Equiatomic quaternary Heusler alloys: A material perspective for spintronic

applications
Lakhan Bainsla, and K. G. Suresh

Citation: Applied Physics Reviews 3, 031101 (2016);

View online: [Link]
View Table of Contents: [Link]
Published by the American Institute of Physics

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 APPLIED PHYSICS REVIEWS 3, 031101 (2016)

APPLIED PHYSICS REVIEWS—FOCUSED REVIEW

Equiatomic quaternary Heusler alloys: A material perspective for spintronic

applications
Lakhan Bainslaa),b) and K. G. Suresha)
Magnetic Materials Lab, Department of Physics, Indian Institute of Technology Bombay, Mumbai 400076, India
(Received 28 March 2016; accepted 5 July 2016; published online 22 July 2016)
Half-metallic ferromagnetic (HMF) materials show high spin polarization and are therefore
interesting to researchers due to their possible applications in spintronic devices. In these materials,
while one spin sub band has a finite density of states at the Fermi level, the other sub band has a
gap. Because of their high Curie temperature (TC) and tunable electronic structure, HMF Heusler
alloys have a special importance among the HMF materials. Full Heusler alloys with the
stoichiometric composition X2YZ (where X and Y are the transition metals and Z is a sp element)
have the cubic L21 structure with four interpenetrating fcc sublattices. When each of these four fcc
sublattices is occupied by different atoms (XX0 YZ), a quaternary Heusler structure with different
structural symmetries (space group F-43m, #216) is obtained. Recently, these equiatomic
quaternary Heusler alloys (EQHAs) with 1:1:1:1 stoichiometry have attracted a lot of attention due
to their superior magnetic and transport properties. A special class of HMF materials identified
recently is known as spin gapless semiconductors (SGS). The difference in this case, compared
with HMFs, is that the density of states for one spin band is just zero at the Fermi level, while the
other has a gap as in the case of HMFs. Some of the reported SGS materials belong to EQHAs
family. This review is dedicated to almost all reported materials belonging to EQHAs family. The
electronic structure and hence the physical properties of Heusler alloys strongly depend on the
degree of structural order and distribution of the atoms in the crystal lattice. A variety of
experimental techniques has been used to probe the structural parameters and degree of order in
these alloys. Their magnetic properties have been investigated using the conventional methods,
while the spin polarization has been probed by point contact Andreev reflection technique. The
experimentally obtained values of saturation magnetization are found to be in agreement with those
estimated using the Slater-Pauling rule in most of the cases. Electrical resistivity and Hall measure-
ments are being used to distinguish between SGS and HMF nature in detail. The current spin polar-
ization value, P ¼ 0.70 6 0.01, for CoFeMnGe is found to be highest among the EQHAs.
CoFeMnSi and CoFeCrGa are found to show SGS behavior with high Curie temperatures, thus
making them suitable substitutes for diluted magnetic semiconductors. CoRuFeSi is found to have
the highest TC among EQHAs. Theoretical prediction of magnetic properties on the basis of elec-
tronic structure calculations has also been reported in a few systems, which are also discussed in
this review. Thus, this review presents a consolidated picture of the magnetic and spintronic proper-
ties of this important, but relatively new class of Heusler alloys. It is expected that this will stimu-
late further interest in these alloys, thereby paving the way for the identification of more HMF and
SGS materials. As a result of this, it is expected that more efficient spintronic devices using these
alloys would emerge in the near future. Published by AIP Publishing.
[[Link]

TABLE OF CONTENTS CoFeMnZ (Z ¼ Al, Ga, Si, and Ge) alloys . .

A. 4
CoFeCrZ (Z ¼ Al and Ga) alloys . . . . . . . . . .
B. 4
CoRuFeZ (Z ¼ Si and Ge) alloys . . . . . . . . . .
C. 5
I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 D.
CoFeTiAl and CoMnVAl alloys. . . . . . . . . . . 5
II. STRUCTURAL PROPERTIES . . . . . . . . . . . . . . . . 3 E.
CoFeCrGe and CoMnCrAl alloys . . . . . . . . . . 5
NiCoMnZ (Z ¼ Al, Ge, and Sn) alloys. . . . . .
F. 6
a)
G.
NiFeMnGa, NiCoMnGa, and CuCoMnGa
Authors to whom correspondence should be addressed. Electronic
alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
addresses: lakhanbainsla@[Link] and suresh@[Link].
b)
Present address: WPI Advanced Institute for Materials Research, Tohoku H. MnNiCuSb alloy . . . . . . . . . . . . . . . . . . . . . . . . 6
University, Sendai 980-8577, Japan. III. MAGNETIC PROPERTIES . . . . . . . . . . . . . . . . . . 7

1931-9401/2016/3(3)/031101/21/$30.00 3, 031101-1 Published by AIP Publishing.

031101-2 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

CoFeMnZ (Z ¼ Al, Si, Ga, and Ge) alloys . .

A. 7 spintronic applications, as they can give rise highly spin polar-
CoFeCrZ (Z ¼ Al and Ga) alloys . . . . . . . . . .
B. 9 ized currents.1–3 HMF nature was predicted in several types of
CoRuFeZ (Z ¼ Si and Ge) alloys . . . . . . . . . .
C. 9 materials such as magnetic oxides,4 dilute magnetic III-V
D.
CoFeTiAl and CoMnVAl alloys. . . . . . . . . . . 9 compound semiconductors,5 and Heusler alloys.2,3,6 Among
E.
CoFeCrGe and CoMnCrAl alloys . . . . . . . . . . 10 these, Heusler alloys have a special importance due to their
NiCoMnZ (Z ¼ Al, Ge, and Sn) alloys. . . . . .
F. 10 higher Curie temperatures (TC) and tunable electronic struc-
G.
NiFeMnGa, NiCoMnGa, and CuCoMnGa ture.2,3,6 Since the prediction of HMF nature in NiMnSb,6
alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 Heusler alloys have received a special attention due to the rea-
H. MnNiCuSb alloy . . . . . . . . . . . . . . . . . . . . . . . . 11 sons mentioned above. In the large family of Heusler alloys,
IV. MAGNETO-TRANSPORT PROPERTIES . . . . . . 11 generally Co based alloys show relatively high Curie tempera-
A. CoFeMnZ (Z ¼ Si and Ge) alloys. . . . . . . . . . 12 ture and high spin polarization.7–16
B. CoFeCrZ (Z ¼ Al and Ga) alloys . . . . . . . . . . 13 HMF materials have potential applications as spin polar-
C. CoRuFeZ (Z ¼ Si and Ge) alloys . . . . . . . . . . 14 ized current sources for current perpendicular to plane giant
V. SPIN POLARIZATION. . . . . . . . . . . . . . . . . . . . . . . 14 magnetoresistance (CPP-GMR),17–19 magnetic tunnel junc-
A. CoFeMnZ (Z ¼ Si and Ge) alloys. . . . . . . . . . 15 tions (MTJs),20,21 non-local spin-valve (NLSV) devices,22,23
B. CoFeCrAl alloy . . . . . . . . . . . . . . . . . . . . . . . . . 15 and spin injectors to semiconductors.24 High magnetoresis-
VI. ELECTRONIC STRUCTURE tance (MR) ratios and large spin accumulation signals in spin-
CALCULATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . 15 tronic devices using Co-based Heusler alloys clearly reflect the
A. CoFeMnZ (Z ¼ Al, Si, Ga, and Ge) alloys . . 15 half-metallic nature of these alloys.17–24 Recently, a very high
B. CoFeCrZ (Z ¼ Al, Ga, Si, and Ge) alloys . . . 17 value of spin polarization was observed for Co-based alloys at
C. CoMnCrAl, CoFeTiAl, and CoMnVAl low temperatures, but a strong degradation in the transport
alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 properties was seen at room temperature.15,17,19,20 Therefore,
D. NiCoMnZ (Z ¼ Al, Ga, Ge, and Sn) alloys . 18 further exploration of HMF Heusler alloys is strongly required
E. NiFeMnGa and CuCoMnGa alloys. . . . . . . . . 18 both from application as well as fundamental points of view.
F. CoFeTiZ (Z ¼ Si, Ge, Sn, and Sb) alloys . . . 18 Recently, a new class of materials in the HMF family,
G. Other equiatomic quaternary Heusler alloys. 19 namely, spin gapless semiconductors (SGS), has started
VII. SUMMARY AND CONCLUSIONS . . . . . . . . . . 19 emerging and their role is expected to be vital in semicon-
ductor spintronic devices.8,10,25–27 SGS materials possess a
I. INTRODUCTION zero band gap for one spin channel, while a band gap is pre-
sent for the other channel, as shown in Fig. 1(d). Therefore,
Spintronics has emerged as one of the most exciting
these materials can serve as a bridge between the HMFs and
topics of research in the field of magnetic materials in the the semiconductors. Some of the unique properties of SGS
recent past. The interest in this topic is two-fold; applied and are: (i) spin polarized current resulting from electrons as
fundamental. Focus on both these aspects has contributed sig- well as spin polarized holes; (ii) ability to switch between n
nificantly as revealed by the number of publications in the last and p type spin polarized carriers by the application of an
five years. Novel methodologies are being adopted in the electric field; and (iii) almost no energy is required to excite
manipulation of spin degree of freedom of the electrons, electrons from the valence band to the conduction band. Due
which has led to a large number of novel and potential devi- to their unique band structure, SGS materials are considered
ces. The most important class of materials useful in spin- as possible candidates to substitute for diluted magnetic
tronics is the half-metallic ferromagnets (HMFs). The semiconductors (DMS). SGS materials have been receiving
electronic band structure of these materials is different from intense research interest since their theoretical prediction.25
that of typical metals (Fig. 1(a)) and semiconductors (Fig. The major drawback of low Curie temperature in DMS28,29
1(b)). Half-metallic ferromagnetic (HMF) materials possess a can be overcome by SGS materials since relatively high TC
conducting channel for one spin and a semiconducting chan- has been obtained for some SGS Heusler alloys.
nel for the other, as shown in Fig. 1(c). HMF materials with Many Heusler alloys are found to possess the SGS band
100% spin polarization are the ideal candidates for metallic structure as revealed by the ab-initio calculations.8,10,25,27,30–32
But, such a behavior is confirmed experimentally only in a
few of them, i.e., Mn2CoAl,26 CoFeMnSi,8 and CoFeCrGa.10
Very recently, thin films of Mn2CoAl were synthesized to
check its applicability in the devices.33,34
Full Heusler alloys (FHAs), with the stoichiometric
composition X2YZ, where X and Y are the transition metals
and Z is a sp (or main group) element, have the cubic L21
structure (space group Fm-3m, #225) with four interpenetrat-
ing fcc sublattices. When each of these sublattices is occu-
pied by different atoms (XX0 YZ), a quaternary Heusler
FIG. 1. Schematic of density of states for a typical (a) nonmagnetic metal,
(b) semiconductor, (c) half-metallic ferromagnet, and (d) spin gapless semi-
structure with a different structural symmetry (space group
conductor. Reprinted with permission from Bainsla et al., Phys. Rev. B 91, F-43m, #216) is obtained. The resulting structure is named
104408 (2015). Copyright 2015 American Physical Society. as LiMgPdSn type (or the so called Y-type structure as per
031101-3 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

