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basic solid state physics

A genomic approach to the stability,

elastic, and electronic properties
of the MAX phases
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Phys. Status Solidi B 251, No. 8, 14801497 (2014) / DOI 10.1002/pssb.201451226

,1

Sitaram Aryal , Ridwan Sakidja , Michel W. Barsoum , and Wai-Yim Ching*

1
2

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

Received 22 March 2014, revised 9 May 2014, accepted 20 May 2014

Published online 24 June 2014
Keywords elastic properties, electronic structure, genomic approaches, MAX phases
* Corresponding

author: e-mail chingw@umkc.edu, Phone: 816-235-2503, Fax: 816-235-5221

In this study, we report a comprehensive assessment on the

elastic and electronic properties of 792 possible MAX
(Mn1AXn) phases with n 14 using ab initio methods.
These crystals are then screened based on their elastic and
thermodynamic stability resulting in a large database of 665
viable crystals. All the experimentally veried MAX phases
passed the screening. Various correlations among and between
them are fully explored. In particular, the key elements in the
interdependence between the elastic properties together with
mechanical parameter derived from them and the electronic
structure are identied. Detailed analysis of various correlation

plots shows that there is a clear correspondence between bulk

modulus K and total bond order density (TBOD). Calculations
show a marked difference between the carbides and nitrides.
This database is also used to test the efcacy of data mining
algorithms for materials genome. We further identied several
thermodynamically stable new MAX phases with unusual
mechanical parameters that have never been synthesized in the
laboratory or theoretically investigated. The complete database
on the elastic and electronic structure together with the
mechanical parameters for these 665 MAX phases compounds
are included in the Supplementary Materials and fully accessible.

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction The anisotropic laminated transition

metal compounds with hexagonal crystal structure called
MAX phases or Mn1AXn are a class of ternary compounds
that possess an unusual combination of vastly different
mechanical and electronic properties [15]. They behave
both like metal and ceramic, which roots from its highly
anisotropic crystal structure and their diverse chemical
composition. Depending on their unique composition,
structural arrangement and bonding pattern, these ternary
alloys possess some of the most diverse and desirable
properties such as damage-tolerance, oxidation resistance,
excellent thermal and electric conductivity, machinability,
etc. suitable for applications as advanced materials in many
different technologies and under extreme conditions. So far,
only about 60 such MAX phases have been conrmed or
synthesized [1]. MAX phases were rst reported in early
sixties [69], but there has been an explosive growth in its
interest and applications since 2000 [1].
A systematic and comprehensive study of the properties
and trends in the MAX phases is of vital importance in

understanding the reason behind their diversied properties

and in the quest for new phases. A fairly large number of
published works both experimental and theoretical already
exists, but they are somewhat scattered and concentrated
mostly on the n 1 or M Ti phases, or those that have been
synthesized [1016]. Here we report an extensive study
using ab initio calculations of the elastic, mechanical, and
electronic properties of 792 MAX phases with n 14.
They are screened for elastic and thermodynamic stability
resulting in a database of 665 viable compounds. This large
database is used to establish general trends, in seeking
correlations on various elastic properties together with
mechanical parameter derived from them and electronic
properties. It should be stated in the very beginning that
the mechanical properties we refer to in this paper are the
general parameters derived from the linear elastic theory and
should not be construed to imply the mechanical properties
measured in the laboratory such as fracture toughness
or failure behaviors even though they may be related in
some complicated way. We also used this database to test
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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

Figure 1 Ball and stick diagrams of M2AX, M3AX2, M4AX3, and

M5AX4.
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understand the connection between the elastic properties and

the electronic structure of MAX phase compounds, which is
still lacking.
The main objective of this work is to esh out various
correlations among and between the elastic and electronic
structures based on the large data set obtained from careful
density functional calculations. What is not included are
topics related to more specic properties such as hardness,
corrosion resistance, magnetic structures, optical, electric
and thermo-conductivities, phonon spectra, superconductivity, and thermoelectric properties, which will be dealt with
elsewhere in future studies. We also want to emphasize that
we are looking mostly for obvious trends and identiable
correlations in MAX phase properties as a distinctive class
of materials with the same structure, and not on individual
MAX phases, whose properties can vary signicantly.
In Section 2, we rst describe the approach we adopt and
the computational methods used in this study. The complete
results on various elastic and electronic properties and their
correlations are presented and discussed in Section 3 and
in the Supplementary Materials section. In Section 4, we
demonstrate the application of the vast data we obtained to
validate the efcacy of data mining algorithm and statistical
machine learning approach for materials genome in support
of the conclusions reached so far. This is followed by
further discussions of a few thermodynamic stable but
hitherto unrecognized MAX phases with unusual correlations (outliers). Finally, a summary and some conclusions
together with future directions for research are presented in
the last section. The complete database for the elastic and
electronic structure properties of the 665 MAX crystals is
available in the Supplementary Materials (SM).
2 Approach and methods We start by assuming the
existence of all possible MAX phases based on the original
suggestion by Barsoum [1] of the M, A, X elements in the
Periodic Table that exist in at least one known synthesized
compound. The elastic constants and the elastic constants
derived for 792 crystals with M Sc, Ti, Zr, H, V, Nb, Ta,
Cr, Mo; A Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, S and,
X C or N, and n 14 are calculated based on fully
relaxed structures using density functional theory (DFT)
based Vienna Ab initio Simulation Package (VASP) [20, 21].
The calculated results are then subjected to two levels of
screening for their elastic and thermodynamic stability.
The rst round of screening is based on the CauchyBorn
elastic stability criteria for hexagonal crystals [22], which
eliminated 71 crystals. Next, we calculated the heat of
formation (HoF) for the same 792 crystals. The HoF was
calculated based on the relative stability of each MAX phase
relative to the formation energy of its elements in their most
stable form at the ground state. As a result, 72 phases with
positive HoF are then eliminated of which 27 crystals
overlap with the rst round elimination. We should reiterate
that since the main goal of this study is to detect the
underlying major trends that dene the elastic properties and
electronic structures of existing and potential MAX phases,
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we purposely avoided the use of the time-consuming

