On the importance of hexagonal phases in

TM (TM = Ti, Zr, and Hf) mono-nitrides

Cite as: J. Appl. Phys. 128, 105106 (2020); https://doi.org/10.1063/5.0018710
Submitted: 16 June 2020 . Accepted: 22 August 2020 . Published Online: 14 September 2020

Mateo Arango-Ramirez, Alejandra Vargas-Calderon, and Andres M. Garay-Tapia

J. Appl. Phys. 128, 105106 (2020); https://doi.org/10.1063/5.0018710 128, 105106

© 2020 Author(s).
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On the importance of hexagonal phases in TM

(TM = Ti, Zr, and Hf ) mono-nitrides
Cite as: J. Appl. Phys. 128, 105106 (2020); doi: 10.1063/5.0018710
Submitted: 16 June 2020 · Accepted: 22 August 2020 · View Online Export Citation CrossMark
Published Online: 14 September 2020

Mateo Arango-Ramirez, Alejandra Vargas-Calderon, and Andres M. Garay-Tapiaa)

AFFILIATIONS
Centro de Investigación en Materiales Avanzados, Unidad Monterrey, Apodaca, Nuevo León CP 66628, Mexico

a)
Author to whom correspondence should be addressed: andres.garay@cimav.edu.mx

ABSTRACT
Phase transitions are an important topic in the understanding of the properties of IVb group mono-nitrides (IVbTMNs) and their applica-
tions. Until now, only structural phase transitions concerning cubic phases that are far away from the ground state have been reported.
However, previous reports have suggested a possible transformation to the Bk(BN-type) hexagonal phase as well. With this in mind, this
work aims to study the stability of phase transitions involving hexagonal phases. Here, we perform a complete theoretical study based on
the density functional theory approach of the crystal and vibrational and electronic structures of several phases for IVbTMN (TM = Ti, Zr,
and Hf ) compounds. Among these, the hexagonal phases are known to be stable in the V−VITMN homologous systems. Our study reveals
the existence of a new pressure-induced phase transformation at the compression regime from B1 (Nacl-type) to Bi (AsTi-type) for ZrN
and from B1 to Bk at the expansion regime for all IVbTMN. In addition, we have found that hexagonal Bi, Bk, and trigonal LiSnS2-type
phases are close to the ground state and are dynamically stable. However, the metal weight plays a crucial role in the stability of hexagonal
phases. The stability of the Bi and Bk hexagonal phases is important since they might represent intermediate states in the cubic B1 to B4
phase transition of the alloyed IVbTMN.

Published under license by AIP Publishing. https://doi.org/10.1063/5.0018710

I. INTRODUCTION
Transition metal mononitrides of the IVb group (IVbTMN),
also known as refractory compounds and its aluminum alloyed
counterparts (IVbTMN-Al), are well known to show unique charac-
teristics. They are ceramic, chemically stable, resistant to chemical
attack, hard, and possess high melting points and conductivity. All
these features are related to the degree of covalency of the metal–
nonmetal bonding interactions.1,2 Over the years, they have been
routinely employed as protective coatings with relative success. To
guarantee they can extend the life-span of industrial materials sub-
jected to harsh conditions,2,3 the fragility and stability of refractory
nitrides need to be optimized and further investigated. For these
compounds, the ground state crystal structure depends considerably
on the TM. In particular, for IVbTMN (TM = Ti, Zr, and Hf ), the
ground state corresponds to a cubic B1 phase (space group fm3m,
NaCl-type), with the metallic atoms forming a cubic fcc sub-lattice
and N atoms placed at interstitial positions of an fcc sub-lattice.2,4
However, in general, refractory nitrides stabilize in structures
resembling those of the pure TM (usually cubic) if the ionic charac-
ter of the compound is high. As the position of the alloying TM in
the periodic table shifts toward nitrogen, the ionic character of the
compound declines, and hexagonal structures are favored.5
Recently, a few density functional theory (DFT)-based theoret-
ical studies have shown that when subjected to pressure, refractory
compounds suffer a structural transformation from the ground
state cubic B1(NaCl-type) phase to cubic and hexagonal
phases.3,6–8 Different hybrid schemes9 allow a reduction of the
coordination number around the TM atoms and facilitate the stabi-
lization of hexagonal phases. For instance, the B8,10,11 Bh,10,12 Bi,9
Bk,9 and B49 hexagonal phases have been observed in the
IIIb−Vb−VIb
TMN systems. These phases have showed outstanding
thermoelectric13 and piezoelectric properties,14 and have even been
considered as potential alternative energy sources.12 Some of them
like the ScN-Bk phase has been reported as metastable.14 However,
the possible stability of these phases for IVbTMN has not been
investigated to this date.
Earlier DFT studies of the stability of IVbTMN under pres-
sure were focused only on the energetic stability of the cubic
phases. Xin Tan et al.7 found phase transformation induced by
high compression from the B1 to the B2 cubic phase. Salguero