disorder in the structure can alter the electronic structure dis-

tinctly. If each of the elements resides at their respective sites,
the resultant will be a well-ordered cubic structure. Several types
of disordered structures have been observed in Heusler alloys.
Some of the possible disordered structures in FHA and/or
EQHA are termed as A2, DO3, and B2 structures.37 The com-
plete disorder in FHA and/or EQHA structure (X, X0 , Y, and Z
distributed randomly) results in the A2 structure with reduced
symmetry and bcc lattice. On the other hand, the random distri-
bution of X and Y or X and Z leads to the DO3 disorder which
results in a BiF3-like structure. B2 type is another frequently
observed structure, in which Y and Z sites become equivalent,
i.e., the disorder is between Y and Z sites only, which leads to a
CsCl-like structure. The crystal structures corresponding to vari-
ous types of structures are given in Fig. 2. Table I summarizes
the various possible disorders [as per Inorganic crystal Structure
Database (ICSD) and Strukturberichte (SB) Database] in the
case of FHA and/or EQHA. Generally, it has been observed that
a highly ordered crystal structure is essential to have a half-
metallic electronic structure.2,37,38
Structural disorder and its determination: As men-
FIG. 2. An overview of the different types of crystal structures in Heusler tioned above, the electronic structure and hence the physical
alloys. Blue, violet, yellowish green, and green circles represent the 4a(0, 0, properties strongly depend on the structural order and distri-
0), 4b(1/2, 1/2, 1/2), 4c(1/4, 1/4, 1/4), and 4d(3/4, 3/4, 3/4). Considering
bution of the atoms in the crystal lattice. Thus, a careful anal-
X@4c(1/4, 1/4, 1/4), X’@4d(3/4, 3/4, 3/4), Y@4b(1/2, 1/2, 1/2), and
Z@4a(0, 0, 0) for an EQHA with Y-type structure. ysis of the crystal structure is required to understand or even
predict the properties of these materials. The band structure
Strukturberichte database). Depending on the occupation of calculations show that even a small amount of atomic disor-
the different lattice sites, three different types of structural der can cause changes in their electronic structure and their
configurations are possible for the Y-type structure.31,35 A magnetic and transport properties.38–40
simple method to conceive a quaternary Heusler alloy such X-ray diffraction (XRD) technique is the easiest experi-
as ABCD with 1:1:1:1 stoichiometry is to consider it as the mental method to examine the crystal structure. In the case
combination of two ternary full Heusler alloys A2BD and of an ordered L21 phase, superlattice reflections (SRs) (111)
A2CD. Because of the 1:1:1:1 stoichiometry, the quaternary and (200) are usually present in the XRD data. A rough esti-
alloys are termed as equiatomic quaternary Heusler alloys mate of chemical order present in the materials can be
(EQHAs). From the application point of view, EQHAs have obtained by calculating the I200/I220 and I111/I220 intensity
some advantages over pseudo-ternary alloys such as ratios. The intensity of the superlattice reflections (111) and
X2Y1aY0 aZ, since the random distribution of Y and Y0 leads (200) is proportional to the order parameters, S2 and
to an additional disorder scattering and thus the spin diffu- S2(12a)2, where S ¼ ((I200/I220)Exp./(I200/I220)Theory)1/2 and
sion length becomes very short.36 Since such a scattering is S(12a) ¼ ((I111/I220)Exp./(I111/I220)Theory)1/2.41 In the case of
absent in EQHAs, the devices based on the EQHAs are A2 disorder, S ¼ 0 and a ¼ 0, and for B2 disorder, S ¼ 1 and
expected to have low power dissipations. a ¼ 0.5. For a well ordered cubic phase, S ¼ 1 and a ¼ 0 are
In the following, a brief review of the structural, mag- expected.
netic, magneto-transport, spin polarization, and electronic When Z element is from the same period as the transi-
structure properties of EQHAs is presented. tion metals, it is very difficult to find out the correct structure
unambiguously by using x-ray or neutron diffraction data.42
II. STRUCTURAL PROPERTIES
In such cases, XRD investigations with synchrotron radiation
Physical properties of Heusler alloys are strongly depen- lead to better structural results, which allow the direct obser-
dent on the atomic arrangements in the crystal. A slight vation of the anti-site disorder. M€ossbauer spectroscopy
TABLE I. Site occupancy, general formula, and structure type (according to different databases) for different atomic orders of Heusler alloys. Space groups
corresponding to various structures are also given.

Site occupancy General formula Structure type (ICSD) Structure type (SB) Space group

X, X0 , Y, Z XX0 YZ LiMgPdSn Y F-43m (#216)

X ¼ X, Y, Z X2YZ Cu2MnAl L21 Fm-3m (#225)
X ¼ X0 , Y ¼ Z X2Y2 CsCl B2 Pm-3m (#221)
X ¼ X0 ¼ Y, Z X3Z BiF3 DO3 Fm-3m (#225)
X ¼ X0 ¼ Y ¼ Z X4 W A2 Im-3m (#229)
031101-4 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

(MS) is another technique which can be used for structural of the fitting procedures used in these techniques. The struc-
investigations, as it measures the hyperfine field (Hhf) at the tural stability of the CoFeMnZ (Z ¼ Si and Ge) alloys was
core M€ ossbauer active atoms such as Fe.43 The nature of the checked by Bainsla et al.,7,8 by performing the differential
obtained spectra indicates the local environment of the thermal analysis (DTA) in the temperature range of
probed atomic species. Extended x-ray absorption fine struc- 400–1450 K. There was no structural transition in the DTA
ture (EXAFS) analysis is another technique, which has been curves for both the alloys. The absence of (111) peak in the
successfully applied to investigate Heusler materials. It XRD pattern of CoFeMnAl indicates the presence of B2 dis-
determines the short range chemical order around the atoms. order as shown by Alijani et al.45 Further studies are needed
For example, Co2MnSi is predicted to be HMF from band to explore the crystal structure of CoFeMnGa as no conclu-
structure calculations in the ordered state; however, EXAFS sions were made by them45 on the basis of room temperature
analysis revealed a distinct amount of disorder between the XRD data. The results obtained from various measurements
Co and the Mn site, which can be the reason for the low mea- are summarized in Table II.
sured spin polarization.44
B. CoFeCrZ (Z 5 Al and Ga) alloys
A. CoFeMnZ (Z 5 Al, Ga, Si, and Ge) alloys
Bainsla et al.9 found that CoFeCrAl alloy exists in B2-
CoFeMnZ (Z ¼ Al, Ga, Si, and Ge) alloys are found to type cubic Heusler structure as revealed by the room temper-
exist in the Y-type structure.45 The room temperature pow- ature powder XRD analysis shown in Fig. 3(c). Absence of
der XRD patterns of CoFeMnZ (Z ¼ Si and Ge) are given in (111) in the XRD pattern indicates that the alloy exists in
Figs. 3(a) and 3(b). Alijani et al.45 found some amount of B2-type structure. Luo et al.47 and Nehra et al.48 also
structural disorder for CoFeMnAl and CoFeMnSi from x-ray observed the B2-type structure for CoFeCrAl on the basis of
diffraction measurements, while it is not confirmed for XRD and M€ossbauer analysis. The degree of long range B2
CoFeMnGe and CoFeCrGa due to similar scattering ampli- order (SB2) was roughly estimated by Bainsla et al.9 and it
tudes of the constituent elements. To further investigate the was found to be 0.89 from the intensity ratio of (200) peak
crystal structure of CoFeMnZ (Z ¼ Si and Ge) alloys, and (400) fundamental peak.49 Such a large value indicates
Bainsla et al.7,8,46 performed EXAFS measurements46 and the presence of a highly ordered B2 structure. The XRD
found large structural disorder in the case of CoFeMnSi, results of Bainsla et al. are found to be in good agreement
while CoFeMnGe was found to exist in well ordered Y- with the reports by Luo et al.47 and Nehra et al.48
phase. Room temperature 57Fe M€ossbauer analysis also CoFeCrGa alloy is found to exist in the Y-type structure
revealed a large structural disorder (DO3) for CoFeMnSi.8 as revealed by the room temperature powder XRD {as given
Some amount of disorder was also obtained for CoFeMnGe in Fig. 3(d)} and M€ossbauer analysis.10 The lattice parameter
from the room temperature M€ossbauer analysis,7 which was of this alloy is found to be 5.79 Å. The superlattice reflec-
contradictory to the EXAFS measurements.46 Exact quantifi- tions [(111) and (200)] were found to absent in the XRD pat-
cation of the disorder using the M€ossbauer or the EXAFS tern due to the nearly equal scattering amplitudes of the Co,
technique is not possible because of the inherent inaccuracies Fe, Cr, and Ga. It is not necessary that the absence of SR in

FIG. 3. Room temperature powder

x-ray diffraction patterns of some
EQHAs. (a) and (b) show the pattern
obtained for the CoFeMnX (X ¼ Si and
Ge) alloys. The inset in Fig. (b) shows
the zoomed version in the region of
26 –33 . (c)–(f) show the patterns for
CoFeCrAl, CoFeCrGa, CoRuFeSi, and
CoRuFeGe, respectively. Data taken
from References 7, 8, 9, 11, and 52.
031101-5 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

TABLE II. Structure type, crystal structure (ordered/disorder), experimental same scattering amplitudes of all the sites. The lattice param-
lattice parameter (aexp.), space group, and corresponding references for vari- eter values of 5.77 and 5.87 Å were obtained for CoRuFeSi
ous EQHAs.
and CoRuFeGe, respectively.
Crystal Bainsla et al.11 further investigated the crystal structure
structure of these alloys by performing the room temperature 57Fe
Structure (ordered/ aexp. Space M€ossbauer spectroscopic analysis. The best fit to the
Alloy type disorder) (Å) group Reference M€ossbauer data was obtained with two sextets (S1 and S2)
CoFeMnAl Y B2 disorder 5.79 F
43m 45 for both the alloys. From this, it was found that both the
CoFeMnSi DO3 disorder 5.66 8 and 45 alloys are fully ferromagnetic (FM) at room temperature as
5.66 no doublet was seen in the M€ossbauer spectra. The cubic
CoFeMnGa To be probed 5.81 45 symmetry in the alloys was confirmed by almost vanishing
in detail values of quadruple shift. In the case of CoRuFeSi, Hhf val-
CoFeMnGe Ordered (Y-type) 5.76 7 and 45 ues of 298 and 314 kOe with relative intensities of 76% and
CoFeCrAl B2 disorder 5.76 9, 47, and 48
24% were obtained for S1 and S2, respectively, while in the
CoFeCrGa DO3 disorder 5.79 10
case of CoRuFeGe, Hhf values of 307 and 328 kOe with rela-
CoFeCrGe Ordered (Y-type) 5.77 52
CoFeTiAl Ordered (Y-type) 5.85 51
tive intensities of 88% and 12% were obtained for S1 and
CoMnVAl Ordered (Y-type) 5.80 51 S2, respectively. The presence of two sextets for both the
CoMnCrAl L21 disorder 5.76 52 alloys indicates the presence of chemical disorder in the unit
CoRuFeSi B2 disorder 5.77 11 and 50 cell. The obtained Hhf values from the fit suggest that Fe also
CoRuFeGe B2 disorder 5.87 11 occupies Z site, which results in the B2 type crystal structure.
NiCoMnAl B2 disorder 5.79 54 The intensities of S1 and S2 were attributed to the Y and B2
NiCoMnGe Ordered (Y-type) 5.78 54 phases, respectively, for CoRuFeSi and CoRuFeGe. Both the
NiCoMnSn Ordered (Y-type) 54 alloys were found to be reasonably ordered at room tempera-
NiCoMnGa To be probed 5.80 55 ture, as revealed by the relative intensities of S1 and S2.
NiFeMnGa in detail 5.80 55
Therefore, it was concluded that the substitution of Ru in
CuCoMnGa 5.85 55
place of Mn in CoFeMnZ (Z ¼ Si and Ge) [which results in
MnNiCuSb Ordered (Y-type) 5.92 56
CoRuFeZ] improves the chemical ordering in these alloys.11
The results of the structural analysis for these alloys are
such cases is due to the presence of structural disorder, as given in Table II.
discussed above in the case of Co2FeZ (Z ¼ Al, Si, Ga, and
Ge) alloys.42 To further investigate the crystal structure of D. CoFeTiAl and CoMnVAl alloys
CoFeCrGa, Bainsla et al.10 performed room temperature Structural details of these alloys were obtained by Basit
57
Fe M€ ossbauer spectroscopic measurements. M€ossbauer et al.51 using the room temperature XRD analysis.
spectrum was best fitted with two sextets having hyperfine According to them, the typical SR (111) and (200) were
field values of 254 and 142 kOe and relative intensities of 58 clearly seen in the XRD pattern of these alloys. The refine-
and 34, respectively, along with a doublet of 8% intensity ment of the XRD data revealed that these alloys exist in
(paramagnetic). In a well ordered Y-type structure, there Y-type structure with lattice parameter values of 5.851 and
must be a single Hhf due to the presence of only one crystal- 5.805 Å for CoFeTiAl and CoMnVAl, respectively, as given
lographic site for Fe. Thus, the presence of second sextet in Table II. The difference between the measured data and
indicates the structural disorder for the alloy. The authors the theoretical data for (200) peak indicated the presence of
thus concluded that CoFeCrGa alloy exists in Y-type crystal some amount of chemical disorder. They tried various com-
structure along with some DO3 disorder. They also checked binations (disorder, interchange of different atoms) to
the phase stability of the crystal structure by performing improve the fitting between experimental and theoretical
DTA in the temperature range of 500–1600 K; a peak in the data in their refinement. However, the exact amount of struc-
DTA curves was obtained around 1000 K, which was attrib- tural disorder in these alloys has not been reported from the
uted to the ordered Y-type to the disordered B2 phase XRD analysis.
transition.
E. CoFeCrGe and CoMnCrAl alloys
C. CoRuFeZ (Z 5 Si and Ge) alloys
Enamullah et al.52 obtained the structural information of
The crystal structure of CoRuFeZ (X ¼ Si and Ge) was these alloys by performing the Rietveld refinement of the
investigated by Bainsla et al.11 and Deka and Srinivasan50 room temperature XRD data. As per their report, these alloys
using XRD and M€ossbauer analysis. (111) and (200) peaks are found to exist in cubic Heusler structure with lattice
were found to be present in the XRD for both the alloys,11 as parameters of 5.77 and 5.76 Å for CoFeCrGe and CoMnCrAl,
shown in Figs. 3(e) and 3(f). However, in the case of respectively (as given in Table II). The intensities of SR (111)
CoRuFeSi, the intensity of (200) peak was high, while (111) and (200) were weak in the case of CoFeCrGe, which may be
reflection was weak, giving an indication of B2 disorder in due to the nearly equal atomic scattering amplitudes of the
CoRuFeSi. However, the superlattice reflections were weak atoms. According to these authors, the best fit between
in the case of CoRuFeGe, which was attributed to the nearly the experimental and calculated intensities was obtained for
031101-6 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