thermodynamic assessment on all potential competing
phases in the MAX ternary phase diagrams as a screening
criterion. Rather, we only employed these two criteria
(CauchyBorn and negative HoF criteria) such that a large
enough sampling can be carried out to enable us to appraise
any major trends. This two-level screening resulted in a
database of 665 crystals for our focused study. In Section 5,
we evaluate the stability of some outliers, at the ground state
based on the relative lattice stability of these MAX phases
against their neighboring and hence competing phases.
The crystal structures for the 792 hypothetical MAX
phases used in the present study are rst optimized by
unconstrained relaxation using VASP to calculate the elastic
tensor. We used projector augmented wave (PAW) [23, 24]
method and GGA PBE [25, 26] for exchange correlation
functional with an energy cutoff of 500 eV as recommended
for a high precision calculation in VASP [27]. We used
stringent convergence criteria of 1.0  107 eV for electronic relaxation and 1.0  105 eV 1 for ionic force
convergence. We also used a large G-centered, k-points
mesh (15  15  3) along with MethfesselPaxton scheme
for smearing since the MAX phases are metallic and a
sufcient number of k-points should be used to ensure high
accuracy.
Once the structures were fully relaxed with minimum
internal stresses, we used the strainstress analysis approach
for elastic properties calculation [28]. A small strain (1%
for present case) for each independent strain element is
applied to the crystal and the structure is relaxed again while
keeping its volume and shape xed. The stress tensor sij
under a set of applied strain ej and the elastic stiffness
constants (Cij) are obtained by solving the following
equation:
X
C ij ej :
1
s ij
ij

From the calculated Cij, we obtain the polycrystalline

elastic bulk properties using the well-tested VoightReuss
Hill (VRH) approximation for polycrystalline aggregates [2931]. The Voight approximation assumes uniform
strain distribution in the structure, which results in an upper
limits of the polycrystalline bulk moduli. On the other hand,
the Reuss approximation assumes a uniform stress distribution resulting in the lower limits. The average of these two
limits gives the so-called Hill approximation, which is more
realistic and can be compared with measured data. The VRH
approximation has been validated in many metallic and
insulating crystals [14, 3237].
The electronic structure and bonding of these phases are
calculated using the Orthogonalized Linear Combination of
Atomic Orbitals (OLCAO) package [38, 39] with the VASP
relaxed structures. The OLCAO method is also a DFT based
method within local density approximation (LDA) developed by us and is extremely efcient for large or complex
materials due to its economic use of the basis expansion. The
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

use of atomic orbitals in the basis expansion makes the

interpretation of results easier and more natural. In the
OLCAO method, three types of basis expansions are used
for different types of properties [38, 39]. The full basis (FB)
is used for the self-consistent potential and electronic
structure calculation; the minimal basis (MB) is used for
effective charge (Q ) and bond order (BO) rab calculations
based on Mullikens scheme [40], which requires more
localized orbitals. They are dened by the following two
equations:
XXX 

C ian C njb Sia;kb ;
2
Qa
i

rab

n:occ j;b

XX

C ian C njb Sia;jb ;

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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et al. [59, 60], which evaluated the elastic properties of a

wide range of 211 MAX phases and Ti-based MAX phases
with various n. Their results are quite close to what we have
obtained for these segments of our database (see the
complete data set in the SM). We do emphasize that due to
the nature of the large database reported in this study, our
goal is not to elaborate on specic comparisons between the
elastic properties obtained by our calculations versus others
as the fundamental DFT approach employed is quite similar.
Rather, our focus is to leverage the large database obtained
from our calculations to probe possible correlations amongst
and between elastic and electronic structure properties. The
MAX phases electronic structures have also been studied
by many authors and they do not always agree with each
other due to mainly the different computational methods
employed. Here, our results are exclusively calculated using
the OLCAO method [32]. As for the correlations between the
elastic properties and electronic structures, there are far less
such studies and mostly using the electronic structure results
to explain the experimentally measured elastic properties in a
somewhat hand-waving style. The availability of a large data
set in the present study offers an opportunity to ameliorate
the situation. For the sake of brevity, the MAX carbides and
nitrides will henceforth referred to as MAC and MAN,
respectively.
3.1 Elastic properties Detailed understanding of the
elastic and mechanical properties is crucial for material
application especially for layered structures such as MAX
phases where anisotropy in one of the most important
properties. It becomes even more critical when they are used
as composites since elastic anisotropy of one may offset the
other under different stress components. Using the approach
outlined in the previous section, the elastic constants and the
mechanical parameters of the 665 MAX crystals that passed
the two level screening were calculated. In Fig. 2, we display
all the data for C11, C33, C44, and C66 for both the carbides
(solid symbols) and nitrides (open symbols). Data for
other components of Cij can be found in Supplementary
Materials. On the left column of Fig. 2, C11 are plotted
against C33; on the right column; C44 against C66. Different
shapes of the symbols represent different M elements and
different colors designate different A elements. In this
display, each symbol along with associated color represents
two Cij values for a particular MAX phase. Both axes in the
gure have the same range and the diagonal lines in the plots
for the 211, 312, 413, and 514 groups guide us to identify the
degree of anisotropy for each MAX phase. The farther the
symbol is away from the diagonal line, the more anisotropic
it is.
Careful analysis of the data of the left column of Fig. 2
shows some interesting trends:
(1) The elastic constants of the MAX phases vary widely
depending on M, A, and X elements.
(2) Despite the wide variations in both C11 and C33, the C11
values appear to be linearly related to C33. MAX
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(3)