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et al.8 recorded the same transition but only for ZrN. Abavare
et al.3 went ahead and studied the stability of the cubic B3
(ZB-type) phase for which a direct transition (B2 to B3) under
compression was found. Additionally, under expansion two
indirect transitions were reported, namely, the (B1–B3) and the
(B2–B3). Interestingly, their phonon spectra calculations predicted
dynamic stability for the B3 phase but not for the B2 phase.
Additionally, Ivashchenko et al.6 also predicted the B2 phase to be
dynamically unstable for the TM(N, C) (TM = Ti and Zr),
although for TiN and ZrN, stabilization was achieved only by
compression above 55 GPa. In contrast, the research of hexagonal
phases for IVbTMN is still ongoing. To our knowledge, there are
only two partial studies on the subject. For ZrN, Salguero et al.8
considered the hexagonal B4 (wurtzite-type) along the three cubic
B1, B2, and B3 phases. Likewise, for ZrN and HfN, Meenaatci
et al.15 included the hexagonal Bh (WC-type) and B8 (NiAs-type)
phases, but only compression data were reported. Thence, no
transition from cubic to hexagonal was observed since these
phases appear only upon expansion. Both studies focused their
attention on the cubic phases and did not research the dynamic
stability of hexagonal phases, which is fundamental to understand
the transformation path from the dynamically stable cubic B1
(NaCl-type) to any hexagonal phase.
In IVbTMN-Al, the exposure to harsh conditions has shown to
trigger a structural transformation from the cubic B1 (Nacl-type) to
less mechanically enhanced hexagonal B4(Wurtzite-type).9,16,17 For
instance, in NbAlN, Holec et al.9 have found two hexagonal meta-
stable phases (B8 and Bi) in the B1–B4 transformation path at high
Nb concentrations. These findings show that the appearance of
hexagonal phases implies a loss of mechanical properties that may
diminish the performance of TMN and TMN-Al when used as
protective coatings.
Therefore, to gain a deeper understanding of pressure ener-
getic promotion of hexagonal over cubic phase stability, a compre-
hensive study including a larger sampling of hexagonal phases is
advised. To that end, we have carried out an extensive computa-
tional analysis concerning the relative stability of several cubic
and hexagonal phases along the pressure induced cubic phase
transformation (B1 to B2) for IVbTMN. Previously observed hex-
agonal phases in IIIb−Vb−VIbTMNs and their Al alloy counterparts
(TMN-Al) have been considered as well. We have focused our
attention on the dynamic stability of hexagonal phases located
energetically close to the ground state cubic B1 phase. We aim to
discern which of them are metastable and to suggest the easiest
transformation path triggered from the cubic B1 (NaCl-type)
phase to the hexagonal B4 (wurtzite-type). The relation between
the dynamic stability of hexagonal phases, their coordination
type, and electronic and structural properties is also addressed. To
clarify the nature of the metal–nonmetal bonding interactions of
such metastable phases, a detailed DOS and electronic band struc-
ture analysis is presented. From this information, we provide the-
oretical evidence that shows the importance of hexagonal phases
involved in transformation. New vibrational data are supplied that
might be useful to compare and guide recent and future experi-
mental investigations of cubic B1(NaCl-type) to hexagonal B4
(wurzite-type) phase transformation for IVbTMN (TM = Ti, Zr,
and Hf ).
J. Appl. Phys. 128, 105106 (2020); doi: 10.1063/5.0018710
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II. METHOD AND CODE
Ab initio calculations under the framework of density func-
tional theory (DFT) using the Vienna ab initio simulation package
(VASP)18,19 were performed. Wave functions were described within
the projector augmented wave method (PAW)20 and exchange–cor-
relation interactions were taken into account through generalized
gradient approximation (GGA) as parameterized in the Perdew–
Burke–Ernzerhoff (PBE) functional.21 Expansion of plane waves
with a 600 eV energy cut-off and a k-point sampling of at least
5000-point/at density Monkhorst-grid22 of the Brillouin zone guar-
anteed convergence criteria of 1 × 10−3 eV in ionic forces.
Pseudopotentials with standard valence electronic configurations of
Ti-3d24s2, Zr-4p64d25s2, Hf-5d26s2, and N-2s22p3 have been used
for calculations.2,3,8,15
Full relaxation of all structural phases was performed. For those
cases for which the original symmetry was not retained after relaxa-
tion, a shape-constrained method was selected (only LiSnS2-type and
Wurzite-type phases). The bulk modulus was derived from a third
order Birch–Murnaghan EOS,23 accounting for a 10% volume change
of the unit cell. Formation enthalpies ΔHf were calculated according
to Eq. (1),24 where Etot is the total energy, x and y are the molar frac-
tions of each component, and E(X) and E(N) stand for the bulk
energy of the metal and molecular nitrogen, respectively,
 