the configuration Ge and Cr at 4a(0, 0, 0) and 4b(1/2, 1/2, 1/2) presence of the (200) peak in the neutron diffraction data, in
octahedral sites, respectively, while Co and Fe at 4c(1/4, 1/4, contrast to the absence of both (111) and (200) reflections in
1/4) and 4d(3/4, 3/4, 3/4) tetrahedral sites, respectively. Ab- the XRD data, shows the importance of the neutron diffrac-
initio calculations by the same researchers also predicted that tion as a probe in such cases [where the transition elements
the configuration which results in the best fit of the XRD data and the main group element belong to the same period].
is indeed the energetically most favorable.52 Thus, Halder et al.54 concluded that B2 type structural disor-
In the case of CoMnCrAl, the superlattice peak (200) der is present in the case of NiCoMnAl.
was found to be more intense as compared with (111) peak In order to get further insight into the order/disorder for
as per the report of Enamullah et al.52 The observed XRD NiCoMnAl and NiCoMnGe alloys, Halder et al.54 performed
data clearly suggested a chemical disorder between the octa- model calculations with varying amounts of disorder. They
hedral sites of the system. Similar to CoFeCrGe, there are quantified the disorder with respect to the Mn-Z and Ni-Co
possibilities of three different configurations for CoMnCrAl sites. Due to the differences in the scattering lengths of neu-
with the exception that in this case, exchange of atoms trons for Ni and Co, they could identify the disorder at Ni
between octahedral sites, i.e., (0, 0, 0) and (1/2, 1/2, 1/2) fcc and Co sites. Thus, on the basis of the observed neutron dif-
sublattices, is also to be considered. Even though the fraction data and model calculations, they concluded that
observed XRD pattern fitted well with all the three configu- there was a complete disorder at Mn-Al sites as well as at
rations, the one in which the octahedral site (1/2, 1/2, 1/2) Ni-Co sites for NiCoMnAl. On the other hand, in the case of
fcc containing the least electronegative element is found to NiCoMnGe, they concluded that there was no disorder at
be energetically the most favorable. Here, Cr and Mn have Mn-Ge sites, but they showed a complete disorder at Ni-Co
the least electronegativity, and hence the two configurations sites. From the temperature variation of neutron diffraction
which contain Cr or Mn at octahedral site are favorable. data, they found that the lattice parameters for both the alloys
Electronegativity of the Al is also of the same order as of Mn increased with increase in temperature. The results of struc-
and Cr, and thus Al tries to occupy (1/2, 1/2, 1/2) fcc sublat- tural analysis for NiCoMnZ (Z ¼ Al, Ge, and Sn) are also
tice in addition to the (0, 0, 0) sublattice. Due to this behav- given in Table II.
ior of Al, the (111) peak is found to be absent from the XRD
pattern. G. NiFeMnGa, NiCoMnGa, and CuCoMnGa alloys
Enamullah et al.52 have also observed that if two or Alijani et al.55 obtained the structural details of these
more atoms possess nearly same electronegativity values, alloys by performing the Rietveld refinement of the room
some degree of disorder could be expected in the crystal temperature XRD patterns. All the alloys were found to exist
structure. They gave the example of CoMnCrAl, CoFeCrAl9 in the cubic Y-type Heusler structure. The SR (111) and
and Co2Cr1xFexAl53 alloys, where disorder is found (200) were not observed in the XRD for these alloys, which
between Cr and Al sites. On the basis of the data available in is due to the nearly equal scattering amplitudes of all the ele-
the literature, they proposed an empirical relation between ments. Thus, a conclusive structural analysis was not possi-
the relative electronegativity values and the occurrence of ble from the measurements, and a deeper structural analysis
disorder. is required for these alloys. According to them, the determi-
nation of exact crystal structure in such cases is possible
F. NiCoMnZ (Z 5 Al, Ge, and Sn) alloys from anomalous XRD and EXAFS measurements. The lat-
Structural analysis of these alloys was done using pow- tice parameters obtained from the refinement of the XRD
der XRD as well as neutron diffraction measurements by data are given in Table II for all the alloys. They also calcu-
Halder et al.54 The Rietveld refinement of the room tempera- lated the bulk moduli of all the alloys and found that the Ni
ture powder XRD data revealed that all the alloys formed in containing alloys are harder as compared with Cu containing
single phase with cubic Heusler structure. The SR (111) and alloy.
(200) were found to be absent for NiCoMnAl and
NiCoMnGe, while they were present in NiCoMnSn. The H. MnNiCuSb alloy
appearance of the (111) and (200) peaks in the XRD pattern The structural properties of MnNiCuSb were investi-
of NiCoMnSn indicates the absence of structural disorder. gated by Haque et al.56 using the powder x-ray diffraction
Halder et al. also mentioned that mere absence of the super- measurements. This alloy was found to exist in single phase
lattice reflections in the XRD of NiCoMnAl and NiCoMnGe with cubic Heusler crystal structure (Y-type) and F43m
should not be taken as the sign of the disordered crystal space group (#216). However, small Cu impurity peak
structure. Thus, to further investigate the crystal structure of (<5%) was observed in the XRD pattern. Lattice parameter
NiCoMnAl and NiCoMnGe, they performed neutron diffrac- value of 5.923 Å was obtained by performing the Rietveld
tion measurements at different temperatures. They analyzed refinement of XRD data, as given in Table II. The superlat-
the neutron diffraction pattern using the Rietveld refinement tice reflections (111) and (200) were present in the XRD
(using the FULLPROF program). The superlattice reflections with moderate intensity, which hint at the ordered crystal
(111) and (200) were observed in the neutron diffraction pat- structure. However, as mentioned earlier, it is very difficult
tern of NiCoMnGe, in contrast to their XRD study. In the to probe the structural disorder in the systems where all the
case of NiCoMnAl, they observed (200) peak in the neutron transition elements belong to the same period in the periodic
diffraction spectrum, while (111) peak was absent. The table. Elemental composition of the alloy was also studied
031101-7 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

by Haque et al.,56 using the energy dispersive X-ray spec- valence electrons in a 2:1:1 and 1:1:1:1 Heusler alloy system
troscopy (EDS) studies. The final stoichiometry of the alloy can be obtained using the relation
was calculated by averaging the data obtained over many
grains and found to be Mn0.97NiCu0.95Sb, which is very close Nv ¼ ½ðouter s and d electrons for transition metalsÞ
to the 1:1:1:1 composition. The homogeneity of the alloy þ ½ðouter s and p electrons for main group elementsÞ:
was also confirmed by the EDS analysis. (3)

In the case of non half-metallic state, the magnetic

III. MAGNETIC PROPERTIES moment value will deviate from Equation (2). According to
the Slater-Pauling rule, ferromagnetic ordering is found to be
Unlike the usual ferromagnets, HMFs exhibit integer absent at Nv ¼ 24, due to a quasi-closed-shell character. The
magnetic moments, usually obeying the modified Slater- phenomenon of half-metallic, fully compensated ferrimagne-
Pauling rule.57–59 The magnetic moment in Heuler alloys, tism was predicted theoretically in certain cases of Heusler
especially in Co2 based alloys, follows the Slater-Pauling alloys with 24 valence electrons.60 In the case of Nv  30,
rule.57–59 In the case of localized moment systems, an aver- the assumption of localized magnetic behavior is not valid.
age magnetic moment (mav) per atom can be defined as55 Heusler alloys with magnetic moment values greater than
6 lB are rarely known. Thus, in the case of high valence elec-
mav ¼ ðnav  6  2nsp ÞlB : (1)
tron concentration (Nv  30), an itinerant Slater-Pauling
Here, nav is the average number of valence electrons per behavior is approximated.61,62 The following relation is valid
atom in the alloy and nsp represents the average number of for such cases:
unbalanced sp electrons. The number 6 arises because Fermi m ¼ ð34  Nv Þl: (4)
level lies in the gap between the occupied and the unoccu-
pied d electron states for spin down states. In half-metallic
ferromagnetic systems, where a band gap is present in one of A. CoFeMnZ (Z 5 Al, Si, Ga, and Ge) alloys
the spin sub bands and all sp electrons are occupied, nsp van-
Magnetic properties of these alloys were first investi-
ishes. There are four atoms in the primitive cell of 2:1:1 and
gated by Alijani et al.45 using a SQUID magnetometer. The
1:1:1:1 Heusler alloys. Thus, the total magnetic moment (m)
corresponding saturation magnetization (MS) and the Curie
in the case of 2:1:1 and 1:1:1:1 half-metallic Heusler alloys
temperature values are given in Table III. They observed
is57–59
that the MS value for all the alloys were higher in compari-
m ¼ ðNv  24ÞlB ; (2) son to the values obtained using Slater-Pauling rule.57–59
They attributed the difference between the experimental
where Nv is the total number of valence electrons in the and theoretical results to the presence of disorder and/or
primitive cell (see details in Ref. 58). The total number of magnetic impurities. As discussed above (Section II),

TABLE III. List of Curie temperature (TC), saturation magnetization (MS), magnetic moment value using Slater-Pauling rule (MS-P) and calculated magnetic
moment (MC) with references for some EQHAs.