(4)

(5)

(6)

(7)

compounds have layered structures, the elastic response

along the c-axis is expected to be different from those
along the a- and b-axes. The matching increase in C11
and C33 is consistent and, to some extent, broadened the
critical nding of Cover et al. [60] on the trends in C11 or
C33 for a given M and A in the 211 phases. Our nding
suggests that not only that both carbides and nitrides
exhibit little differentiating effect as far as each of the
C11 and C33 value are concerned (all types of carbide or
nitride points with a given M and A are reasonably
paired up to some extent), but also that these two values
increase proportionately. Similar trends can be observed
in the higher n MAX phases.
Some MAX phases are isotropic (C11 C33), some are
anisotropic with C11 > C33, in others C33 > C11.
Remarkably, and despite of the increasing c/a ratios,
MAX phases with higher n values, the degree of C33/C11
ratio remains largely close to 1, which is indicative of the
strong correlation exhibited by these two elastic
constants.
Despite of the generally linear correlation between C11
and C33, most of the MAX phases show at least some
elastic anisotropy and we can still distinguish the
difference in MAC and MAN. In general, the nitrides
tend to be slightly concentrated in the region where C33
is higher than C11, whereas carbides exhibit the opposite
trend, i.e., having C33 lower than C11. This difference in
anisotropic feature could be due to different bonding
patterns of the N or C layers with M layers in the axial
and planar directions and will be elaborated later.
For n 1 or the 211 phases, the data are distributed
almost equally above and below the diagonal line. For
most of the nitrides C33 > C11; the opposite is true of the
carbides. In general, both C11 and C33 increase with n.
However, the increases in C11 are larger than those in
C33 resulting in an increased number of anisotropic
carbides compared to nitrides with the notable exception
of the scandium containing MAX phases. This anomaly
in the Sc-based carbides is quite perplexing since the
nitrides show no such marked difference.
As n increases, the distribution of the data points shifts
more toward below the diagonal line with C11 being
larger than C33. The MAX phases that exhibit higher
anisotropy depend on the specic M element in both
carbides and nitrides, especially for M Cr or Mo.
The A element in the MAX phases which connects
blocks of layered Mn1Xn show discernable effects on
C11 versus C33 resulting in clustered regions of the same
A elements (same colored symbols in Fig. 2). These
A-based clusters become less obvious as n increases
indicating a gradual loss of inuence on elastic
properties when n increases as the structure progressively moves toward the binary Mn1Xn compounds.

We now shift our discussion to the right column of

Fig. 2, which plots all shear elastic constants C44 versus C66.
The difculty in describing the degree of shear anisotropy in
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Figure 2 Calculated C11 versus C33 (left) and

C44 versus C66 (right) of MAX phases. Solid
circles for carbides and open circles for
nitrides. Diagonal lines help indicate no
elastic anisotropy for MAX phases.

a hexagonal crystal structure is well known [61]. Thus, for

this reason, we have employed the simplest representation of
the shear anisotropy, namely the C66 to C44 ratio, which
corresponds to a simple physical strain. In addition, the three
alternative anisotropy factors involving Cij, which are also
known to represent the degree of anisotropy [61] can be
easily calculated using the data presented in Supplementary
Tables. The distributions of the C66 versus C44 data are far
more scattered in comparison to those of C11 versus C33 on
the left and the anisotropic behavior between C44 and C66 is
far more pronounced.
Similar to the C11 versus C33, the C44 versus C66 for the
carbides and nitrides tends to be concentrated in different
regions. Most of the carbides have larger C66 than C44 and
are located above the diagonal line. In contrast, the nitrides
have larger C44 than C66 and are more concentrated below
the diagonal line. With increasing n, the demarcation that
highlights this difference in shear anisotropy in carbides
versus nitrides becomes much more evident. With the 514
MAX phases, for example, there is barely an overlap
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

between those of carbides versus those of nitrides as shown

in Fig. 2. So to some extent, this gives an added complexity
to the notion that X exerts little inuence on some of the
elastic constants of MAX phases as suggested by Cover [60].
While this argument may be true for C11 and C33, the same
case could not be made for C44 nor C66. Furthermore, a wider
variation in terms of the degree of anisotropy in both cases
become much more pronounced with increasing n, indicating clearly that A still plays a major factor despite its lower
content in say the 514 MAX phases. In contrast, this is not
case for the C11 and C33 values, where the variation is clearly
less. Thus, A exerts a critical inuence on the shear
resistance in all MAX phases. This phenomenon subsequently is also manifested in a similarly strong inuence of A
on shear modulus G.
As noted above, from the calculated Cij, the polycrystalline bulk (K), shear (G), and Youngs (E) moduli as well as
Poissons ratio (h) can be obtained. They are presented in
tabular form in the SM together with the Cij values. These
bulk elastic properties clearly spread over a wide range
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indicating the possibility of a broad range of potential

applications in different areas. Bulk and shear moduli, which
represent resistance to change in volume and shape,
respectively, are the most important parameters, whereas
the Poissons ratio or the Pugh moduli ratio G/K gives a
balanced overall assessment of the mechanical properties. In
Fig. 3a, we plot the K versus G values for all screened 655
MAX phases. In general, the nitrides have smaller G values
than the carbides. Larger K and smaller G values result in
easier bond angle changes without changing bond length
(BL) which, according to Pughs criteria based on ductility
analyses of various polycrystalline metals [19], G/K is a

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good indication of a possible increase in its relative ductility

in pure metals. The extension of such an analysis to
intermetallic compounds like MAX phases, however, is
more far-fetched. Actually, our results show that there is
little correlation between the G/K ratio to say the hardness
values of the MAX phases.
In Fig. 3b, we plot the G versus K results for all screened
665 MAX phases and compare them to those for metallic
compounds and select binary MX compounds [62]. We note
that the MAX phases cover a wide region of bulk and shear
moduli, overlapping with those of the common metals.
Clearly, if there was any correlation between the G/K ratio