xE(X) þ yE(N)
ΔHf ¼ Etot (Xx Ny )  : (1)
xþy
First-principles phonon calculations were carried out to
describe the dynamic behavior of the crystal lattice. The finite dis-
placement method with a supercell approach was employed as
implemented in Phonopy software.25 For each phase, supercell size
was chosen to have at least 10Å length on each crystallographic
direction. Also, the Bader code26 was employed to analyze the elec-
tronic charge transfer.
III. RESULTS
In this section, the stability phase relation of the cubic and
hexagonal phases of IVbTMN is presented. For each studied phase,
the corresponding crystal structure is shown in Fig. 1, while labels,
space groups, and crystal structure types are listed in Table I. From
now on, Strukturbericht notation will be employed as a reference.
In total, nine phases were considered: three cubic structures (B1,
B2, and B3), five hexagonal (B4, Bh, Bi, B8, and Bk), and one trigo-
nal LiSnS2. The hexagonal Bi, B8, Bk, and the trigonal LiSnS2-type
have never been considered in a stability study of IVbTMN.
A. Structural stability and formation enthalpy
The ground-state lattice constants, bulk modulus (B0), and forma-
tion enthalpies obtained from ab initio calculations are summarized in
Table II, and available experimental and theoretical data are reported
as well. For all IVbTMN, the calculated lattice constants have less than
0.3% difference from experimental values, while for bulk modulus, the
difference ranges from 1% to 3%, and formation enthalpies differ as
much as 13% for the B1 phase. All these values are within the expected
accuracy of the PBE exchange–correlation functional.
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FIG. 1. Conventional cell of the

studied phases: (a) B1 (NaCl-type), (b)
Bi (AsTi-type), (c) LiSnS2 type, (d) B3
(ZB-type), (e) B8 (NiAs-type), (f ) Bh
(WC-type), (g) B4 (wurtzite-type), (h)
B2 (CsCl-type), and Bk (BN-type).

A comparison of calculated formation enthalpies allows the Wyckoff position (2a), while in the trigonal LiSnS2 structure, this
evaluation of thermodynamic stability of each phase. Accordingly, position is split into two (1a and 1b). On average, the “intermediate”
structural phases are listed from the most to the least energetically group (B8, B3) is 0.2–0.4 eV away from the ground state, and finally,
favorable in Table III. As previously reported,27 this parameter pre- the “least favorable” group (Bh, B4, and B2) reaches a 0.4–1 eV ener-
dicts the favorability of the cubic B1 phase over all other phases. For getic difference. The Bi hexagonal phase in the “most favorable”
IVb
TMNs, three main groups can be distinguished based on their rel- group is always nearest to the ground state phase (B1), and the cubic
ative stability concerning the ground state cubic B1 phase (ΔE). The B2 of the “least favorable” group is always the most distant. The
“most favorable” group includes phases that are less than 0.2 eV order of stability inside each group is similar for all three IVbTMN.
away from the ground state (Bi, LiSnS2, and Bk). It is worth noting Nevertheless, there is a change in the relative stability of the phases
that within this group, all phases have hexagonal symmetry except that depends on the transition metal TM. The three phases of the
for the LiSnS2 phase. In the Bi phase, N atoms occupy the same “most favorable” group for TiN are ΔE ∼ 0.1 eV away from the B1
ground state cubic phase. For ZrN and HfN, the phases are no
longer degenerated, the Bi and LiSnS2 phases get closer to the cubic
TABLE I. The symmetry group, space group, type, and Strukturbericht notation of B1 (ΔE < 0.05 eV) and the Bk phase loses stability (ΔE ∼ 0.15–0.2 eV
each studied phase. for Zr and Hf, respectively). There are no significant changes in the
relative stability of the “intermediate” group regarding the TM. Both
Strukturbericht the hexagonal B8 and the cubic B3 remain ∼0.3 eV away from the
Symmetry group Space group Phase type notation ground state. All the aforementioned show that Bi, LiSnS2, Bk, and
Fm3m 225 NaCl B1 B8 hexagonal structures remain close enough to the ground state to
P63/mmc 194 AsTi Bi be regarded as possible metastable phases. In Sec. III D, we investi-
P3m1 164 LiSnS2 … gate its possible role in cubic to hexagonal (B1 to B4) phase transfor-
F43m 216 ZB B3 mation for IVbTMN (TM = Ti, Zr, and Hf).
P63mmc 194 NiAs B8
P6m2 187 WC Bh B. Chemical bonding, bulk modulus, and lattice
P63mc 186 Wurt. B4 constants relation
Pm3m 221 CsCl B2
P63/mmc 194 BN Bk The structural parameters variability as a function of the
TM reflects differences in the chemical bonding interactions.

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TABLE II. Lattice constant, formation enthalpy, and bulk modulus of the studied phase for IVbTMN. We have indicated other theoretical and experimental (expt) results found in
the literature.