Alloy MS (lB/f.u.) [experimental] MC (lB/f.u.) [calculated] MS-P (lB/f.u.) TC (K) References

CoFeMnAl 3.1 (at 5 K) and 2.7 (at 300 K) 3.0 3.0 553 45
CoFeMnSi 4.1 (at 5 K) and 3.7 (at 300 K) 4.0 4.0 623 45
3.7 (at 3 K) 4.0 8
CoFeMnGa 3.2 (at 5 K) and 2.8 (at 300 K) 3.0 3.0 567 45
CoFeMnGe 4.2 (at 3 K) and 3.8 (at 300 K) 4.0 4.0 711 8 and 45
CoFeCrAl 2.0 2.0 2.0 460 9
CoFeCrGa 2.1 2.0 2.0 Above 400 10
CoFeCrGe 3.0 3.0 3.0 866 52
CoFeTiAl 0 0 51
CoMnVAl 0 0 51
CoMnCrAl 0.9 1.0 1.0 358 52
CoRuFeSi 4.8 5.0 867 11
CoRuFeGe 5.0 5.0 833 11
NiCoMnAl 4.7 5.0 5.0 54
NiCoMnGa 4.5 5.1 5.0 646 55
NiCoMnGe 4.1 4.9 6.0 54
NiCoMnSn 4.8 5.1 6.0 54
NiFeMnGa 3.4 4.0 4.0 326 55
CuCoMnGa 2.3 4.3 4.0 631 55
MnNiCuSb 3.9 690 56
031101-8 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

structural disorder was observed in the case of CoFeMnAl magnetic moment (2.5 lB). They also found that the
and CoFeMnSi, while Alijani et al.45 could not obtain any moment of Co sites is stable against the variation of the Z
structural disorder for CoFeMnGa and CoFeMnGe. element or the number of valence electrons and exhibits a
However, they were not able to identify the impurities from value of 0.8 lB. The most interesting observation of these
the XRD analysis for both CoFeMnGa and CoFeMnGe. authors is that the moment at Fe sites strongly varied with the
Bainsla et al.7,8 further investigated the magnetic properties number of valance electrons and it even changed sign as the
of CoFeMnZ (Z ¼ Si and Ge) alloys, and they obtained the number of valence electrons changed from 27 to 28. In
values of 3.7 and 4.2 lB/f.u. at 3 K for CoFeMnSi and CoFeMnAl and CoFeMnGa alloys, the Fe atoms were found to
CoFeMnGe, respectively, as shown in Fig. 4(a). The MS be in antiparallel alignment with Co and Mn atoms, i.e., in fer-
values of 4.1 and 4.2 lB/f.u. at 5 K were obtained for rimagnetic order. In a Y-type structure, the nearest neighbors of
CoFeMnSi and CoFeMnGe, respectively, by Alijani et al.45 Mn are Co and Fe. Thus, it can be supposed that magnetic
The difference between the MS values for CoFeMnSi could moment at Fe sites is induced by the neighboring Mn spins.
be attributed to the large structural disorder observed by Alijani et al.45 observed that the stability of the Co and Mn
Bainsla et al.8,46 moments together with the Slater-Pauling rule dictates whether
The Curie temperatures of all the alloys were first deter- the moment at Fe sites is aligned parallel or antiparallel to Mn.
mined using the temperature dependent magnetization meas- Further investigation on the local magnetic moment and
urements by Alijani et al.45 and TC was found to be much other magnetic properties was made by Klaer et al.63 using
above room temperature for all of them, as given in Table the circular dichroism in x-ray-absorption spectroscopy
III. High values of TC facilitate in technological applications (XAS/XMCD). They performed XAS/XMCD measurements
of these materials. Bainsla et al.7,8 used differential thermal at the Mn, Fe, and Co L3,2 edges. The shape of the spectra
analysis to estimate the Curie temperature of CoFeMnZ was found to be pairwise similar for CoFeMnAl(Ga) and for
(Z ¼ Si and Ge) alloys and obtained values close to 620 and CoFeMnSi(Ge), which was expected due to the same crystal
750 K, in comparison to the 623 and 711 K (obtained by structure and isoelectronic nature of the pairs. According to
Alijani et al.45) for CoFeMnSi and CoFeMnGe, respectively. them, the largest change in XMCD spectra was observed for
In order to understand the magnetic properties further, Mn. The magnetic moment at Mn site changes from 0.96 lB
the magnetic behavior of these alloys was studied using ab- to 2.22 lB for Z ¼ Al to Z ¼ Si, respectively. The maxima at
initio calculations by Alijani et al.45 The calculated values of L3,2 edge appear much sharper for Co and Fe for Z ¼ Si and
MS were found to be integer, typical for half-metallic ferro- Ge, in comparison to Z ¼ Al and Ga. The variation of Z in
magnets. As per the Slate-Pauling rule, MS adopts values of CoFeMnZ alloys shows no significant effect on the Co and
3 lB/f.u. for Z ¼ Al and Ga, while 4 lB/f.u. for Z ¼ Si and Fe moments, but in contrast, the increase in the number of
Ge. The site specific magnetic moment calculations by valence electrons causes a considerable increase in the Mn
Alijani et al. revealed that the magnetic properties are mainly moment. The total moment values derived from SQUID
determined by the Mn atoms, which contribute the highest measurements (as performed by Alijani et al.45) were found

FIG. 4. Isothermal magnetization

curves obtained for certain equiatomic
quaternary Heusler alloys at low tem-
peratures. Figs. (a) and (b) represent
the M vs. H curves for CoFeMnZ
(Z ¼ Si and Ge) and CoRuFeZ (Z ¼ Si
and Ge), respectively. (c) shows the
curves for CoFeCrZ (Z ¼ Al and Ga)
alloys at 8 K, while (d) shows the
isothermal curves for CoMnCrAl
and CoFeCrGe alloys at a temperature of
5 K. Data taken from References 7, 8, 9,
11, and 52.
031101-9 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

to be in good agreement with those obtained using XMCD value (2.0 lB/f.u.) using Slater-Pauling rule. According to
analysis by Klaer et al.63 this rule, integer values of the total moment are possible in
As discussed above, depending on the occupancy of dif- the case of the half-metallic ferromagnetic systems. The iso-
ferent lattice sites, three different structural configurations thermal magnetization curve at 8 K and under ambient pres-
are possible for Y-type structure. Klaer et al.63 tried to find sure for CoFeCrGa is given in Fig. 4(c). As discussed above,
out the correct crystal structure for these alloys by comparing the pressure independent MS value is a sign of half-metallic
the theoretically obtained individual magnetic moment val- ferromagnetic nature in CoFeCrGa.
ues with those obtained using the XMCD analysis. They Bainsla et al.10 also performed ab-initio calculations to
found that theoretically obtained crystal structure is in agree- get better insight into the magnetic behavior of CoFeCrGa
ment with XMCD analysis for Z ¼ Si and Ge, while element alloy. As per these calculations, the total magnetic moment
specific magnetic moment observations using XMCD ruled was found to be constant as a function of lattice parameter,
out the theoretical predictions for Z ¼ Al and Ga. which supports their experimental claims. The Fe moment
was found to be aligned antiferromagnetically to Co and Cr
B. CoFeCrZ (Z 5 Al and Ga) alloys for all lattice parameter values. The Co moment remains
constant under the application of hydrostatic pressure, while
Magnetic properties of CoFeCrAl alloy were first mea-
it causes a decrease in the moments of antiferromagnetically
sured by Luo et al.47 Curie temperature of 460 K for the alloy
coupled Fe and Cr and collectively results in a constant total
was obtained using the thermomagnetic curves recorded by
magnetic moment.
them. Nehra et al.48 also studied the magnetic properties of
the as-melted as well as quenched CoFeCrAl alloy and found C. CoRuFeZ (Z 5 Si and Ge) alloys
a bifurcation between the zero field cooled and the field
cooled thermomagnetic data. They also observed that the dif- Magnetic properties of CoRuFeSi alloy were first studied
ference between these two data decreases with increase in the by Deka and Srinivasan,50 using a vibrating sample magne-
cooling field and entirely disappears in a cooling field of 1.5 tometer. The MS value of 5.0 lB/f.u. was obtained at 300 K
kOe. These authors attributed the magnetic behavior to the by them for CoRuFeSi. Bainsla et al.,11 investigated the mag-
antiferromagnetic interactions between Cr-Co/Fe and Cr at netic properties of the CoRuFeZ (Z ¼ Si and Ge) alloys by
ordinary sites with Cr at the anti (Al) sites. The TC values of studying the isothermal magnetization curves at different tem-
410 and 515 K were obtained for as-melted and quenched peratures and thermomagnetic curves up to 1100 K. The satu-
CoFeCrAl samples, respectively.48 Bainsla et al.9 further ration magnetization values of 4.8 and 5.0 lB/f.u. at 5 K were
investigated the magnetic properties of CoFeCrAl alloy and obtained for CoRuFeSi and CoRuFeGe, respectively, as
found that TC value was more than 400 K. shown in Fig. 4(b) and Table III. The MS values are found to
The saturation magnetization value of 2.07 lB/f.u. was be slightly different at room temperature (300 K), 4.6 and
obtained for CoFeCrAl at 5 K by Luo et al.,47 which was 4.7 lB/f.u. for CoRuFeSi and CoRuFeGe, respectively. The
found to be in agreement with their theoretically predicted obtained MS values at 5 K are found to be in good agreement
value of 2.0 lB/f.u. Bainsla et al.9 also investigated the mag- with those estimated using the Slater-Pauling rule.57–59 Thus,
netic properties of CoFeCrAl alloy by performing the pres- the moment value of 5.0 lB/f.u. (5 K) obtained for CoRuFeGe
sure dependent isothermal magnetization measurements at gives a strong indication of the half-metallic nature.
8 K. The MS value of 2.0 lB/f.u. was obtained under the The Curie temperature of the alloys was determined by
ambient pressure as shown in Fig. 4(c) and given in Table Bainsla et al.11 by recording the thermomagnetic curves under
III, and it is found to be invariant under pressure up to 12 a field of 50 Oe in the range of 300–1100 K as shown in Figs.
kbar. The invariance of MS was observed earlier in the case 5(a) and 5(b). TC values of 867 and 833 K were obtained for
of Co2VGa64 and it was attributed as a characteristic of half- CoRuFeSi and CoRuFeGe, respectively, in which the former
metallic ferromagnets. The theoretically predicted MS value is found to be the highest among all the known equiatomic
(1.97 lB/f.u.) by Bainsla et al.9 is found to be in good agree- quaternary Heusler alloys.7–11,45,46,52,63 The relatively high
ment with the value (2.0 lB/f.u.) obtained using Slater- value of TC in these alloys gives a possibility of retaining high
Pauling rule.57–59 The effect of lattice compression in certain spin polarization at elevated temperatures.
Heusler alloys was studied by Picozzi et al.38 using ab-initio
D. CoFeTiAl and CoMnVAl alloys
calculations, and they found that the half-metallic nature can
be preserved under lattice parameter variation of 3%–5%. The magnetic properties for these alloys were studied by
Bainsla et al.,10 studied the magnetic properties of Basit et al.51 by measuring the magnetization isotherms at dif-
CoFeCrGa alloy by recording the thermomagnetic curves in ferent temperatures for CoFe1þxTi1xAl and CoMn1þxV1xAl
the temperature range of 5–400 K with applied magnetic alloys. These authors observed that the parent alloys, namely,
field of 500 Oe. Curie temperature value is expected to be CoFeTiAl and CoMnVAl, do not show any moment at 5 K,
more than 400 K as no magnetic transitions were observed in which is in agreement with the Slater-Pauling rule. Due to the
the thermomagnetic curves up to that temperature. The iso- better structural stability in CoMn1þxV1xAl alloys as com-
thermal magnetization curves were recorded with different pared with CoFe1þxTi1xAl alloys, they performed ab-initio
values of applied pressure (up to 9.8 kbar) at 8 K. The pres- calculations in CoMn1þxV1xAl alloys to understand the elec-
sure independent MS value of 2.1 lB/f.u. was obtained and tronic structure. The absence of magnetic moment in the par-
it was found to be in good agreement with the estimated ent CoMnVAl was already expected from the Slater-Pauling
031101-10 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