Figure 3 (a) Calculated bulk modulus K

versus shear modulus G of MAX phases. Solid
and open symbols represent carbides and
nitrides, respectively. (b) Plot of bulk modulus
versus shear modulus for all screened MAX
phases. Solid circles and open circles are used
for carbides and nitrides, respectively. Different color is used for different n in Mn1AXn.
The gure also shows the location of other
metals and binary MC and MN compounds.
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and mechanical properties then the MAX phases should

exhibit similar ductility as the values for metals/alloys and
MAX phases overlap. This is clearly not observed for the
simple reason that ductility requires at least ve independent
slip systems; the MAX phases that have been experimentally
found so far [1] possess only two such systems. Furthermore,
the Vickers hardness values of the MAX phases span a
relatively narrow range of 28 GPa, a fact that is not reected
in Fig. 3b. Said otherwise, our results clearly show that the
Pugh ratio cannot be used as any indicator of ductility, at
least for the MAX phases.
With these caveats it is still instructive to understand the
changes in the G/K ratio as a function of MAX structure and
chemistries. As shown in Fig. 3b, the G/K ratio ranges from
0.12 to 0.8, with the MAX carbides appear to concentrate
mostly above G/K 0.42. The MAX nitrides, on the other
hand, especially those with a higher n values, possess
relatively lower G/K values. In general, the MAX phases
with higher n values have higher bulk moduli (K) than those
with lower n values. Some of the MAX phases with higher n
values, mostly carbides, have both K and G values close to
those of the binary carbides. The higher n MAX nitrides, on
the other hand, display a much wider range of G resulting in
some phases with low G/K value. This implies that, unlike
the MAX carbides, the G values of the MAX nitrides
are more sensitive to the nature of the A group elements. We
view this widening of the G/K range as an additional means
to tune the elastic properties of the MAX nitrides, especially
those of higher n values. It is worth noting here however
almost none of the high n MAX nitrides have been
synthesized to date. It is important to note that in the absence
of A, the shear moduli of binary MN compounds are
generally large and of a limited range, resulting in a narrow
range of G/K. This result highlights one more time that the
mechanical behavior of the MAX phases is quite distinct
from their parent mono-carbides/nitrides.
The calculated Poissons ratio, h, which is closely related
to the G/K ratio for the original 792 hypothetical MAX phases
are presented in Fig. 4 in the form of an innovative map
that resembles a portion of the Periodic Table. Here, the
M elements are plotted on the y-axes and the A elements along
the x-axes. The color of each small square represents the h
value of the particular MAX phase along with other
information such as whether the phase has been synthesized
or not. The phases that have been eliminated by the Cauchy
Born and HoF criteria are marked with and , respectively.
The experimentally conrmed phases are marked by a white
star. It is gratifying to see that none of the experimentally
conrmed phases are among the ones judged to be unstable
and there are many boxes of different colors without the white
star suggesting the possible existence of myriad of unexplored
MAX phases. While the elastic properties of MAX phases can
vary over a wide range as indicated by the variations in color
for the different squares in Fig. 4, we are able to delineate
the boundaries of MAXs materials properties within which
optimized functionalities can be further explored. Additional
information on the elastic properties of the MAX phases is
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shown in SM. Supplementary Figure S1 displays the linear

elastic anisotropy ratio C11/C33 in all MAX phases in the form
of innovative maps similar to Fig. 4. Supplementary Figures
S2 and S3 show similar maps but for the Pugh ratio G/K and K,
respectively.
3.2 Electronic structure and bonding Given the
large diversity in the elastic properties of MAX phases
depending their chemistry and n, the natural question arises:
how does their electronic properties vary and can a
correlation be found between the elastic and electronic
properties. We therefore now shift our focus to the electronic
structure of these potentially stable MAX phases. Typically,
the electronic structure consist of the band structure, the
density of states (DOS), atom-resolved partial DOS (PDOS),
effective charges on each atom and the BO (also called bond
overlap population between all pairs of atoms in all MAX
phases (see method Section 3.2). Since we have calculated
all potentially stable MAX phases comprising of a large set
of M, A, and X elements, it is not practical to include the
band structures and DOS in our presentation even though
they are all available. On the other hand, the DOS at the
Fermi-level N(EF) is a quantitative measure representing the
relative metallic character of the crystals and are included in
the database and our discussion. We also report the effective
charge (Q ) for each element and the BO values between
each pair of atoms. Together with N(EF), these three
parameters exemplify the quintessence of electronic
structures. They are discussed below.
The BO measures the relative strength of a bond between
two atoms. The TBO of a crystal is the sum of all the BO
values in that crystal. When the TBO is divided by the
volume of the crystal, the TBOD is obtained. The MAX
phases have a layered structure and it is of great interest to
ascertain how the bonding pattern evolves between the
layers and their variations with n. There are four types of BO
in the MAX phases or the PBOD, MX, MA, MM, and
AA with the MX bonding dominating. The TBOD values
for the AA bonds are quite small and depend on the
particular MAX phase. Although detailed quantitative
information on the BO values for each MAX phases are
all available, it is not practical or necessary to present them in
detail. Instead, we show in Fig. 5 the percentages of each
bonding type to the TBO for 211, 312, 413, and 514 carbides
(ad, respectively) and the nitrides (eh, respectively) in
the form of pie charts. There is considerable difference in
the contributions to the TBO in the carbides and nitrides. The
carbides have noticeably larger contributions from the MX
pairs than the nitrides. On the other hand, the nitrides have
signicantly larger contributions from the MA pairs.
Contributions from the bonding in the M layer (MM
bonding) appear to be slightly higher in the nitrides. The
AA bonding contributes the least and appears to be slightly
larger in the carbides.
As n increases the MX TBO percentage increases in
both the carbides and nitrides since the fraction of the A
layers systematically decreases as n increases. It should also
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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
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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