Lattice constant Formation enthalpies Bulk modulus Relative energy

Calculated Other works Calculated Other works Calculated Other works EB1 − Ephase
TMN Phase a (Å) c (Å) a (Å) c (Å) ΔHf (eV/at.) B0 (GPa) ΔE
TiN B1 4.255 … 4.256 7
… −1.687 −1.734 -expt
39
293.3 260 3
0
4.24438-expt 280.87
31840-expt
28831-expt
Bi 2.940 5.132 −1.581 289.7 −0.106
Bk 3.526 4.224 −1.580 237.3 −0.107
LiSnS2 2.96 5.085 −1.576 289.2 −0.111
B8 2.978 5.182 −1.472 278.1 −0.215
B3 4.613 … 4.5956 … −1.367 212.1 22241 −0.320
Bh 2.908 2.696 2.8996 2.6966 −1.359 −1.340 27
273.6 −0.328
B4 3.317 5.175 −1.276 203.6 −0.411
B2 2.634 … 2.6357 … −0.832 268.4 25841 −0.855
ZrN B1 4.596 … 4.5967 … −1.765 −1.87643-expt 248.7 24828 0
4 5898 2778
4.6342-expt 238.03
21530-expt
25031-expt
Bi 3.193 5.496 3.20844 5.52044 −1.718 244.6 207.46 44 −0.047
LiSnS2 3.195 5.492 3.20944 5.51744 −1.715 244.5 207.3844 −0.05
Bk 3.781 4.596 −1.608 200.3 −0.157
B3 4.969 … 4.9788 … −1.435 180 18028 −0.33
1768
182.73
B8 3.201 5.691 −1.415 227.5 23841 −0.35
Bh 3.137 2.920 −1.379 −1.35527 223.7 24141 −0.386
B4 3.564 5.556 3.5378 −1.308 172.1 1678 −0.457
B2 2.839 … 2.8307 … −0.866 224.6 2418 −0.899
2.8845 216.23
HfN B1 4.532 … 4.5197 … −1.786 −2.0637 285 28528 0
4.5246-expt 243.03
30630-expt
27631-expt
Bi 3.148 5.436 −1.757 280.4 250.5444 −0.029
LiSnS2 3.153 5.421 −1.753 280.3 −0.033
Bk 3.749 4.512 −1.608 228.7 −0.178
B3 4.912 … … −1.486 205 20128 −0.3
180.53
19741
B8 3.147 5.643 −1.434 258.9 −0.352
Bh 3.091 2.897 −1.394 −1.38627 254.4 −0.392
B4 3.489 5.634 −1.307 197.8 −0.479
B2 2.804 … 2.8007 … −0.814 245.8 230.93 −0.972
2.8645

As expected, in Table II, the bulk modulus of any given structural
phase decreases while the lattice constants increase from TiN to
HfN. That is to say, when a heavier element is used, electronic
repulsion lowers the cohesion energy promoting larger bond
lengths.7 The effect is particularly important for Zr that presents
an increment of lattice constants higher than Hf. This points out
to an increment of the ionic character for Zr. The subtleties of
the electronic structure of each alloying element will be addressed
in Sec. III F. Now, for a given TM, the behavior of the structural
parameters reflects its coordination-type in each phase. Chen and

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TABLE III. Phase transition pressures of the IVb