FIG. 5. Thermomagnetic curves obtained

for different equiatomic quaternary
Heusler alloys in the range of 300–
1100 K. Figs. (a) and (b) represent the
curves for CoRuFeSi and CoRuFeGe,
respectively. While (c) and (d) show the
curves for CoFeCrGe and CoMnCrAl,
respectively. Data taken from References
11 and 52.

rule. The experiments performed by them did not give any also performed by them on these alloys.52 The calculated
information on the magnetic order of CoMnVAl. However, the magnetic moment values of 1.0 and 3.0 lB/f.u. were
possibility of a fully compensated half-metallic ferrimagnetism found for CoMnCrAl and CoFeCrGe, respectively, which
(FCHMF) could not be ruled out,60,65 with a ferromagnetic- follow the Slater-Pauling rule.
paramagnetic transition taking place at temperatures below
5 K. Ab-initio calculations have shown a non spin-polarized F. NiCoMnZ (Z 5 Al, Ge, and Sn) alloys
ground state for CoMnVAl and it was obtained independently Halder et al.54 studied the magnetic properties of these
of the method using starting parameters involving ferromag- alloys using magnetization and neutron diffraction measure-
netic or different types of ferrimagnetic order. Therefore, fully ments. Thermomagnetic curves were obtained under an
compensated half-metallic ferrrimagnetic ground state can be applied field of 500 Oe for all the alloys and the TC values
excluded as the ground state. were found to be higher than 583 K. Isothermal magnetiza-
tion curves were obtained at different temperatures for all
E. CoFeCrGe and CoMnCrAl alloys
the alloys over a field range of 50 kOe by them. The M vs. H
The magnetic properties of these alloys were studied by curves at 5 K showed a soft ferromagnetic nature as revealed
Enamullah et al.,52 using a Physical Property Measurement by negligible hysteresis. The obtained MS values at 5 K and
System. Enamullah et al.52 recorded thermomagnetic curves corresponding magnetic moment values from ab-initio calcu-
under a field of 500 Oe for both the alloys as shown in Figs. lations for all the alloys are given in Table III. The MS values
5(c) and 5(d). The values of 358 and 866 K were obtained estimated using the Slater-Pauling rule are found to be 5.0,
for CoMnCrAl and CoFeCrGe, respectively. The TC value 6.0, and 6.0 lB/f.u. for NiCoMnAl, NiCoMnGe, and
estimated for the CoFeCrGe alloy is found to be nearly equal NiCoMnSn alloys, respectively, in comparison to the experi-
to the highest TC (867 K) value which was obtained for mentally obtained values of 4.7, 4.1, and 4.8 lB/f.u. The ab-
CoRuFeSi. initio calculation predicted that the half-metallic nature was
Enamullah et al.52 also recorded isothermal magnetiza- absent for both NiCoMnGe and NiCoMnSn, and the mag-
tion curves at different temperatures. The soft ferromagnetic netic moment was less than 6.0 lB/f.u. According to this
nature was observed for these alloys, as there was no hystere- study, one of the possible reasons for the absence of half-
sis found in the M-H curves. Both the alloys show saturation metallic nature is that the Ni remains almost paramagnetic in
in magnetization at 5 K {as shown in Fig. 4(d)} and 300 K. Ni based quaternary Heusler alloys and cannot carry a large
The saturation magnetization values of 3.0 and 0.9 lB/f.u. magnetic moment. The discrepancy between the experimen-
were obtained at 5 K for CoFeCrGe and CoMnCrAl, respec- tally obtained MS values and the calculated magnetic
tively, while the MS values of 3.0 and 1.0 lB/f.u. were esti- moment values was attributed to the presence of structural
mated using the Slater-Pauling rule.57–59 The presence of disorder as discussed in Section II F.
structural disorder in CoMnCrAl might be the possible rea- Halder et al.54 further investigated the magnetic proper-
son for the deviation in MS value. Ab-initio calculations were ties of these alloys by performing the neutron diffraction
031101-11 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

measurements for NiCoMnAl and NiCoMnGe alloys. The and TC ¼ 690 K was obtained. Isothermal magnetization curve
analysis of the neutron diffraction data reveals the ferromag- at 5 K shows negligible hysteresis and thus a soft ferromagnetic
netic ordering of Co and Mn moments for both the alloys. nature. The MS value of 3.85 lB/f.u. was obtained at 5 K using
However, no ordered moment of the Ni atom could be the M vs. H curve.
refined satisfactory in both the alloys. The magnetic moment
values of 0.97(6) and 2.95(4) lB/f.u. were obtained for Co IV. MAGNETO-TRANSPORT PROPERTIES
and Mn, respectively, at 6 K in the case of NiCoMnGe. In
Electrical resistivity (q) is an intrinsic property of a
the case of NiCoMnAl, moment values of 1.08(9) and
solid, which quantifies how strongly it opposes the flow of
3.13(7) lB/f.u. were obtained for Co and Mn, respectively, at
electric current. Thus, q describes the response of a system
6 K. due to an external electric field. These measurements are
very effective and useful in probing the magnetic state of the
G. NiFeMnGa, NiCoMnGa, and CuCoMnGa alloys
materials because of the strong coupling between the elec-
The magnetic properties of these alloys were studied by tron mobility and the magnetic state. The origin of electrical
Alijani et al.55 using the SQUID magnetometer. Isothermal resistivity in metals and alloys is the scattering of charge car-
magnetization curves show negligible hysteresis, revealing riers, viz., the conduction electrons by lattice defects, ther-
the soft ferromagnetic nature. The MS and TC values of these mally excited lattice vibrations (phonons), spin waves
alloys are summarized in Table III. The MS values of 3.4, (magnons), spin fluctuations, etc. Another contribution arises
4.5, and 2.3 lB/f.u. were obtained at 5 K for NiFeMnGa, from the electron-electron interaction, mainly at low temper-
NiCoMnGa, and CuCoMnGa alloys, respectively. According atures. The conduction band in these materials is mainly con-
the Slater-Pauling rule57–59 and ab-initio calculations by stituted by the s-electrons. Due to their large effective mass,
Alijani et al., the moment values of 4.0 and 5.0 lB/f.u. were the contribution to the conductivity from the d-electrons is
obtained for NiFeMnGa and NiCoMnGa, respectively. As quite negligible. However, d-electrons play an important role
can be noted, there is a large discrepancy between experi- in determining the resistivity and its variation due to the
mentally obtained MS values and calculated values, which large density of states of the d-band. This is due to the fact
could be attributed to the structural disorder. But these that scattering probability depends on the DOS into which
authors observed that the difference was too high to be dedi- the electrons are scattered. Therefore, s-d scattering plays an
cated only to the disorder effect. Impurities below the detec- important role in the electrical resistivity behavior in metal-
tion limit of XRD (approximately 5%) may also contribute lic systems. In the case of magnetically ordered systems, the
to this difference. They also mentioned the possibility of a change in the long-range order is reflected in q behavior and
canted spin structure, which was found energetically unsta- often manifests as a change in the slope of a q vs. T curve at
ble for these alloys as per their calculations. the transition temperatures.
The total moment of CuCoMnGa was estimated to be The total resistivity of magnetic alloys is generally
6.0 lB/f.u. when assuming half-metallicity and localized found to obey the Matthiessen’s rule.66 According to this
Slater-Pauling behavior,57–59 which was found to be in dis- rule, the contributions from different factors to the total
agreement with experiment.55 The magnetic moment of resistivity are independent of one another and thus additive.
4.0 lB/f.u. was estimated when considering an itinerant The total resistivity can be written as
Slater-Pauling behavior.55,61,62 The experimentally obtained
low value of moment in the case of CuCoMnGa was qðTÞ ¼ q0 þ qph ðTÞ þ qmag ðTÞ: (5)
explained by a vanishing contribution of Cu to the magnetic
properties. Although the results of ab-initio calculations pre- Here, q0 is the residual resistivity, which is temperature
dict absence of half-metallic nature, the experimental MS independent and originates from the scattering of conduction
electrons by the lattice defects, impurities, etc., qph and qmag
value is so small to compare in the case of CuCoMnGa.
arise due to the scattering by phonons and magnons, respec-
According to Alijani et al.,55 MS values for NiFeMnGa
tively, and are temperature dependent. The phononic part of
and NiCoMnGa show fair agreement with the Slater-Pauling
the scattering process (qph) can be described by the Bloch-
rule57–59 and a possible half-metallic ferromagnetic behav-
Gr€uneisen relation67
ior, making them suitable for spintronic applications. TC val-
ues of 326, 646, and 631 K were obtained for NiFeMnGa,  5 hDð=T
NiCoMnGa, and CuCoMnGa, respectively. The relatively T x5
qph ¼ 4R dx; (6)
high TC in half-metallic NiCoMnGa makes it even more hD ð1  ex Þðex  1Þ
attractive for the applications. Thermomagnetic curves 0

recorded by Alijani et al.55 show the conventional ferromag-

where R includes the electron-phonon coupling constant and
netic behavior for NiCoMnGa and CuCoMnGa, while
atomic masses of different type of atoms, and hD is the
NiFeMnGa shows a sharp drop in magnetization around TC.
Debye temperature. In the high temperature limit, i.e.,
T > hD, qph varies linearly with temperature. For the low
H. MnNiCuSb alloy
temperature limit, i.e., T < hD, qph shows a T5 dependence.
Haque et al.56 investigated the magnetic properties of At low temperatures, the electrical resistivity of a mate-
MnNiCuSb using the SQUID magnetometer. Thermomagnetic rial originates from the (i) electron-electron scattering,68 (ii)
curve was recorded in the temperature range of 300–1000 K, electron-magnon scattering,69,70 and (iii) electron-phonon
031101-12 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