Figure 4 Poissons ratio maps for all the

MAX phases according to M (y-axis) and A (xaxis) elements. Left column for carbides and
right column for nitrides. Color in the box
represents calculated G/K values as indicated
in the color bar. Stars in the box indicate this
phase has been synthesized. The sign stands
for elastic instability and the  sign indicates
the phase is screened out for thermodynamic
instability due to positive heat of formation.

charge in the neutral atom represents the charge transfer DQ

for this atom. Positive values represent charge loss, whereas
negative values indicate charge gain. Note that these values
should not be confused with the popular notion of chemical
valence. Figure 6 displays DQ in all 665 screened MAX
phases. The top panel is for carbides; the lower for nitrides.
Within each stacked panel of four segments (211, 312, 413,
and 513) from left to right, the vertical axis represents the
charge transfer values DQM, DQA and DQX, respectively,
and the horizontal axis stand for the columns of M series in
the sequence of Al-Ga-In-Tl-Si-Ge-Sn-Pb-P-As-S for the A
elements within each column. Admittedly, this is a busy
gure that warrants very careful analysis, but this is also the
best way to present all the data points in a concise gure
showing the overall trends in charge transfer.
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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.

As can be seen in Fig. 6, all the M atoms lose electrons to

the A and X elements but the magnitudes of DQ depend on
the specic MAX phases. DQM, Sc has the largest loss of
charge whereas, Nb, Cr, and Mo, which have half-lled 3d or
4d electrons, lose relatively small amounts of charge. All the
rest of the M elements have comparable loss of charge.
Loss of charge in M also depends on the specic A and X
elements. In carbides (top panels), DQM is more scattered
with A in 211 MAX but become smoother as n increases and
the structure approaches that of a binary compound. The
DQA remains quite scattered for all n. In the Sc-based MAX,
DQA becomes smaller (smaller negative number) as n
increases, while for other M elements, it remains pretty much
the same. As expected, the DQX is the least affected by the A
elements since they are screened by the M layers. Another
observation is that DQ values in carbides and nitrides
are quite similar. Striking difference can only be seen in the
Sc-based MAX phases for DQA. In nitrides, DQA slightly
increases with n but the trend is opposite in the carbides
where a large increase is observed with increasing n. A
smaller charge gain by the A elements in the Sc-based MAX
carbides is noted when n increases without apparent changes
in M and C, indicating a softening of the MA bonds. This
plethora of DQ variations is a testimony to the complexity of
the electronic structure and bonding in this remarkable class
of ternary compounds. It also accentuates the need for a large
database that can expose a complete overview of charge
transfer effect in these phases. For specic details of each
types of MAX phases, we must resort to the band structure,
the DOS and PDOS of each individual MAX crystal,
something that we are avoiding in this paper.
The DOS at the Fermi level (EF) or N(EF) is a crucial
parameter for metallic systems. In MAX phases, N(EF) is a
strong function of composition. Some values are close to
zero, whereas others are quite large. The calculated N(EF) is
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

found to be reasonably correlated with the total valance

electron number per volume (Nval (3) as presented in
Fig. 7. The total valance number is calculated as the sum of
the formal valance electrons of individual atoms in the
crystal. In general, the larger the Nval (3) the larger is N
(EF) as expected. Also, as n increases, Nval (3) increases,
and the slope of the data distribution decreases.
In general, the nitrides have larger N(EF) than the
carbides. The Sc-based carbides are a notable exception.
They have signicantly higher N(EF) than their nitride
counterparts. The Sc-based carbides (solid symbols), but not
the nitrides (open symbols), also show a marked deviation
from the trend of N(EF) versus Nval (3) with increasing n.
The approximate positive linear correlation between the two
properties becomes more pronounced with increasing n.
To some extent, one can relate this linear trend to a
similar behavior observed in the binary mono-carbides or
nitrides [1]. We should point out a real distinction here with
respect to the MAX phases due to the profound role of A,
which is absent in binary mono-carbides/nitrides. The
presence of the A element appears to signicantly lessen
the degree of the linear correlation or the increase in the
scattering of the data (see Fig. 7 for MAX 211). It is only
at higher n values, where the A content is reduced and
consequently the bonding characteristics are less inuenced
by A, that a stronger correlation between the two properties
emerges (see Fig. 7 for MAX 514), mimicking those of
binary mono-carbides/nitrides. However, this lessening role
in A with higher n values is not always the norm. As shown
previously with respect to the C44/C66 as well as for shear
modulus G, the inuence of A remains quite high even with
MAX phases of higher n values. For the electronic structures
of a specic MAX compound, detailed band structures, DOS
and PDOS, which are all available from us upon request
must be individually analyzed.
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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).

Some researchers have tried to nd correlations between

the valence electron concentrations (VEC) and the Cijs.
However, VEC is not the same as Nval, since it does not
take into account the unit cell volume. For example, Wang
and Zhou [57] reported a linear positive correlation between
C44 and VEC in the M2AlC phases. Our expanded evaluation
for a similar correlation on all of the MAX carbide phases
did not verify the existence of such a positive correlation.
There are apparent scatters in the data precluding a linear
relationship especially for low n carbide phases (see
Supplementary Fig. S6 in SM).
www.pss-b.com

Similar to the case of N(EF), we found that the MAC

phases with higher n values seems to exhibit a better linear
correlation, presumably due to the reduced effect of A.
Unlike MAC, the MAN phases tend to deviate from this
positive correlation. In fact, we see no evidence that such a
positive correlation between C44 and Nval nor Nval (3) that
can be rmly established. This nding is quite consistent
with the apparent lack of a trend between G and K in the
MAN phases. That is, there is a signicant portion of MAN
phases that possess much lower values of G, despite of their
high K values. The only exception to this rule appears to be
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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.