TMN for some phases close to the D. Transformations
ground state B1.
In Fig. 2, the main structural transformations induced by pres-
Pressure (GPa) sure of IVbTMN can be identified. The calculated transformation
pressures along with ab initio theoretical data from the literature are
Transformation TiN ZrN HfN listed in Table III. In the compression zone, the main cubic B1–B2
B1 → B2 281–304 222.3 237.3–190 transformation takes place at a higher pressure for TiN (281 GPa),
3393 2093 3813 followed by HfN (237 GPa) and ZrN (222 GPa). Several experimental
3477 277 (245)8 1637 studies have found the same trend.30,31 It is interesting to note that
3546 2087 for ZrN, we have detected a new transformation taking place before
2096 the commonly observed B1–B2 transformation. The point a0 in
B1 → B3 17.2 14.8 14.4 Fig. 2(b) indicates that the B1 phase transforms into the hexagonal
153 133 93 Bi phase at a lower pressure (201 GPa) than the B1–B2 (222 GPa).
1628 528 For TiN, the calculated transition pressure is lower than the theoreti-
B3 → B2 32 27 31 cal values reported in Table III. This difference arises because the
353 273 313 value of the transformation pressure depends mainly on the ener-
B1 → Bk 8.37 11.6 13.4 getic difference of the two phases, but the bulk modulus that models
B1 → B4 20.69 20.9 20.2 the shape of the curves can also modify the calculated transition
B1 → Bi … 201 … pressure. We have found a substantial difference between our calcu-
lated bulk modulus and the reported theoretical values. Compared to
experimental values,30,31 we have predicted with higher accuracy the
bulk modulus for three IVbTMN. For instance, in the B1 phase, our
Jiang28 have pointed out that the cubic sites of the B2 CsCl-type calculated bulk modulus deviates 1.8%, 0.51%, and 3.28% (for TiN,
structure (coordination number 8) are much closer to its neigh- ZrN, and HfN, respectively) from the experimental results of
bors compared to the octahedral sites of the cubic B1 NaCl-type Gubanov et al.31 These differences are smaller to the error found in
phase (coordination number 6). Hence, the inter-ionic distances the theoretical bulk modulus calculated by Abavare et al.3 Therefore,
and thus lattice constants of the B2 phase (Table II) are smaller our calculated transition pressure can be considered as a better
than those of the B1 phase. Only phases with the same symmetry approximation.
(either cubic or hexagonal) obey this tendency. Since the bulk
modulus increases with the coordination number, phases with E. Vibrational properties
coordination number 6 (B1, Bi, LiSnS2, B8, and Bh) have a higher
bulk modulus than the fivefold (Bk) and fourfold (B3 and B4) To study the dynamic stability of IVbTMN, we have calculated
coordinated phases. The hexagonal Bi, Bk, B8, and LiSnS2 are the phonon spectra of each phase, and results are presented in Fig. 3.
possible metastable phases and have higher bulk modulus than Depending on the transition metal, the dispersion phonon spectra
B4 (wurtzite-type). Therefore, the retention of these metastable display several characteristic features. For instance, in all studied
phases instead of the B4 (wurtzite-type) phase might compromise phases, acoustic branches are dominated by metallic atoms.
in a lesser degree the performance of these nitrides as protective Therefore, as the mass of the metal increases, the branches lie from
coatings. higher to lower frequencies, being TiN (0–10 THz) the lightest metal
followed by ZrN (0–7 THz) and HfN (0–5 THz) the heaviest one.
Among the three IVbTMN, HfN possesses the lowest sound velocity.
Since the specific heat is inversely proportional to the cube of sound
C. EOS velocity, this is consistent with HfN having the highest specific heat
The calculated total energy evolution as a function of the of IVbTMN at low temperatures.13 At the high-frequency regime, the
atomic volume of the nine phases is presented in Fig. 2. For all behavior of optical branches is dominated by the lightest nonmetallic
three IVbTMN, the ground state is accurately predicted to be the atoms (N), but the influence of the metal–non-metal interactions is
sixfold coordinated B1 cubic phase. Taking the ground state as a present as well. As discussed in Sec. III B for any given phase, TiN
point of departure, two regions of energetic stability can be distin- has the highest bulk modulus followed by HfN and ZrN (Table II),
guished. In the compression zone, the volume reduction compels indicating an increase in bond lengths in that order. Consequently,
charge redistribution around the atoms,29 rising the metallic atom’s following the same trend phonon optical branches are found at
coordination number. Then, phases with coordination number higher frequencies for TiN, then HfN, and finally ZrN.
equal or higher to 6 have their energetic minima inside the com- Previously reported characteristic features of the phonon dis-
pression zone (B2, Bi, and LiSnS2). Likewise, phases with lower persion curves for the ground state cubic NaCl (B1) and the ZB
coordination numbers (5,4) are located in the expansion zone (B3, (B3) phases6,13,32–34 are observed as well. For instance, both phases
B4, and Bk). The three metals hold well the rule aside from the B8 show a frequency gap between acoustic and optical branches for
IVb
and Bh phases. Although they are sixfold coordinated, such phases TMN. In agreement with the experimental report of Kress, for
are slightly displaced to the expansion zone. Presumably, because TiN33 and ZrN,32 the ground state cubic B1 phase exhibits a small
electronic repulsion increases from Ti to Hf and a higher volume is softening of the longitudinal acoustic (LA) branches in the Γ-X
required to reach stability. direction [Fig. 3(a)]. This effect is less pronounced as the atomic

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FIG. 2. Total energy as a function of volume of the studied phases: B1, B2, B3, B4, B8, Bh, Bk, Bi, and LiSnS2 for (a) TiN, (b) ZrN, and (c) HfN, respectively. The letters
a0 , a, b, c, and d represent the points where the following transformations occur: (B1–Bi), (B1–B2), (B1–Bk), (B1–B3), and (B3–B2), respectively.