scattering.68 The electron-phonon contribution is relatively quadratic field dependence in the paramagnetic region.74
smaller at low temperatures and thus q is mainly contributed Positive MR is obtained in many antiferromagnetic materials,
by the electron-electron and electron-magnon scatterings. In which originates from the enhancement of spin fluctuations by
the case of ideal HMFs, electron-magnon scattering is found the application of a magnetic field. The change in the mag-
to be absent due to unavailability of the minority carriers at netic structure of materials, especially in antiferromagnets,
the EF. As the temperature increases, the half metallic trend often leads to the creation of a superzones in their band struc-
decreases and the electron-magnon contribution appears. ture and thus gives rise to positive MR.75 The HMF materials
However, a double magnon process is possible in HMFs. generally show low MR values due to the absence of spin
Therefore, the major contributions to the resistivity in a fluctuations.9,76–78
HMF arise due to (i) electron-electron (T2 dependence),68 In Subsections IV A–IV C, a brief discussion on the vari-
(ii) electron-phonon (T dependence),68 and (iii) double mag- ous magneto-transport measurements reported for some
non scattering (T9/2 at low temperatures and T7/2 at high EQHAs is given.
temperatures).71,72
The change in the resistivity on the application of an A. CoFeMnZ (Z 5 Si and Ge) alloys
external magnetic field is known as magnetoresistance (MR),
Bainsla et al.8 studied the temperature dependencies of
which can be used as a probe to study magnetic systems. MR
the electrical conductivity [rxx(T)] and the carrier concentra-
can be estimated from the field dependence of the resistivity
tion [n(T)] in case of CoFeMnSi; the curves are shown in
data and is given by the relation
Figs. 6(a) and 6(b). rxx(T) was measured under different
  applied magnetic fields (0 and 50 kOe) in the temperature
qðT; H Þ  qðT; 0Þ
MR% ¼  100; (7) range of 5–300 K. Electrical conductivity increases with
qðT; 0Þ
increase in temperature, indicating a non-metallic conduc-
where q(T,H) and q(T,0) are the resistivity values of the mate- tion. rxx(T) ¼ 2980 and 3000 S/cm were obtained at 300 K
rial at temperature T under the application of an applied mag- under the fields of 0 and 50 kOe, respectively. The obtained
netic H and in the absence of the field, respectively. In any electrical conductivity value at 300 K was found to be slightly
material, the application of a magnetic field deviates conduc- higher than that observed for Mn2CoAl (i.e., 2440 S/cm)
tion electrons from their path and thus leads to an increase in reported by Ouardi et al.26 Linear behavior in rxx(T) was
the resistivity value, thereby a positive MR. The positive observed in the high temperature region, while a non-linear
increase in the MR is termed as Lorentz contribution.73 In behavior was observed at low temperatures for CoFeMnSi.
spite of the presence of the Lorentz contribution, intermetallic The non-linear behavior was attributed to the disorder
compounds, in general, show a decrease in the resistivity, enhanced coherent scattering of conduction electrons.79 The
thereby resulting in negative MR, which may originate from conductivity behavior for CoFeMnSi is reported to be unusual
the suppression of the spin fluctuations by the field or by the and different from that of the normal metals or semiconduc-
decrease in the spin disorder scattering. The negative MR aris- tors. The carrier concentration (n) value of the CoFeMnSi was
ing from the suppression of the spin fluctuations follows calculated using the Hall coefficient (RH) measurements, and

FIG. 6. (a) and (b) represent the carrier

concentration and electrical conductiv-
ity curves for the CoFeMnSi and
CoFeCrGa alloys, respectively, in the
temperature range of 5–300 K. (c)
shows the electrical resistivity curves
for the CoFeCrAl and CoFeMnGe
alloys, while (d) shows the electrical
resistivity curves for the CoRuFeZ
(Z ¼ Si and Ge) alloy. Data taken from
References 7, 8, 9, 10, and 11.
031101-13 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

a nearly temperature independent carrier concentration was regions, i.e., between 5 and 85 K and between 85 and 300 K.
obtained in the range of 5–300 K which is typical of spin gap- The resistivity trend was found to fit well with the relation,
less semiconductors.26,80 The carrier concentration value of q(T) ¼ q0  AT1/2 þ BT2 þ CT9/2 in the low temperature region,
4  1019 cm3 was observed at 300 K for CoFeMnSi, which is while the best fit is given by q(T) ¼ q0 þ DT þ ET7/2 in the
comparable to that observed for HgCdTe (1015–1017 cm3), high temperature region. T1/2 term was found to be dominat-
Mn2CoAl (1017 cm3), and Fe2VAl (1021 cm3).81 It may be ing over the other two contributions in the low temperature
noted that the physical origin behind such a temperature region, which may be due to the presence of disorder. Thus,
dependence in carrier concentration of gapless semiconduc- the minimum seen in the q(T) plot was attributed to the struc-
tors is well established.80,82 The carrier concentration in the tural disorder. In the high temperature region, the linear depen-
case of gapless semiconductors could be written as80 dence due to the electron-phonon contribution dominates, but
 3=2 along with a weak negative contribution from the T7/2 term.
kB T Therefore, the resistivity data analysis for CoFeMnGe shows
ni ¼ pi ¼ 2me mh1=2 ; (8)
2ph2 the possibility of half-metallic ferromagnetic nature even at
elevated temperatures.
where me and mh are the effective masses of the electrons
and holes. A good fit to this expression revealed the spin B. CoFeCrZ (Z 5 Al and Ga) alloys
gapless semiconducting behavior in CoFeMnSi.8 Thus, the
behavior of rxx(T) and n(T) strongly supports the SGS behav- Bainsla et al.9 obtained the q(T) data for CoFeCrAl
ior in CoFeMnSi. The observations of low carrier concentra- alloy using four probe technique, which shows a linear
tion and high resistivity show the exceptional stability of behavior up to 150 K as shown in Fig. 6(c) and is described
electronic structure and its insensitivity to the structural dis- very well by the relation q(T) ¼ q0 þ a*T. Here, the first and
order in CoFeMnSi. According to Bainsla et al.,8 this is the second terms represent residual resistivity and the electron-
first EQHA material to show SGS behavior. phonon interaction term, respectively. Electrical resistivity
Bainsla et al.8 further investigated CoFeMnSi by calcu- behavior of this kind has been observed earlier for half-
lating the anomalous Hall conductivity rxy ¼ qxy/qxx2 at metallic ferromagnetic NiMnSb and PtMnSb at low tempera-
5 K, which was obtained from the magnetic field dependent tures (up to nearly 20 K).86 In the case of CoFeCrAl, q(T)
transport measurements in order to study the low field follows a linear behavior up to relatively higher temperatures
behavior in more detail. Hall conductivity behavior was (up to 150 K), indicating that the possibility of half-metallic
found to follow the same behavior as that of magnetization nature at temperatures as high as 150 K. q(T) was fitted well
isotherm. The anomalous Hall conductivity (rxy0) value of with the relation q (T) ¼ q0 þ b*Tn, with n ¼ 0.2 in the range
162 S/cm was obtained, which is defined as the difference of 150–300 K (region 2). The T2 term arising due to the
in rxy values at zero and the saturation fields. The obtained electron-magnon interaction was found to be absent for q(T)
(rxy0) value for CoFeMnSi was found to be higher than that up to 300 K by Bainsla et al.,9 implying the absence of
observed in Mn2CoAl (22 S/cm),26 but less than that of minority states at the Fermi level. The ab-initio calcula-
the half metallic Co2FeSi (200 S/cm at 300 K)69 and tions,9 which found a large half-metallic band gap of
Co2MnAl (2000 S/cm).83 0.31 eV, also support the statement derived from the temper-
Electrical resistivity measurements were done under the ature dependence of resistivity data. Bainsla et al.9 also
magnetic field of 0 and 50 kOe in the range of 5–300 K for obtained a non-saturating magnetoresistance with field for
CoFeMnGe by Bainsla et al.,7 as shown in Fig. 6(c). CoFeCrAl, with a value of 1.6% at 5 K for 50 kOe.
Resistivity value of 3.1 lX m was found for CoFeMnGe, The temperature dependencies of electrical conductivity
which is relatively high as compared with that of (rxx) with zero applied field and carrier concentration [n(T)]
Co2Fe(Ga0.5Ge0.5) (0.6 lX m) alloy.36 They attributed this to for CoFeCrGa are shown in Figs. 6(a) and 6(b). A nonmetal-
the presence of larger DO3 disorder in CoFeMnGe. The lic conduction behavior was observed for rxx, which
residual resistivity ratio [q300K/q5K] was found to be low increases with increase in the temperature. The obtained
(1.02), which confirms the large disorder in the alloy. A min- value of rxx ¼ 3233 S/cm at 300 K was found to be slightly
imum in the resistivity curve was found near 40 K, which higher than that observed for other SGS Heusler alloys, e.g.,
was followed by an upturn at lower temperatures. Such a Mn2CoAl ¼ 2440 S/cm (Ref. 26) and CoFeMnSi ¼ 3000 S/
behavior has been reported in many Heusler alloys84 and is cm.8 The carrier concentration determined from the Hall
typically attributed to the disorder enhanced coherent scatter- coefficient measurements in the range of 5–280 K was found
ing of conduction electrons.79 It was found that for some to be of the order of 1020 cm3 and nearly temperature inde-
alloys, such a minimum has been explained on the basis of pendent up to 250 K, above which it increases abruptly.
Kondo effect.85 Resistivity behavior for CoFeMnGe was Bainsla et al.10 found that the observations in CoFeCrGa are
analyzed in the temperature range of 5–300 K, considering more or less identical to those of CoFeMnSi, except for the
different scattering mechanisms.7 In addition to the contribu- abrupt jump in the n(T). They mentioned that the abrupt
tions mentioned above, a term representing the structural dis- change in n(T) above 250 K may arise due to the onset of
order with a temperature dependence of T1/2 is also present thermal excitations that dominate over the half metallic
in systems with non-negligible disorder.84 Keeping all the (minority) band gap. Thus, a clear evidence of SGS behavior
above points in mind, Bainsla et al.7 analyzed the resistivity was seen in CoFeCrGa. They10 also obtained the anomalous
data by performing the fitting in two different temperature Hall conductivity (rxy) at 5 K using the magnetic-field-
031101-14 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