the Sc-based phases where the linear correlation is quite

apparent irrespective of the types of n, A or X used. We
postulate that this could be due to the absence of d-electrons
in Sc, limiting the contribution of pd hybridization in the
Sc-containing MAX phases.
3.3 Correlations between mechanical properties
and electronic structure In the two preceding subsections, the elastic properties and the electronic structures
of 665 MAX phases were discussed separately. In this
subsection, we try to establish correlations between the two,
a nontrivial exercise rendered more difcult because: (i) of
the layered nature of the MAX phases and (ii) vast amount of
data available, and (iii) the diverse properties explored. Here,
we try to meet this challenge by making use of the vast
amount of high quality data and various correlation plots. As
pointed out above, TBO or TBOD is a good measure of
the strengths of the crystal. In principle, the latter should
correlate with elastic properties. As already pointed out
above, the TBO and TBOD can be further resolved into
partial components of different pairs of bonds (MM, MA,
MX, and AA). The partial BO values are especially
illuminating for crystal cohesion in relation to atomic scale
geometry of different atomic species in the crystal. In Fig. 5,
we showed that the MX BO dominate the bonding (48
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

81%) followed by the MA BO (1537%) and MM BO

(5.911.4%) depending on n and X. Although the AA
bonds have small contributions and the AX bonds
apparently do not form, there are some MAX compounds
where the BO values of the AA bonds are actually higher
than the corresponding MA bonds especially when A is Al
or In.
In the MAX structure (Fig. 1), there are interlayer bonds
and intra-layer bonds; the latter are neither aligned in the
axial direction or in the basal plane. It follows that a portion
of the interlayer MX bonds are inclined in a direction
favoring stiffness along the basal plane. On the other hand,
interlayer bonds between M and A are more inclined toward
the c-axis, enhancing the stiffness along the [0001] direction.
The degree of inclination of the weak or strong bonds will
have an inuence upon the stiffness values along the c-axes
or the ab plane. Thus atomic arrangements together with the
chemical diversity lead to complex correlations between
bonding and elastic properties discussed below.
Based on the extensive data obtained, we plotted 160
correlations plots of C11, C33, C44, C66, K, G, E, and
Poissons ratio against the TBOD and its MX, MA, MM,
and AA components for n 14. Such extensive correlation plots (not shown) enabled us to identify any existing
correlations (or lack thereof) between the elastic properties
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Phys. Status Solidi B 251, No. 8 (2014)

with the electronic structures embodied in the TBOD or its

partial components. Figure 8 plots K (left panel) and G (right
panel) versus TBOD in the 211, 312, 413, 514 MAC and
MAN compounds, respectively. It is evident that K correlates
with TBOD better than G. This is not too surprising since K
is a measure of the resistances to change in BL, which is
directly related to BO values. We also note that the TBODs
of the nitrides are larger than those of the carbides. Closer
observation reveals that for n > 2, there are roughly four
groups of correlated bands, two for the carbides and two for
the nitrides based on TBOD. The MAX phases based on Sc,
Zr, Hf, and Nb have smaller TBODs than those of Ti, V, Cr,
Mo, Ta, and this trend becomes more evident as n increases.
This is mainly due to the nature of denition of the MB
adopted for these two groups. The atoms in the second group
do not contain the empty valence shell p-orbitals in the MB
in order for the MB to be more localized. Nevertheless, the
generally positive trend that links the TBOD with K remains
quite evident. Some of the trends on the elastic property
correlations in a more limited MAX 211 phases have also
observed by Cover et al. [60].

1491

In Fig. 9, we plot K against the MA (left panel) and MX

(right panel) portions of the TBODs. It is apparent that the
correlation with MA BOD is far better than the correlations
with TBOD shown in the left panel of Fig. 8. Also K is better
correlated with the MA than the MX TBOD, even though
the contribution from MA bonds to the TBOD is smaller than
that MX. The approximate slope of the linear correlation
increases with increasing n. This nding again points to the
important role played by element A in all MAX phases.
There are also strong correlations between the elastic
constants and the TBODs, which are shown in gures in SM.
Supplementary Figure S4 shows such correlation for C11
(left column) and C33 (right column) with TBOD. The
difference in the degree of correlations reects the difference
in the bonding related to planer and axial components of the
elastic tensor elements. In Supplementary Fig. S5, we show
similar plots for C44 (left column) and C66 (right column)
showing a similarly positive correlation with TBOD with all
n; the latter however have more scatters with some MAX
phases actually exhibit a negative correlation, e.g., Cr-based
MAN phases (see highlighted dotted lines).

Figure 8 Correlation plots of: (left) bulk and

(right) shear moduli versus TBOD for all
MAX phases.
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S. Aryal et al.: A genomic approach to stability and properties of the MAX phases

Figure 9 Correlation plots of bulk modulus

(K) versus (left) MA part of the TBOD and
(right) MX part of the TBOD for all MAX
phases.