mass of the TM increases. As for the longitudinal optical (LO)
branches, for the B1 phase, the calculated frequencies at Γ are
15.51, 14.27, and 14.94 THz for TiN, ZrN, and HfN, respectively,
while experimental studies have reported 14.933 and 1432 THz for
TiN and ZrN.
As mentioned by Isaev et al.,2 an outstanding feature of
the cubic B1, B2, and B3 phases [Figs. 3(a)–3(c)] is the appear-
ance of a degenerate transverse acoustic mode along the high
symmetry points. Furthermore, imaginary frequency modes
along the high symmetry X-W-Γ direction of TiN and ZrN
reveal that these compounds are not dynamically stable in the
B2 CsCl-type phase [Fig. 3(b)], which has been mentioned
before by Abavare et al.3 In contrast, HfN does possess
dynamic stability. Because of the high symmetry of the Fm3m
space group, it is reasonable to expect a degeneration of trans-
versal modes except in the region around W. In such a region,
there is a high interaction between acoustic and optical modes
that give rise to dynamic instabilities. For TiN, imaginary fre-
quencies are observed in both acoustic and optical transverse
modes. As the TM weight increases (ZrN), the imaginary trans-
verse optical modes disappear, but no significant difference in
the acoustic transverse modes is observed regarding TiN. For
heavier TM (HfN), both transversal modes are no longer imag-
inary, making HfN stable in the B2 phase.
Regarding the hexagonal phases, B4 wurtzite-type seems to be
stable for TiN. In contrast, dynamic instabilities are observed for

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for IVbTMN and IVbTMN-Al, it is less feasible to stabilize the hex-

agonal B4 phase for mononitrides mainly composed of Zr and Hf
compared to Ti. Similarly, to the cubic B1 phase, the hexagonal Bk
phase [Fig. 3(d)] presents a notable softening of the acoustic
branches. Nevertheless, there are no dynamical instabilities in the
vibrational dispersion curves. This demonstrates that from an ener-
getic and vibrational point of view [Sec. III A; Fig. 3(d)], the Bk
phase is stable and might represent an intermediate phase involved
in the B1 to B4 transformation for IVbTMN and IVbTMN-Al. The
rest of hexagonal phases [Figs. 3(d), 3(e), 3(h), and 3(i)] along with
the trigonal LiSnS2 [Fig. 3(f )] are dynamically stable for all three
metals and do not show anomalies on any direction of the acoustic
branches. Compared to the cubic phases, hexagonal phases have a
narrower frequency gap between the optic and acoustic branches
which increases the probability of anharmonic phonon scattering.35
Therefore, the low-frequency optical branches can be regarded as
scattering centers that reduce the thermal properties of hexagonal
phases compared to cubic phases.36

F. Electronic properties
1. Charge density
In Sec. III D, it has been demonstrated that the main transfor-
mations B1–B2 and B1–B4 are mediated by two possible metastable
hexagonal phases, namely, the Bi and Bk phases. Additionally, their
phonon spectra have shown that they are dynamically stable. To
gain insight into the metal–nonmetal bonding character of such
phases, an analysis of the electronic charge distribution for
IVb
TMN is presented. Electron charge transfer from metallic
(Ti–Zr–Hf ) to nonmetallic (N) atoms grants refractory compounds
an important ionic character. However, a certain degree of cova-
lency in the bonding interactions is responsible for the enhanced
mechanical and thermal properties of these compounds. This
degree of covalency has been described by Schwarz1 as a strong
overlapping of atomic orbitals with comparable energy. We have
looked at the charge enclosed within the Bader volume as an

TABLE IV. Calculation of the electronic charge transferred from IVbTM (VE-BC) in
IVb
TMN for the B1, B4, Bk, and Bi phases, calculated through valence electrons
(VEs) and Bader charge (BC).

Valence electrons Total charge VE–BC

IVb
TM Phase (VE) (e−) (BC) (e−) (e−)
Ti B1 4 2.463 1.537
Zr 12 10.148 1.852
Hf 4 2.282 1.718
FIG. 3. Phonon dispersion relation along high-symmetry directions in the Ti B4 4 2.473 1.527
Brillouin zone for IVbTMN in (a) B1, (b) B2, (c) B3, (d) Bk, (e) Bi, (f ) LiSnS2, (g)
Zr 12 10.165 1.835
B4, (h) Bh, and (i) B8 phases.
Hf 4 2.306 1.694
Ti Bk 4 2.469 1.531
Zr 12 10.151 1.849
ZrN and HfN, hence, as the mass of the TM increases imaginary Hf 4 2.280 1.720
frequencies appear and become deeper. Although the B4 hexagonal Ti Bi 4 2.503 1.497
phase is not the ground state structure of IVbTMN, for IVbTMN-Al Zr 12 10.194 1.806
alloyed nitrides, Holec et al.16 have found the same characteristic Hf 4 2.326 1.674
stability behavior through x-ray diffraction patterns. That is to say,

