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Department of Physics and Astronomy, University of Missouri-Kansas City, Kansas City, Missouri 64110, USA
Department of Materials Science and Engineering College of Engineering, Drexel University, Philadelphia, Pennsylvania 19104, USA
Original
Paper
Phys. Status Solidi B 251, No. 8 (2014)
the efcacy of the data-mining, machine-learning algorithms [17] in a genomic approach [18] for this class of
materials.
The MAX phases are layered hexagonal crystals (space
group: P63/mmc NO 194). Figure 1 displays the MAX
crystals for n 14. (From now on, we will refer them as
211, 312, 413, and 514 phases.) Also, in this paper, the term
MAX phases we refer to are for these crystals even though
phases with n 5 are known to exist. Most of the existing
experimental work on the MAX phases has been on the
211 and 312 carbides. The reason for the scarcity of
MAX nitrides, especially with for higher n, has not been
elaborated. An important feature to be recognized is that in
MAX compounds, layer A remains constant whereas layers
of M and X increase with n in Mn1AXn. The X layers are
always in between the M layers and blocks of MX layers are
connected by single A layer, which can signicantly affect
the properties of a MAX phase. It is anticipated that the
elastic properties of MAX phases will vary over a wide range
depending on M, A, X, and n. The Poissons ratio h, which is
closely related to Pugh moduli ratio (G/K) [19], and the total
bond order density (TBOD) (to be described in the next
section), which is an indicator of the strength of interatomic
bonding in a crystal are designated as the key parameters,
respectively, for their mechanical and electronic properties
of the MAX phases. Of fundamental importance is to
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S. Aryal et al.: A genomic approach to stability and properties of the MAX phases
rab
n:occ j;b
XX
n:occ i;j
where C njb are the eigenvector coefcients of the nth band, jth
orbital and bth atom, and Sia,jb are the overlap integrals
between the ith orbital of the a atom and jth orbital of the bth
atom. The extended basis (EB) is used to study spectroscopic
properties, which require higher accuracy for states high
above the Fermi level. The combination of VASP and
OLCAO packages to study the structure and properties of
complex crystals and has been successfully demonstrated in
many recent publications [37, 4147].
In the present study, the investigation of the electronic
structure focuses on the BO using a MB. It is well known that
the Mulliken scheme is basis-dependent and should use
more localized orbitals, which cannot be precisely dened
so there may be some uncertainty when applied to the MAX
phases with different M elements. There are other methods
in calculating BO or similar quantities such as Bader
analysis [48]. However, to obtain quantitative results for a
large number of crystals, and for structures with low
symmetry such as in MAX phases, we opted to employ the
Mulliken scheme due to its simplicity and easy to use. The
summation of all pairs of BO values in the crystal gives
the total bond order (TBO). When divided by the crystal
volume, it gives the TBOD. The latter can be resolved into
partial bond order density (PBOD) components. For the
MAX phases, we calculated the PBODs for the MX, MA,
MM, and AA pairs, (see Section 3.3).
3 Results and discussion The results of the elastic
properties and the electronic structure for the 665 MAX
phases are presented in the following three subsections.
Section 3.1 is for elastic properties and correlations among
them. Section 3.2 is on the electronic structures and their
specic trends and features. Section 3.3 concentrates on the
correlations between elastic properties and electronic
structure, the central theme of this paper. The MAX phases
elastic properties have been calculated by many groups [34,
4957] including us [58]. These calculations use different
methods and targeted different MAX phases. They generally
agree well with each other for most of the MAX phases.
In particular, the comprehensive evaluation by Covers
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Phys. Status Solidi B 251, No. 8 (2014)
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(3)
(4)
(5)
(6)
(7)
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S. Aryal et al.: A genomic approach to stability and properties of the MAX phases
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Phys. Status Solidi B 251, No. 8 (2014)
1487
MAX-211-Nitrides
MAX-211-Carbides
0.42
Nb
0.31
0.29
0.26
0.21
Zr
0.19
0.36
0.31
0.34
0.29
0.26
Hf
0.24
Zr
0.19
0.21
Ti
IIIA
Ti
Sc
Ga
In
IIIB
Tl
Si
Ge
Sn
IVB
Pb
As
VB
Sc
Al
S
VIB
Ga
In
IIIB
MAX-312-Carbides
Ta
0.36
Nb
0.31
0.34
0.29
Hf
0.24
Zr
0.19
S
VIB
0.44
0.41
0.39
0.36
0.31
0.34
0.29
0.26
Hf
0.24
Zr
0.19
0.21
Ti
IIIA
Sc
Ga
In
IIIB
Tl
Si
Ge
Sn
IVB
Pb
As
VB
Sc
Al
S
VIB
Ga
In
IIIB
MAX-413-Carbides
Tl
Si
Ge Sn
IVB
Pb
As
VB
S
VIB
MAX-413-Nitrides
Mo
Ta
0.36
Nb
0.31
0.34
0.29
0.26
Hf
0.24
Zr
0.19
0.41
Cr
Poisson's Ratio
0.39
0.44
VIA
0.41
Cr
VA
VIA
0.44
0.39
Ta
0.36
Nb
0.31
0.34
0.29
IVA
0.21
Ti
0.26
Hf
0.24
Zr
0.19
Poisson's Ratio
IIIA
As
VB
VIA
0.21
Mo
VA
Nb
IVA
IVA
0.26
Al
IVA
Pb
Ta
Ti
0.21
Ti
IIIA
IIIA
Sn
IVB
Cr
Poisson's Ratio
VA
0.39
VA
VIA
0.41
Sc
Al
Ga
In
IIIB
Tl
Si
Ge
Sn
IVB
Pb
As
VB
Sc
S
VIB
Al
Ga
In
IIIB
Tl
Si
Ge Sn
IVB
Pb
As
VB
S
VIB
MAX-514-Nitrides
MAX-514-Carbides
Mo
VIA
0.44
0.41
Ta
0.36
Nb
0.31
0.34
0.29
0.26
VA
0.39
Zr
0.19
IVA
0.21
0.39
Ta
0.36
Nb
0.31
0.34
0.29
0.24
Hf
0.41
Cr
Poisson's Ratio
Cr
0.44
VIA
Mo
VA
Ge
Mo
0.44
Cr
IVA
Si
MAX-312-Nitrides
Mo
0.26
Hf
0.24
Zr
0.19
0.21
Ti
IIIA
Ti
IIIA
Tl
Poisson's Ratio
Al
Sc
Al
Ga
In
IIIB
Tl
Si
Ge
Sn
IVB
Pb
As
VB
S
VIB
Sc
Al
Ga
In
IIIB
Tl
Si
Ge
Sn
IVB
be noted that the TBO and TBOD are two different quantities
with different physical units. The latter accounts for the
effect of the crystal volume, which differs signicantly in the
MAX phases due to their diverse chemical compositions.