dependent transport measurements. rxy (¼qxy/qxx2) value parameter from application point of view. The values of P
obtained for CoFeCrGa was found to be comparable to that and PC are same when the Fermi velocities of both the spin
obtained for other half-metallic Heusler alloys and it follows currents are equal.87,88
the same behavior as the magnetization isotherms. The Point contact Andreev reflection (PCAR) spectroscopy
anomalous Hall conductivity was calculated as the difference is the most widely used technique to measure PC in HMFs.
in rxy values in zero and the saturation fields and it attains a In the measurement of PC by PCAR, one measures the con-
value of 185 S/cm, which is quite identical to that obtained ductance curves across the ferromagnetic (FM)/superconduc-
in CoFeMnSi.8 tor (SC) contact and the spin polarization for a ballistic
contact can be expressed by Equation (10). The nature of the
C. CoRuFeZ (Z 5 Si and Ge) alloys conductance curves for a normal ferromagnet and a HMF is
different due to the spin polarization in the latter. In the rest
Electrical resistivity measurements for CoRuFeZ
of the discussion, the measured current spin polarization is
(Z ¼ Si and Ge) alloys were performed under the applied denoted as P instead of PC. Since this is not a conventional
field of 0 and 50 kOe in the range of 5–300 K (Ref. 11) and experimental tool, a few details regarding its working are
the curves under zero field are given in Fig. 6(d). The value described below.
of q is found to be almost constant with the variation of field PCAR spectroscopy: This spectroscopy relies on the
for both the alloys. Resistivity fittings were performed in two non-linearity in the current-voltage (I-V) characteristics of a
different temperature regimes, and low temperature curves ballistic contact (when contact diameter is less than the elec-
were fitted using qðTÞ ¼ q0 þ a  T n , while qðTÞ ¼ q0 þ b tronic mean free (l) path, it defined as ballistic contact) with
 T þ c  T 2 ¼ q0 þ qph: þ qmag: were fitted to the high a normal metal (N) on one side and a superconductor (S) on
temperature region. At low temperatures (5–50 K), the resistiv- other side. PCAR spectroscopy is somewhat similar to the
ity was found to be independent of the temperature for tunneling spectroscopy (TS), though there are some impor-
CoRuFeSi, thus indicating the absence of spin flip scattering in tant differences such as TS is spin independent in the
that region. Such a behavior was observed earlier for Co2FeSi, absence of magnetic field, while Andreev reflection is spin
which was proved to be half-metallic ferromagnetic in nature dependent. Electrical transport through a N/S point contact
up to a temperature of 103 K (band gap ¼ 8.9 meV).69 Thus, at can be divided into different regimes based on the ratio of
low temperatures, a perfect half-metallic ferromagnetic nature the contact diameter (a) and the electron mean free path
is expected for CoRuFeSi (up to 50 K). An indirect evidence (l).89 A brief discussion for different regimes is given below.
of the half-metallic nature was also seen for CoRuFeGe at low The ballistic regime (when a < elastic (le) or inelastic
temperatures.11 In the high temperature region, the fitting of (li) scattering): In this regime, electrons do not undergo any
the resistivity curves indicates the absence of half-metallic scattering while passing through the point contact. The con-
nature.11 ductance is represented by the sum of individual quantized
conduction channels. To create a scattering-free region
V. SPIN POLARIZATION where the kinetic energy of the electron can be increased in a
As mentioned earlier, in the case of HMF materials, one controllable fashion with the help of a voltage is the role of a
of the spin bands is metallic-like, while the other is ballistic contact in point contact spectroscopy. The funda-
mental principle of PCAR spectroscopy relies on the concept
semiconductor-like. This results in a ferromagnet with elec-
that the kinetic energy of the electron is varied while inject-
trons of only one spin direction at the Fermi level and gives
ing it from normal metal to a superconductor through a bal-
rise to highly spin polarized currents, useful for spintronic
listic N/S interface and conductance curves are measured at
devices. In general, the spin polarization of a material is
N/S interface for different kinetic energies. The extreme
defined as
limit of a ballistic point contact is the quantum point contact.
n" ðEF Þ  n# ðEF Þ The contact diameter is of the order of (1–2 Å) de-Broglie
P¼ ; (9) wavelength of the electron in quantum point contact.
n" ðEF Þ þ n# ðEF Þ
However, it is very difficult to achieve it in conventional
where n"(#)(EF) is the number of up(down) spin carriers at point contact measurements.
the Fermi level. Therefore, half metallic ferromagnets pos- Diffusive regime (lin > a > le): In this regime, there is no
sess a conducting channel for one spin and band gap for the inelastic scattering, but electron can undergo elastic scatter-
other spin. The intrinsic spin polarization of a material is ing in the point contact region. A diffusive transport comes
defined by Equation (9), while the transport spin polarization into play in the spin polarization in itinerant ferromagnets in
(PC) can be expressed as the imbalance in the majority and PCAR.
minority spin currents87,88 To make a ballistic point contact which is essential for
PCAR, the tip has to be very fine. Different methods are
n" ðEF ÞvF"  n# ðEF ÞvF# used to make the fine tips depending on the material of the
PC ¼ ; (10)
n" ðEF ÞvF" þ n# ðEF ÞvF# tip. Superconducting metals like niobium (Nb), gold (Au),
tungsten (W), etc., can be prepared using electrochemical
where n"(#)(EF) and vF"(#) are the DOS at the Fermi level and etching. The starting diameter of the wire is usually 100–300
Fermi velocity for up(down) spin carriers, respectively. The lm. The tip diameter after the processing is reduced to a few
transport spin polarization is the most realistic and relevant tens of nanometers (Fig. 7). However, the final contact
031101-15 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

for CoFeMnSi by extrapolating the P vs. Z data to Z ¼ 0 is

shown in Fig. 8. The current spin polarization value of 0.64
was deduced from the P vs. Z curve, which was found to be
comparable to the P value obtained for some high spin polar-
ization materials using the PCAR technique.9,12–15 Thus, P
was found to robust against structural disorder (as discussed
above) in the case of CoFeMnSi, as expected for SGS
materials.25,26
The current spin polarization value of 0.70 6 0.01 was
FIG. 7. (a) Sample-tip configuration in PCAR. (b) A cartoon showing the reported from the P vs. Z plot for CoFeMnGe by Bainsla
original superconducting wire. (c) Superconducting wire after electrochemi- et al.,7 as shown in Fig. 8. The high value of spin polariza-
cal etching.
tion obtained for this bulk alloy is found to be comparable to
that obtained for bulk Co2Fe(Ga0.5Ge0.5) (P ¼ 0.69 6 0.02),15
diameter is controlled by applying a suitable pressure on the
which has been proved to be one of the best FM Heusler
tip. Thus, the pressure on the contact will determine whether
alloys for CPP-GMR devices.18,19 The work by Bainsla et al.
it is in ballistic regime or not. Another requirement for
on CoFeMnGe7 appears to be the first spin polarization mea-
obtaining a good ballistic contact is the quality of the sample.
surement in any EQHA.
The smooth sample surface makes it easier to obtain a ballis-
tic point contact and hence it is often required that sample B. CoFeCrAl alloy
(polycrystalline bulk/foils/single crystals) surface is cleaned
properly and polished to give an almost mirror finish prior Bainsla et al.9 measured the current spin polarization of
for mounting. CoFeCrAl using PCAR technique (Fig. 8). The estimated
The sharp Nb tips prepared using electrochemical pol- P ¼ 0.67 6 0.02 in this alloy is found to be comparable to
ishing are generally used to make superconducting point that value reported for CoFeMnGe. The obtained value of P
contacts. Tip is attached to a drive shaft, which is capable of for CoFeCrAl is found to be higher than that of many ternary
moving up and down, with the help of micrometer mecha- or quaternary Heusler alloys.13,14,92
nism capable of moving the point contact linearly. The trans- In Section VI, a summary of various electronic structure
port measurements are made with the conventional four calculations reported in different EQHAs is presented.
probe arrangement, while the point contact and sample are
kept at constant temperature (at 4.2 K). The dI/dV data (dif- VI. ELECTRONIC STRUCTURE CALCULATIONS
ferential conductance curves) are obtained using the ac lock Apart from the volume of experimental studies on these
in techniques at a frequency of 2 kHz. The measured data are alloys, a reasonable amount of work has been reported on
analyzed using Blonder, Tinkham, and Klapwijk (BTK) their electronic structure by means of theoretical calculations
model;88 a multiple parameter least squares fitting is carried using various tools. Some of the important findings in this
out to deduce spin polarization using dimensionless interfa- regard are presented below.
cial scattering parameter (Z), superconducting band gap (D),
and P as variables The shape of the differential conductance A. CoFeMnZ (Z 5 Al, Si, Ga, and Ge) alloys
curves depends on the value of Z, for low Z values curves
Ab initio electronic structure calculations were per-
become flat near D, while for high Z values a peak appear
formed for CoFeMnZ (Z ¼ Al, Si, Ga, and Ge) alloys by
close to D. The obtained D values corresponding to the best
Alijani et al.45 As mentioned above, depending on the occu-
fit are found to be lower than the bulk superconducting band
pancy of the different sites, three different structural configu-
gap of Nb (1.5 meV), which is attributed to the multiple con-
rations are possible for a Y-type structure.45 The structural
tacts at the interface.91 The intrinsic value of current spin
optimization using ab-initio calculations showed that type I
polarization is estimated by recording the conductance curve
structure with Co(4d)Fe(c)Mn(4b)Z(4a) exhibits the lowest
at Z ¼ 0.
energy. The total energy for a type I structure was found to
In Subsections V A–V C, a review of the spin polariza-
be 270 meV lower than the type II structure. They also
tion studies reported with the help of PCAR technique on
compared the optimized lattice parameter (ath) values with
EQHAs is presented. As can be seen, only very few reports
the experimentally obtained values (aexp.) and found that ath
are available on the spin polarization measurements, which
values are 1% lower than the aexp., as shown in Table II.
is an important aspect to be considered for the further pro-
The discrepancy between calculated and experimental results
gress of this topic.
could be attributed to the temperature effect (XRD measure-
ment at room temperature), to disorder and/or other struc-
A. CoFeMnZ (Z 5 Si and Ge) alloys
tural effects. Thus, Alijani et al.45 used optimized lattice
Spin polarization of these alloys was measured using the parameter values for electronic structure and magnetic prop-
PCAR technique90 by Bainsla et al.7,8 Z ¼ 0.10 was the erties calculations.
minimum value that was achieved in the measurement of the The electronic structure calculations showed a typical
differential conductance curves for CoFeMnSi and fully spin polarized half-metallic ferromagnetic band struc-
CoFeMnGe.7,8 The estimated current spin polarization value ture for all the alloys. A typical Heusler alloy hybridization
031101-16 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

FIG. 8. (a), (c), and (e) show the normalized differential conductance curves corresponding to the lowest achievable Z values at 4.2 K for CoFeMnGe, CoFeMnSi, and
CoFeCrAl, respectively. (b), (d), and (f) represent the P vs. Z curves for CoFeMnGe, CoFeMnSi, and CoFeCrAl, respectively. Data taken from References 7, 8, and 9.

gap was observed between the low lying s-bands and remain- CoFeMnSi was predicted to be SGS from another ab-initio
ing high lying valence bands (which mainly p and d states) calculation by Xu et al.30 The predicted SGS behavior also
for CoFeMnZ (Z ¼ Al, Ga, Si, and Ge) alloys. The small supports the experimental claims (SGS behavior) made by
value of sp gap was found for CoFeMnAl alloy which points Bainsla et al.8 Therefore, it is understood that to resolve the
towards the weak hybridization and thus indicates structural discrepancy obtained in the findings for CoFeMnSi regarding
instability. The predicted weak hybridization may be the reason HMF vs. SGS bevahiour, very careful measurements and ab-
for the experimentally observed antisite disorder in the case of initio calculations are necessary.
€
CoFeMnAl (as discussed in the structural properties). Ozdogan Since it has been observed that the thin films based on
31
et al. also predicted HMF behavior for CoFeMnZ (Z ¼ Al the Heusler alloys lose their predicted high spin polariza-
and Si) using ab-initio electronic structure calculations. tion owing to the structural disorder,37–40 Feng et al.95 stud-
Bainsla et al.8 further investigated the electronic struc- ied the effect of structural disorder on the electronic and
ture of the CoFeMnSi alloy using the spin-polarized density magnetic properties of CoFeMnSi using the ab-initio calcu-
functional theory (DFT) within Vienna ab initio simulation lations. The effect of various types of antisite and swap dis-
package (VASP)93 with a projected augmented-wave basis94 orders on the electronic and magnetic properties of
using Generalized Gradient Approximation (GGA) exchange CoFeMnSi alloy was studied comprehensively. The reduc-
correlation functional. In order to make one-to-one compari- tion in spin down energy gap of disordered structures was
son between theory and experiment, they used experimental found, and their DoS moves entirely towards the lower
lattice parameter for their calculations. The calculated spin- zone. Feng et al.95 also found that the HMF nature is main-
polarized band structure and density of states (DoS) for an tained under different antisite and/or swap disorders in
energetically most favorable state are given in Fig. 9. It can CoFeMnSi, except for Co(Mn)-, Co(Si)-antisite, and Co-
be noticed that DoS exhibits a band gap 0.62 eV for one Mn, Co-Si swap disorder. Therefore, Feng et al.95 predicted
spin channel, while Fermi level falls within negligible gap in that HMF nature of CoFeMnSi is robust against structural
the other spin channel. The unique band structure obtained disorder, which supports the experimental observations by
by Bainsla et al.8 suggests that CoFeMnSi to be a close SGS. Bainsla et al.8
031101-17 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

FIG. 9. Band structure and density of

states for CoFeMnSi. (a) Majority-spin
band, (b) density of states, and (c)
minority-spin states. Reprinted with
permission from Bainsla et al., Phys.
Rev. B 91, 104408 (2015). Copyright
2015 American Physical Society.