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 Journal of
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approximation to the atomic electronic charge.26 The so-called
Bader charge (BC) for all three metals is reported in Table IV. The
degree of ionicity of the N–TM bonding (VE–BC) has been esti-
mated as the difference between the isolated-metal valence elec-
trons (VE) and its corresponding Bader charge in the crystal (BC).
As the difference increases, the ionic character does as well, and it
has been higher for ZrN followed by HfN and finally TiN. To
obtain a qualitative view of this phenomenon, the corresponding
charge density isosurfaces are shown in Fig. 4. For TiN, all phases
show a greater amount of electron charge density between the
atoms compared to HfN, and this difference is even higher for
ZrN. Accordingly, among the three TM, Ti exhibits a lesser
amount of charge transfer (VE–BC) (Table IV) and the lowest ionic
character. There is only a slight difference between the HfN and
TiN electron charge density. The d–d orbital interactions between
metallic atoms is smaller for HfN, as a result there is a higher
charge transfer (VE–BC) compared to TiN (Table IV). The ZrN
FIG. 4. Electron charge density for the IVbTMN (TM = Ti, Zr, and Hf) where (a), (e), and (i) B1 in the (100) plane; (b), (f ), and ( j) Bk in the (110) plane; (c), (g), and (k) Bi
in the (110) plane; and (d), (h), and (l) B4 in the (110) plane. The electron charge density is shown as isosurfaces of 0.1 (black), 0.06 (red), 0.04 (green), and 0.025
(salmon) (e−/A3).
J. Appl. Phys. 128, 105106 (2020); doi: 10.1063/5.0018710
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phases present the highest ionic character because there is less
charge density localization between atoms. As discussed in Sec. III C,
this feature is the reason why larger lattice constants were obtained
for ZrN (Table II). Now for each metal, the charge density plots
are placed from top to bottom in a descending energetic stability
trend. The electron charge density is rather homogeneous for the
ground state B1 and Bi phases. But for the less energetically favor-
able Bk and B4 phases, the charge distribution is less uniform, and
charge depleted layers appear along the c direction. This feature
explains the outstanding stability of the B1 phase and the loss of
mechanical properties of IVbTMN in the hexagonal B4 phase
found experimentally.
2. Band structure and DOS
The calculated DOS and the band structure along the high
symmetry paths of the ground state B1 phase and the Bi, Bk, and
128, 105106-8
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Applied Physics

B4 hexagonal phases are shown in Fig. 5. Occupation of states at
the Fermi level indicates a metallic character for all phases. Besides,
compared to the hexagonal phases, the B1 phase band structure
shows a marked dispersion compatible with a stronger metallic
character and higher electron mobility. According to Schwarz,1 the
chemical bonding of IVbTMN depends on two interactions: a weak
d state metal–metal interaction TM(d)–TM(d) and a stronger d
state metal–nonmetal interaction TM(d)–N(p). The B1 phase for
IVb
TMN [Figs. 5(a)–5(c)] has a bottom band around −15 eV that
corresponds mostly to N-s states and does not represent bonding

FIG. 5. Band structure along high symmetry directions in the Brillouin zone, and the partial and total density of states for IVbTMN (TM = Ti, Zr, and Hf) for (a)–(c) B1,
(d)–(f ) Bk, (g)–(i) Bi, and ( j)–(l) B4 phases. The atomic orbital contribution is depicted as: N-s (light purple), N-p (red), TM-s (yellow), TM-p (blue), TM-dt2g (green), and
TM-deg (dark purple).