4 Data-mining approach The complete data set on

665 MAX phase properties enables us to test the efcacy of
data-mining statistical learning approach being applied to
materials property predictions [6365] that has been quite
popular in recent years. The success of data mining method
is predicated upon the use of statistical tools to recognize
patterns among multivariate data sets. In particular, we
employed on one of the simplest data-mining approach, i.e.,
the multiple linear regression y w0 w1 x1 w2 x2
   wk xk whereby the weight (wi) of each linear factor (xi) is
estimated from a designated training set. We applied this
approach as implemented in a well-known data-mining code
WEKA [66] to obtain a linear pattern that links the complex
mechanical properties as a function of a combination of
electronic structure factors. From the previous sections, it is
quite clear that while TBOD yields correlations with a
variety of elastic properties, this correlation is often times
also marked by data scatters that may indicate no single
electronic factor alone can be used to predict these elastic
properties. The statistical methodologies employed in this
data mining approach allow us to construct an empirical, but
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

quantitative, formula that links properties of interest. It

further enables us to test the strengths of correlation between
properties. Of particular interest here is the link between bulk
modulus and Poissons ratio and electronic structures. We
should note that the DFT calculations on these mechanical
parameters can be quite time-consuming whereas those for
the electronic structure, on the other hand, can be acquired
quite readily depending on the method of calculation. Thus,
if a correlation can be established, then one may be able to
utilize this new approach as an expedited route to obtain
information related to mechanical properties solely based on
electronic structure properties. For this purpose, we used the
entire database wherein, 50% of the data set was used as a
training set to predict K and Poissons ratio for the other
50%. We employed only the electronic structure factors as
the variables to predict K and Poissons ratio. Table 1 lists
the coefcients of the linear superposition of these factors
that have been optimized to predict the two properties.
Figure 10 (left panel) shows the comparison between K
obtained from ab initio calculations versus those obtained
from the formulas derived from the data-mining algorithm
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Phys. Status Solidi B 251, No. 8 (2014)

1493

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

relative contributions of each of the electronic structure

factors used to predict K. We further identied the four most
important factors, viz. TBOD, MA BOD, MX BOD, and
the charge transfer for the X elements consistent with those

Figure 10 Left panel: Comparative plots of

bulk modulus from ab initio DFT calculations
versus that from data-mining algorithm
using half of randomly chosen MAX phases:
(a) 211, (b) 312, (c) 413, and (d) 514. In each
panel on the left, there is a pie-chart inset
showing the average relative contributions
of each electronic structure factors to the
predicted bulk modulus based on the datamining algorithm. Right panel: Similar comparative plots for the Poissons ratio: (e) 211,
(f) 312, (g) 413, and (h) 514 MAX phases.

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already discussed in Section 3.3. Based on the coefcients

listed in Table 1 and the pie charts (Fig. 10), TBOD clearly
stands out as the most important factor in determining K for
all MAX phases. Figure 10 (right panel) shows the similar
prediction for Poissons ratio using the similar procedure.
Although it is less impressive than that for K, the prediction
for the Poissons ratio obtained from data mining is still
reasonably good, with correlation coefcients around 80%
or higher. In addition, as shown in Table 1, one can also see
that the Poissons ratio is also strongly affected by the TBO
although it is a negative correlation unlike the positive one
exhibited by K. The linear correlation is less denitive
probably due to the fact that Poissons ratio as well as the
G/K ratio are more inuenced by the nature of the A element,
an effect that apparently is not fully represented by the a
linear combination of electronic structure parameters used in
this analysis. It is possible that there should be a nonlinearity
in the regression model better suited for the Poissons ratio.
Nevertheless, a reasonably good estimate on these two
properties can indeed be established solely from a linear
combination of electronic structure factors. Furthermore, the
TBDO emerges as a signicant variable that controls these
elastic properties in agreement with the nding from the
previous sections. This data mining approach also demonstrates that a simple correlation can be quantied to link
elastic parameters such as Poissons ratio or the Pugh ratio to
a series of electronic structure indicators. Further, the use of
only 50% of the data as a training set gives credence to the
particular machine learning software and the philosophy
lying behind it. To some extent the success can be explained
by the nature of our database and the strategy we employed
to establish the database. In general, the data mining
method that is applied to materials property predictions
utilizes a heterogeneous set of databases extracted from
various different sources experimentally or computationally.
In our case, we employed a well-tested DFT-based approach
to generate the required large database with a systematic
compositional variation in M, A, X, and n.
5 Special analysis of outliers The completeness of
the MAX database encompassing a wide combination of M,
A, and X affords us the unique capability to identify certain
phases that qualify as outliers. For some of these outliers, we
further evaluated their thermodynamic stability at the ground
state.
One of our objectives in this study is to identify
compounds with relatively low G/K ratios. In addition, we
also focus on the Sc-based MAX phases due to their unique
elastic and electronic properties as already detailed in
the previous sections. For these two objectives, we have
extended our evaluation on the relative stability of the MAX
phases to include their neighboring binary and/or ternary
phases. The thermodynamic information on the competing
phases were obtained from the ground-state thermodynamic
calculations and the lattice stability analysis follows the
implementation of the Calphad method [67]. Since no
temperature and its effect on the Gibbs free energy are
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

included in this thermodynamic consideration, we have

allowed a small positive enthalpy variation (SH  0.05 eV
atom1), to reect the contribution from the vibration
energy, which is not included in the calculations. Using this
simplied approach, we were able to identify examples of
possibly stable MAX phase outliers showing relatively low
G/K as well as a number of Sc-based MAX phases. They are
listed in Table 2. None of these phases has been synthesized
to the best of our knowledge. Certainly, there are other
methodologies by which outliers can be identied which are
beyond the scope of this paper. We do want to stress that
the ability to identify outliers effectively is based on the
capability to generate a sufciently large database from
which an unusual deviation from the norm can be detected.
Our approach here is unique in that regard since we used only
one methodology to furnish all of the elastic properties of the
MAX phases. While the accuracy of materials properties
obtained using the DFT calculations is crucial as demonstrated in our previous study [58], the real benet of using this
singular methodology is to avoid complications arising from
variations in data due to different methodologies employed.
Such variations can potentially be large enough to mask the
identication of outliers. We should also point out that by no
means these identied outliers are reective of an exhaustive
search of the outliers. It only serves to demonstrate that with
the availability of a large database set for MAX phases with
possibly unique properties can be more readily identied and
examined further.
6 Summary and conclusions In this paper, we
conducted an extensive investigation on the Mn1AXn
phases with n varying from 1 to 4. The focus is on the elastic
properties and electronic structure and the correlations
between the two. Based on a carefully designed screening
strategy, the data for 669 MAX compounds are obtained and
made available to all readers. In spite the anisotropic
structure, and related complications, a wide range of elastic
properties and electronic structures were calculated and
trends and correlations between them established. Most
importantly, the elusive correlations between these two
classes of properties are captured. From these correlations,
possible new MAX phases with some unique properties that
have never been synthesized have been identied and their
thermodynamic stability assessed. This was only possible
because of the large and credible database we developed.
Based on this database, we tested the efcacy of the genomic
approach of data mining and concluded that this approach
is promising, especially if the integrity and quality of a
sufciently large data base is carefully scrutinized. This
approach enables us to use a faster screening route based on
easily calculated properties on much larger samples of
potential candidates and predict other properties that are
either too onerous to evaluate or too expansive to measure
experimentally. The massive amount of data and the
scattered nature of the properties calculated require an
innovative way in presenting these results without consuming an unacceptably large amount of journal space. To that
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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