We found that a better correlation can be established when
the TBO is normalized to the unit volume. This implies that it
is the concentration of the BO within the crystal structures
that actually exerts the strongest inuence to the elastic
properties as far as electronic structure factors as concerned.
This also reasserts the importance that all crystal structures in
the present study are fully optimized with high accuracy so
that the unit volume can be accurately obtained.
The effective charges Q on each atom in the 665 MAX
phases according to Eq. (3) using the MB in the OLCAO
method [39] were calculated. The deviation of Q from its
www.pss-b.com
Pb
As
VB
S
VIB
Poisson's Ratio
IIIA
0.39
Nb
0.24
Hf
0.42
Ta
IVA
VA
0.34
VA
0.36
Ta
0.44
Cr
Poisson's Ratio
0.39
Poisson's Ratio
VIA
0.44
Cr
IVA
Mo
VIA
Mo
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54.18%
69.81%
(a)
4.4%
31.71%
62.48%
(f)
4.36%
11.35%
25.2%
80.65%
(d)
1.78%
5.9%
14.68%
19.97%
(e)
(c)
2.25%
6.69%
3.01%
7.21%
9.71%
46.98%
37.31%
76.38%
(b)
69.63%
2.81%
9.51%
18.72%
11.68%
(g)
2.19%
9.46%
74.48%
15.05%
M-M
M-A
M-X
A-A
(h)
1.72%
8.76%
Figure 5 Contributions from MM, MA, MX, AA bond pairs to the total bond order (TBO) in the form of pie charts: (a) 211, (b) 312,
(c) 413, (d) 514 carbides, (e) 211, (f) 312, (g) 413, and (h) 514 nitrides.
Original
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Phys. Status Solidi B 251, No. 8 (2014)
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Figure 6 Effective charge transfer DQ for M, A, X elements in all MAX phases. Top: Carbides. Bottom: Nitrides. Positive values
represent electron loss, whereas negative values denote electron gain (see text for details).
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Figure 7 Plot of DOS at Fermi level N(EF) against total number of valence electrons per unit volume in the crystal. Note the outlier nature
of M Sc.
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Phys. Status Solidi B 251, No. 8 (2014)
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Table 1 List of coefcients for K and G/K estimates from data-mining algorithm using a linear superposition: Y C(0) C(1)*
TB_Dens C(2)*MM_TBO C(3)*MA_TBO C(4)*MX_TBO C(5)*AA_TBO C(6)*AX_TBO C(7)*X_Q C(8)*
N_EF.
Y
C(0)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
correlation
coefficient
K(211)
K(312)
K(413)
K(514)
Poisson
Poisson
Poisson
Poisson
206.84
187.74
230.35
237.71
0.389
0.443
0.392
0.479
5038.87
3970.89
4110.44
4366.93
3.0584
2.7664
1.9542
1.7623
6.1583
2.9706
4.6844
2.6619
0.0091
0.0149
0.0203
0.0091
3.2376
11.89
11.738
12.386
0.0144
0
0
0
10.199
7.2138
5.487
4.663
0
0
0.023
0.0019
28.091
22.733
21.675
20.655
0.0332
0.0253
0.011
0.0133
100.743
7.2138
262.329
186.82
0.28
0.2349
0
0.3082
107.34
82.193
126.4
116.11
0.174
0.191
0.156
0.219
4.18E-01
1.31E-01
0.00E 00
4.27E-02
1.40E-03
1.10E-03
1.10E-03
6.33E-04
0.915
0.9323
0.9516
0.9565
0.8009
0.8504
0.8919
0.7955
ratio
ratio
ratio
ratio
(211)
(312)
(413)
(514)
for the other 50% of the 211, 312, 413, and 514 MAX
phases, respectively. An excellent correlation with over 90%
correlations on each type of MAX phases for the K values is
obtained. Figure 10 also shows the pie charts comparing the
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Table 2 Examples
P of MAX phase
P outliers, either Sc-based or with a relatively low G/K and potentially thermodynamically stable, i.e.,
with a negative DH or with DH 0.053 eV.
P
MAX
G/K
chemical equilibria
DH (eV atom1)
Mo2GeC
Ti2AsC
Ta2GeC
Ta3GeC2
Sc3TlN2
Sc3InN2
Sc3SC2
Sc3SnN2
Sc3AlN2
Sc3SN2
0.375
0.430
0.671
0.700
0.685
0.701
0.610
0.715
0.737
0.739
0.05216
0.02150
0.03134
0.00045
0.20233
0.01623
0.00272
0.05022
0.01350
0.00185
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S. Aryal et al.: A genomic approach to stability and properties of the MAX phases
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2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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