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 Journal of
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states. Nevertheless, there is a small contribution of the TM-s states
around gamma (Γ). The bonding states are associated with bands
located around −6 eV and −3 eV showing extensive hybridization
of the N(p) -TM(d) states.37 For these bands, the TM-deg
orbitals have a higher contribution and are more spread along
the high symmetry directions compared to the TM-dt2g states
[Figs. 5(a)–5(c)]. No-bonding states (located around −2 to 5 eV)
comprise five bands predominantly occupied by Ti(3d), Zr(4d),
and Hf(5d) states just below the Fermi level occupied by TM-dt2g
states. These states do not modify the bonding properties but give
the compound a metallic character.1,3 This is not the case for TMN
nitrides to the right of the periodic table with more than nine
valence electrons, which become unstable in the cubic B1 phase
due to the occupation of anti-bonding states.37 Several characteris-
tic features of the ground-state cubic B1 phase DOS reported by
Xin et al.7 and Schwartz1 have been corroborated in this study. For
IVb
TMN [Figs. 5(a)–5(c)], a pseudogap is formed causing a separa-
tion between bonding and anti-bonding/non-bonding states. The
pseudogap is located around −2 eV for TiN and between −2 to
−3 eV for HfN and ZrN,8 respectively. There are some interesting
differences in B1 DOS for TiN, ZrN, and HfN. In agreement with
Saha et al.,13 the hybridization of N(p)–TM(d) bonding states is
higher for TiN and HfN compared to ZrN. For this last, around
−6 to −3 eV, the electronic band dispersion is dominated by N(p)
states [depicted in red; Fig. 5(b)]. This points out to weaker
bonding interactions for ZrN explaining the smaller bulk modulus
(Table II) and a greater ionic character (Table IV) found for this
nitride compared to TiN and HfN.
As mentioned in Sec. III B, the hexagonal Bi and Bk phases
are located energetically closer to the ground-state cubic B1 phase.
Despite having different coordination numbers (6 and 5, respec-
tively), the Bk and the B1 phase electronic structures share
common features that indicate similar chemical behavior. For
instance, both of them have a distinctive pseudogap below the
Fermi level and high hybridization at the bonding region (−6 to
−3 eV) [Figs. 5(a)–5(f )]. Additionally, in the Bk phase, ZrN
behaves just as discussed earlier for the B1 phase, that is, the band
dispersion at the bonding states region is dominated by N(p) states
in contrast to TiN and HfN for which hybridization of N(p)–TM
(d) bonding states is higher. Unlike Bk, the Bi hexagonal phase does
not have a pseudogap. Instead, only a widening of the DOS is
observed [Figs. 5(g)–5(i)]. Moreover, there is a considerable
decrease in the DOS around the bonding region (−6 to −3 eV)
meaning that the TM(p)–N(p) and TM(d)–N(p) interactions are
weaker in this phase. Finally, we remark the appearance of anti-
bonding states at the Fermi level mainly dominated by TM-deg
states at Gamma (Γ) [depicted in purple, Figs. 5(g)–5(i)] which
might be an indication of instability. The Wurtzite B4 phase elec-
tronic structure shows characteristic features that explain the diffi-
culty of IVbTMN to stabilize on this structure. First of all, there is a
high contribution of the TM(d) states at the DOS Fermi level
[Figs. 5( j)–5(l)], which is usually associated with structural
instability.6 In addition, a gap separates bonding and antibonding
states, but in contrast to the B1 and Bk phases where antibonding
states are not occupied, in the B4 phase, antibonding states are
occupied around the Fermi level. Therefore, B4 is considered unsta-
ble for IVbTMN.
J. Appl. Phys. 128, 105106 (2020); doi: 10.1063/5.0018710
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IV. CONCLUSIONS
To understand the pressure-induced transformation from the
cubic B1 to the hexagonal phases in IVbTMN (TM = Ti, Z, and Hf )
nitrides, a crystal, electronic structure, and phonon dispersion
study was performed employing first principle calculations. Nine
different phases were addressed, including both cubic and hexago-
nal phases. The calculated structural parameters, bulk modulus,
and formation enthalpies were in alignment with experimental and
theoretical studies. Among the studied phases, we have found that
the hexagonal Bi and Bk phases are energetically closer to the cubic
B1 ground state. Aside from the cubic B1–B2 transformation, two
additional transformations were found. A B1–Bi in the compression
zone for ZrN alone took place at a smaller pressure (201 GPa) than
the B1–B2 transformation (222.3 GPa), and a B1–Bk transformation
in the expansion zone for all IVbTMN. Phonon calculations showed
that IVbTMN studied is dynamically stable in the hexagonal Bi, Bk,
Bh, B8, and in the trigonal LiSnS2 phases. In contrast, ZrN, HfN in
the B4, and TiN, ZrN in the B2 presented imaginary frequencies
[Figs. 3(b)–3(g)]. Additionally, it was observed that the hexagonal
and trigonal phases have low thermal properties due to the interac-
tion between acoustic and optical branches. The charge density and
Bader charge analysis showed that all Zr composed nitrides have a
higher ionic character compared to Ti and Hf. Therefore, a lower
electron sharing between Zr and N in these compounds is related
to ZrN longer bond lengths and longer lattice constants compared
to TiN and HfN in all the phases. The electronic structure and
DOS calculations showed that B1 and Bk exhibit strong hybridiza-
tion of the TM(d) and N(p) orbitals in the bonding region just
below the characteristic pseudogap placed around −2 eV. A metallic
character is granted by the TM(d)–TM(d) non-bonding states
around the Fermi level for both B1 and Bk phases. The Bi band
structure showed distinct characteristics. For this phase, occupied
antibonding states around the Fermi level were observed, which are
related to electronic instabilities. Furthermore, it lacks the charac-
teristic pseudogap and high hybridization of the TM(d)-N(p) states
of refractory nitrides. For the B4 phase, there is a noticeable gap
between −1 and −4 eV that separates the bonding and antibonding
states. DOS calculations showed antibonding states at the Fermi
level, which are associated with instabilities in the B4 phase.
Therefore, it is more feasible for IVbTMN and IVbTMN-Al to stabi-
lize in the Bk phase instead of the Bi or B4 phases.
ACKNOWLEDGMENTS
M.A. and A.V.C. acknowledge support from Conacyt-Mexico
through fellowship 701218 and 230032. The authors acknowledge
computer resources, technical advise, and support provided by
Laboratorio Nacional de Supercómputo del Sureste de México
(LNS), a member of the CONACYT national laboratories, with
Project No. 201903070N.
DATA AVAILABILITY
The data that support the findings of this study are available
within the article and from the corresponding author upon reason-
able request.
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