coordi-
nated by another site of six B2 atom and two Tc atoms, while B2
atom is seven folded with four B (3B1 + 1B2) atoms and three Tc
atoms. More interestingly, there is an energetically competitive
phase hP8-TcB3 (P-3m1, No. 164). The formation enthalpy of hP8-
TcB3 is 1.397 eV, which is close to that (1.422 eV) of hP4-TcB3.
This might be related to similar structural characteristics of the
two phases. For hP8-TcB3, the B atoms form two different types
of layers, as seen in Fig. 1(d). One type is wrinkled B3 layers, and
the other one is formed by two parallel wrinkled B layers con-
nected by B1-B2 (1.680 Å) dimer in the vertical direction. Mean-
while, the B1-B2 (1.680 Å) dimer in hP8-TcB3 is slightly larger
Fig. 3. The calculated total and partial density of states for Tc-B system: (a) oC16-TcB, (b) hP6-TcB2, (c) hP4-TcB3, and (d) hP10-TcB4. The vertical dotted line at zero indicates
the Fermi energy level.
157
than that of B2-B2 (1.632 Å) dimer in hP4-TcB3. The other type of
B layer is also a wrinkled graphitelike layer. The characteristic of
M layer in the hP8-TcB3 (M-M distance is 2.879 Å) structure is sim-
ilar to that of the hP4-TcB3 (M-M distance is 2.872 Å).
For the highest boron content technetium tetraboride, a univer-
sally stable hP10-TcB4 (P63/mmc, No. 194) is predicted with a =
2.890, c = 10.682 Å, which is close agreement with the previously
theoretical studies [21] with a maximum deviation of 1.45%
(Table 1). The hP10-TcB4 contains two f.u. in unit cell with the Tc
atoms at sites 2d (2/3, 1/3, 1/4), and the B atoms at 4f (2/3, 1/3,
Zi), and 4f (1/3, 2/3, Zi) (Zi = 0.884, 0.458, 0.615, and 0.041) sites.
Each Tc atom, located at the center of the hexagonal prism, is coor-
dinated by eight B atoms. One B atom is coordinated by seven B
atoms and one Tc atom, and the other boron atom is seven folded
with four B atoms and three Tc atoms.
3.2. Mechanical stability and electronic properties of Tc-B system
The elastic stability is a necessary condition for a crystal to
exist. According to the mechanical stable criteria for orthorhombic
and hexagonal structures [38], all the energetically most stable
phases are mechanically stable (Table 1). As shown in Table 1, large
C33 value demonstrates high incompressibility along c axis. The
hP6-TcB2 has the largest C33 values of 1021 GPa, which is in excel-
lent agreement with the previously theoretical value of 1022 GPa
[14], and also close to the value of 937 GPa from GGA approxima-
tion [15]. Meanwhile, the hP10-TcB4 exhibits considerable large
C33 value of 1013 GPa, which is close to that (1063 GPa) of ReB2
[39] within 4.7%. The hP6-TcB2 has the highest shear modulus of
269 GPa, and smallest Poisson’s ratio of 0.188, followed by hP10-
TcB4 (239 GPa and 0.200), and then hP4-TcB3 (237 GPa and
0.209), which are comparable to experimental data (267 GPa and
0.15) of ReB2 [39]. Furthermore, Young’s modulus is an important
factor, which is necessary to the technological and engineering
158 C. Ying et al. / Computational Materials Science 144 (2018) 154–160

applications of a material. From the Table 2, it is clearly seen that
the predicted hP6-TcB2, hP10-TcB4, and hP4-TcB3 exhibit large
Young’s moduli of 640, 574, and 574 GPa, respectively, which are
also comparable to that (614 GPa) of ReB2 [39]. For superhard or
ultra-incompressible materials, they generally exhibit the extre-
mely high Debye temperatures. For instance, diamond has the
highest Debye temperature of 2230 K, and it is the hardest material
up to date. It is seen from the Table 2 that hP10-TcB4 has the high-
est Debye temperature of 1027 K, and followed by hP4-TcB3 (977
K) and then hP6-TcB2 (951 K). In addition, the predicted hP6-TcB2,
hP10-TcB4, and hP4-TcB3 are brittle in nature because the calcu-
lated B/G ratios are less than 1.75, which is the critical value to sep-
arating ductility and brittleness [40]. Well known to us, the elastic
moduli are the most important factors for identifying the hardness
of solids and it was suggested that a close correlation exist
between the shear modulus and Vickers hardness [41–43]. The
Vickers hardness estimated for studied compounds (Table 2) is
the average value of the results from Tian’s [41], Chen’s [42], and
Zhao’s [43] models. As expected, the calculated high hardness
arranged as 39.3, 32.4, and 30.7 GPa for the hP6-TcB2, hP10-TcB4,
and hP4-TcB3, respectively. These are comparable to that (38.2
GPa) of B6O [44]. This indicates the hP6-TcB2, hP10-TcB4, and
hP4-TcB3 might be candidates for hard or ultra-incompressible
materials. The anisotropic properties of ultra-incompressible tech-
netium borides are important, so the universal anisotropic index AU
[45] and the shear anisotropy factors A1, A2, and A3 [46] are calcu-
lated. All compounds exhibit anisotropic nature. The oC16-TcB
exhibits less anisotropy than other compounds (Table 2).
The calculated total and partial density of states (DOSs) are
plotted in Fig. 3. The total DOS is dominated by covalent contribu-
tion of Tc-4d and B-2p states. From Fig. 3, it is clearly to see that all
the DOS profiles are very similar: a wide valley separates the bond-
ing and antibonding states, which is called as ‘‘pseudogap”. The
Fermi level is located at ‘‘pseudogap”, indicating that all the bond-

Fig. 4. The convex hulls of Tc-B system at a pressure of (a) 0 GPa, and (b) 100 GPa. The solid line denotes the ground-state convex hull. The hex-Tc and a-B are used as the
reference states.