3Mo2C 2MoGe2 C 4Mo2GeC

TiC TiAs Ti2AsC
Ta2C TaC TaGe2 2Ta2GeC
Ta2C 3TaC TaGe2 2Ta3GeC
Tl Sc 2ScN Sc3TlN2
8ScN 2Sc3InN ScIn3 5Sc3InN2
8Sc4C3 2Sc15C19 31ScS 31Sc3SC2
Sc5Sn3 2ScSn2 14ScN 7Sc3SnN2
ScAl 2ScN Sc3AlN2
ScS 2ScN Sc3SN2

effect we present them in maps mimicking the Periodic

Table or in correlation plots with data representing individual
MAX compounds clearly identiable. Such visual presentation of large data set is important in facilitating the rapid
dissemination of main correlations and a deeper comprehension of the properties of MAX phases.
In conclusion, we have established the following trends
and correlations that to date had not been well recognized
or sufciently elaborated in the literature due to the lack of
a comprehensive data set. We conclude that: (i) there are
marked differences between the elastic and electronic
properties of the carbides and nitrides; (ii) there are clear
trends in the properties and variations with increasing n. This
trend is intimately related to the dependence on the single
layer of element A; (iii) the Sc-based carbides stand out in
the nine metallic elements in its properties and correlations,
which is related to the total valence electron density and the
Fermi level position which lies below the pseudo gap in the
DOS; (iv) general trends in the charge transfer among M, A,
and X elements, although quite complex, are established.
All M atoms lose charge to the A and X elements; (v) the
importance and usefulness of using the concept of TBOD
and partial TBOD has been fully demonstrated; (vi) With
the notable exception of the Sc-based carbides, a simple
correlation exists between N(EF) and the density of valence
electrons, rst pointed out by Barsoum [1] is afrmed;
(vii) The unique role of the A layer in MAX compound is
emphasized regardless of n; (viii) We have also established
several major correlations between elastic properties and
electronic structures among themselves and between the
two. The most important ones include: (i) correlations of C11
versus C33 and C66 versus C44 and (ii) correlations or lack
thereof between: K, G, E, h, G/K, C11, C33, C44, C66 and
electronic properties in the forms of TBOD and their
components for different n values.
We have also tested and validated the data-mining,
machine learning approach, and algorithms using our data
set as inputs. The most important parameter in the electronic
structure in predicting the elastic properties is the TBOD of
the crystal. We further identied ten outliers with unusual
properties that are thermodynamically stable against their
competing phases.
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0.05216
0.02150
0.03134
0.00045
0.20233
0.01623
0.00272
0.05022
0.01350
0.00185

The present work focuses on two properties, elastic

properties, and electronic structures. There are many other
properties such as vibrational, spectroscopic, transport,
corrosion resistance, electric conductivity, superconductivity, thermo-conductivity etc. just to mention a few, which are
all intimately related to the electronic structures and some to
the elastic properties. It is possible to extend the genomic
approach used here to explore these properties. Some of
these are currently in progress. Moreover, the current
database covers only the Mn1AXn phases with n 14
comprising 11 M elements and 9 A elements. It is possible to
expand this list to include the early transition metals such
as La, W and Sb, and Bi, Se and Te for the A elements, to
further enlarge the data base. Very recently, with the
discovery of Mn2GaC [68], Mn can now be added to the list
of M elements. Another fruitful route is to consider solid
solutions between some of the more promising MAX phases,
which can further optimize properties. Another direction is to
investigate the materials beyond the MAX phases to those
of its derivations such as MXenes [69, 70] or articial
MAX-like layered structures by inserting multiple layers of
selective A elements into the MX layers of the MXenes.
The time is also ripe to extend such studies to defects and
microstructures in MAX phases using a similar approach.
There are endless opportunities for future work that all
originate from this fascinating class of ternary intermetallic
compounds, the MAX phases.
Finally, the strategy used in this work can be applied to a
wider range of crystal structure prototypes whereby the
abundance in experimental and/or theoretical database is
absent and thus, correlations amongst their materials
properties cannot be readily obtained. By evaluating the
effect of various constituents of the crystal structure
systematically, these trends can potentially be identied
and further rened. Furthermore, such a strategy, a genomic
approach, can also be used to assist the identication of
outliers.
Acknowledgements This work was supported by National
Energy Technology Laboratory (NETL) of the U.S. Department of
Energy (DOE) under Grant No. DE-FE0005865. This research
used the resources of the National Energy Research Scientic
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solidi

status

physica

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1496

S. Aryal et al.: A genomic approach to stability and properties of the MAX phases

Computing Center (NERSC) supported by the Ofce of Basic

Science of DOE under Contract No. DE-AC03-76SF00098. M.W.
B. was partially supported by DMR-1310245.

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