Fig. 5. The calculated phonon dispersions for Tc-B system: (a) oC16-TcB, (b) hP6-TcB2, (c) hP4-TcB3, and (d) hP10-TcB4 at ambient conditions.
 C. Ying et al. / Computational Materials Science 144 (2018) 154–160
ing states are occupied, while the antibonding states are not. As
seen in Fig. 3a, Fermi levels are located at the peak for oC16-TcB
and hP10-TcB4, meaning that they are structurally unstable at
ambient conditions. For hP6-TcB2 and hP4-TcB3 (Fig. 3b and c),
Fermi levels are almost located at the valley, indicating that they
are structurally stable. For the predicted compounds, the finite
states at Fermi level indicate metallic nature.
3.3. Phase stability and dynamical response of Tc-B system
In order to understand phase stability for applying them in
industry, we calculated the convex hull (Fig. 4), where a point lying
on the tie line is absolutely stable against decomposition into the
neighboring phases [47]. From Fig. 4(a), it is clearly to see that
the energetically most stable phases, competitive or comparable
phases are listed for each special composition of Tc-B system under
ambient conditions. As expected, the experimentally observed
oC16-Tc3B, hP20-Tc7B3 and hP6-TcB2 were indeed located on the
convex hull. For TcB, all the predicted compounds with negative
formation enthalpy lie above the convex hull, indicating that they
are metastable (Fig. 4a). On the boron-rich side, the predicted new
phase hP4-TcB3 is located on the convex hull, indicating that it is
the ground state phase. Among the predicted compounds for
TcB4, hP10-TcB4 is the most stable, which is in agreement with
the previous results [21]. However, hP10-TcB4 located slightly
above (about 16.65 meV/atom) the convex hull, meaning that it
decomposes into neighboring phases under the ambient
conditions.
Since oP8-TcB is more stable than oC16-TcB above 50 GPa, the
convex hull at 100 GPa is also calculated. As expected that hP10-
TcB4 becomes the absolutely stable phase with the increase of
the pressures, and locates on the tie line of the convex hull at
100 GPa (Fig. 4b). However, all the predicted structures for TcB still
lie above the convex hull, indicating that the stability of these
structures is not obviously improved even under high pressures.
The phonon dispersion curves are calculated to identify the
dynamical stability of most stable one at special composition for
the Tc-B system and shown in Fig. 5. A dynamically stable crystal
requires that all the phonon frequencies be positive, otherwise, it
would be dynamically unstable [48]. The calculated results show
that no imaginary phonon frequency is detected in the whole Bril-
louin zone for oC16-TcB, hP6-TcB2, hP4-TcB3, and hP10-TcB4,
implying that they are dynamically stable at both ambient and
high pressure conditions (the high pressure phonon dispersions
are plotted in Fig. S1 of the Supplementary Materials).
4. Conclusions
The structural stability, elastic, thermodynamic and electronic
properties of predicted compounds for technetium borides have
been systematically studied by using the density functional theory
combined with the particle-swarm optimization (PSO) method. A
new ground state phase hP4-TcB3 (P-6m2, No. 187) is predicted
for the first time, and it exhibits large shear modulus of 237 GPa
and high hardness about 30.7 GPa. Based on the calculated convex
hull and phonon dispersion, hP10-TcB4 becomes the absolutely
stable phase at 100 GPa. For TcB group, the most stable oC16-TcB
transforms to oP8-TcB above 50 GPa, and the phase transformation
is related to coordination number and loss of ionicity. For TcB2, the
most stable phase hP6-TcB2 is predicted and in good agreement
with experiment. The crystal structure and mechanical properties
of hP6-TcB2 is in excellent agreement with previous experimental
and theoretical results. Total DOS is dominated by covalent contri-
bution of Tc-4d and B-2p states. These findings may lead to new
discoveries of technetium borides, especially on the boron-rich
159
side of phase diagram, producing a significantly expanded family
of Tc-B system with novel properties. Further experimental work
is thus strongly recommended.
Acknowledgement
This work is supported by the National Natural Science Founda-
tion of China (Grant Nos. 21261013, 2016030132, 2016030320 and
51702168), the Program for Young Talents of Science and Technol-
ogy in Universities of Inner Mongolia Autonomous Region (NJYT-
15-B16), the Program for Innovative Research Team in Universities
of Inner Mongolia Autonomous Region (NMGIRT-A1603), the Nat-
ural Science Foundation of Inner Mongolia Autonomous Region
(Grant Nos. 2015MS0120 and 2011BS0104), the Key Science
Research Project of Inner Mongolia University of Technology
(Grant No. ZD201715).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.commatsci.2017.12.
023.
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