B. CoFeCrZ (Z 5 Al, Ga, Si, and Ge) alloys Bainsla et al.10 further investigated the electronic struc-
ture of CoFeCrGa alloy. The calculations with aexp. and most
Electronic structure of the CoFeCrZ (Z ¼ Al, Ga, Si, and
stable structural configuration predicted a closed band gap
Ge) alloys was first studied by Gao et al.96 using the first-
character for majority-spin state and open band character for
principles full-potential linearized augmented plane-wave
minority-spin state near the EF, which suggest that CoFeCrGa
(FPLAPW) method with the WIEN2k package.97 CoFeCrGa
behaves like SGS. The value of minority-spin band gap was
and CoFeCrGe are found to have nearly HMF band structure,
found to be small (0.07 eV). They studied the effect of lat-
while CoFeCrAl and CoFeCrSi are reported to exhibit excel-
lent HMF behavior with large half-metallic gaps of 0.16 and tice contraction on the electronic and magnetic properties of
0.28 Ev, respectively, as per the report of Gao et al.96 The the CoFeCrGa using ab-initio calculations. The predicted DoS
HMF nature in CoFeCrAl and CoFeCrSi found to be robust versus lattice parameter plots are shown in Fig. 10. As can be
against the lattice compression. Gao et al.96 also predicted seen, the behavior of CoFeCrGa changes from SGS to HMF
that the HMF nature of CoFeCrAl and CoFeCrGa is lost, with decrease in lattice parameter. Note that the value of half-
while it is preserved in CoFeCrSi and CoFeCrGe, while metallic band gap in minority spin state at EF was found to
Coulomb interactions are considered. Xu et al.30 also studied increase with decrease in lattice parameter.
the CoFeCrAl alloy using ab-initio calculations and referred Electronic structure of CoFeCrGe was further studied by
€
it a SGS material. Ozdogan et al.31 also predicted CoFeCrAl Enamullah et al.52 Fully spin-polarized band structure was
as having SGS nature, while HMF behavior was predicted obtained with finite DoS at EF for majority-spin states and
for CoFeCrSi. half-metallic gap in the minority-spin states for CoFeCrGe.
As discussed above, the contradictory reports on the The theoretically predicted HMF nature and ordered crystal
physical nature (SGS vs. HMF) of CoFeCrAl prompted structure (Y-type) obtained by them make CoFeCrGe a
Bainsla et al.9 to do more careful first principles band struc- promising candidate for the spintronic applications.
ture calculations with spin-polarized DFT using VASP.93,94
They calculated the spin resolved band structure and DoS of C. CoMnCrAl, CoFeTiAl, and CoMnVAl alloys
CoFeCrAl for the most stable structural configuration. The
calculations were performed with both the experimental lat- Enamullah et al.52 also calculated the electronic struc-
tice parameter (aexp. ¼ 5.756 Å) and the relaxed lattice ture of CoMnCrAl using a spin polarized DFT implemented
parameter (arelax ¼ 5.690 Å), with HMF nature in both cases. within VASP93 with a projected augmented-wave basis.94
The value of the half-metallic band gap was found to be HMF band structure and DoS were obtained with experimen-
slightly higher (0.37 eV) in the case of arelax as compared tal lattice parameter and most stable structural configuration.
with the experimental value (0.31 eV). The band structure As discussed in Section II, a signature of the L21 disorder
calculations exhibit an open band gap (0.31 eV) for the was seen in the room temperature powder XRD patterns of
minority-spin states across the Fermi level (EF), while some CoMnCrAl by Enamullah et al.52 The electronic structure of
valence bands are found to cross the EF in the majority-spin HMF materials is generally known to be extremely sensitive
band and give rise to finite DoS at EF. Therefore, the elec- to any disorder.37–40 Therefore, the effect of structural disor-
tronic structure calculations by Bainsla et al.9 suggest HMF der on the stability and electronic structure of CoMnCrAl
nature for CoFeCrAl, which was confirmed by experimental was studied by Enamullah et al.52 HMF nature is found to be
results discussed earlier (electrical resistivity and current preserved under small amounts of structural disorder, while
spin polarization). it changes to metallic antiferromagnetic state beyond a
031101-18 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

FIG. 10. DoS vs. aexp. for CoFeCrGa

alloy. (a) 5.79 Å (aexp.), (b) 5.71 Å, (c)
5.60 Å, and (d) 5.50 Å. Reprinted with
permission from Bainsla et al., Phys.
Rev. B 92, 045201 (2015). Copyright
2015 American Physical Society.

€
certain excess Al in the alloy. Ozdogan et al.31 also predicted structure for all the alloys using ab-initio calculations. The
HMF nature for CoMnCrAl alloy. electronic structure calculations with type I crystal structure
The electronic structure of CoFeTiAl and CoMnVAl and optimized lattice parameter value (5.796 Å) predicted a
was first studied by Basit et al.51 Studies on CoMnVAl HMF nature for NiCoMnAl alloy, while a normal ferromag-
were carried out in more detail due to its better structural netic nature was predicted for NiCoMnGe and NiCoMnSn
stability (using experimental analysis) and possibility of alloys. These calculations suggest a spin polarization value
fully compensated half-metallic ferrimagnetism (FCHMF). of 56% and 60% for NiCoMnGe and NiCoMnSn, respec-
The ab-initio calculations of the electronic structure for tively. The theoretically predicted values of magnetic
CoMnVAl predicted a nonspin-polarized band structure, moment, 5.0, 4.93, and 5.14 lB for NiCoMnAl, NiCoMnGe,
and this was obtained independent of the starting parame- and NiCoMnSn, respectively, also indicate the HMF nature
ters and methods used (ferromagnetic and/or different types in NiCoMnAl. Due to the presence of B2 structural disorder
of ferrimagnetic order). Therefore, Basit et al.,51 on the in NiCoMnAl (as discussed in Section II), ab-initio calcula-
basis of their ab-initio calculations, completely excluded tions were performed with B2 disorder, and a pseudogap was
the possibility of FCHMF ground state for CoMnVAl. Both seen at approximately 0.15 eV below the Fermi level. Alijani
CoFeTiAl and CoMnVAl were found to have nonspin- et al.,55 calculated the electronic structure of NiCoMnGa
€
polarized band structure.51 Ozdogan et al.31 predicted that alloy. The spin-polarized band structure and DoS calcula-
both CoFeTiAl and CoMnVAl behave like semiconductors, tions were performed with the most stable structural configu-
similar to the other Heusler alloy with 24 valence electrons, ration and it was found to exhibit a HMF ground state.
i.e., FeMnCrAl, FeMnVSi, FeCrVAs, FeMnTiAs, CoCrVSi,
CoMnTiSi, and CoCrTiAs. E. NiFeMnGa and CuCoMnGa alloys
Lin et al.98 studied the effect of anti-site disorder on the Electronic structure calculations for these alloys were
electronic and magnetic properties of CoFeTiAl by perform- performed by Alijani et al.55 The optimization of the cubic
ing the spin-polarized band structure calculations. An inter- structure was the starting point for the calculations.
esting behavior with the antisite disorder was seen by Lin Furthermore, the stability of the cubic structure was studied
et al.;98 Co-Ti and Fe-Ti antisite disorder can induce a by calculating the elastic constants cij. On the basis of the cij
diluted magnetism in CoFeTiAl. Moreover, the Fe-Ti disor- values, NiFeMnGa was found to be structurally stable, while
der can induce a 100% spin polarization at EF. Thus, diluted CuCoMnGa is structurally unstable. The calculated spin-
magnetism can be induced in CoFeTiAl by antisite disorder polarized band structure and DoS predicted a HMF nature
instead of adding a magnetic element. for NiFeMnGa, while CuCoMnGa is found to be a normal
ferrromagnet.
D. NiCoMnZ (Z 5 Al, Ga, Ge, and Sn) alloys
F. CoFeTiZ (Z 5 Si, Ge, Sn, and Sb) alloys
Electronic structure calculations for NiCoMnZ (Z ¼ Al,
Ge, and Sn) alloys were performed using the FLAPW Zhang et al.99 calculated the electronic structure of
method by Halder et al.54 Type I structure {where Ni@4c(1/ CoFeTiZ (Z ¼ Si, Ge, and Sn) alloys by employing the
4, 1/4, 1/4), Co@4d(/4, 3/4, 3/4), Mn@4b(1/2, 1/2, 1/2), and Cambridge Serial Total Energy Package (CASTEP)100 based
Z@4c(0, 0, 0)} was found to be more favorable crystal on the DFT plane-wave pseudopotential method. It was
031101-19 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

found that at the equilibrium lattice parameter, total energy TABLE IV. Results of the electronic structure and magnetic properties cal-
of the ferromagnetic state is lower than that of the paramag- culations for various EQHAs, with composition, theoretical lattice parameter
(ath.), calculated magnetic moment (MC), and magnetic moment estimated
netic state for all these alloys. Thus, Zhang et al.99 per- using Slater-Pauling rule (MS-P), physical nature, and corresponding referen-
formed the calculations while considering the ferromagnetic €
ces. Ozdogan et al.31 also performed ab-initio calculations on various
ground state for all alloys. According to them, CoFeTiSi and EQHA systems in order to view their HMF and/or SGS properties.
CoFeTiGe were found to have half-metallic ferrimagnetic
band structure, while CoFeTiSn exhibited a quasi half- ath. MC MS-P Physical
Alloy (Å) (lB/f.u.) (lB/f.u.) nature References
metallic ferrimagnetic nature. In the case of CoFeTiSn,
Fermi level was found to move slightly into the valence CoFeMnAl 5.692 3.0 3.0 HMF 45
band for the minority spin electrons, which means that it CoFeMnSi 5.610 4.01–4.0 4.0 SGS 8
possesses a high spin polarization (nearly 100%), thus it is CoFeMnGa 5.708 3.0 3.0 HMF 45
called as quasi half-metallic ferrimagnet. The total mag- CoFeMnGe 5.710 4.0 4.0 HMF 7
netic moment value follows the Slater-Pauling behav- CoFeMnAs 5.740 4.99–5.0 5.0 HMF 102
CoFeMnSb 5.981 5.0 5.0 HMF 102
ior.57–59 With the variation Z ¼ Si ! Ge ! Sn, the size of
CoFeCrAl 5.69 1.97 2.0 HMF 9 and 96
the gap in minority spin band decreases and Fermi level
CoFeCrSi 5.63 3.0 3.0 HMF 31 and 96
was found to move from the bottom of the minority unoccu- CoFeCrGa 5.73 2.0 2.0 HMF 10
pied states to the top of the minority occupied states. The CoFeCrGe 5.72 2.99–3.0 3.0 HMF 52 and 96
half-metallic nature of the alloys was checked under lattice CoMnCrAl 5.71 0.98 1.0 HMF 31 and 52
compression (up to 6%) and was found to retain in the CoMnVAl … 0 0 SC 31 and 51
case of Z ¼ Si and Ge. In the case of Z ¼ Sn, transition from NiCoMnAl … 5.0 5.0 HMF 54
quasi half-metallic to half-metallic was estimated with lat- NiCoMnGa 5.784 5.07 5.0 HMF 55
tice compression of 1%. NiCoMnGe 5.796 4.93 6.0 FM 54
Berri et al.101 calculated the structural, magnetic, and NiCoMnSn … 5.14 6.0 FM 54
electronic properties of CoFeTiSb using full-potential linear- NiFeMnGa 5.755 4.01–4.0 4.0 HMF 55
CuCoMnGa 5.846 4.32 4.0 FM 55
ized augmented plane wave (FPLAPW) scheme within the
CoFeTiAl … 0 0 SC 31 and 51
GGA. The electronic structure calculations predicted a HMF
CoFeTiSi 5.73 1.0 1.0 HMF 99
band structure for CoFeTiSb, with half-metallic gap of CoFeTiGe 5.81 1.0 1.0 HMF 99
0.53 eV. The calculated total magnetic moment (2.0 lB) CoFeTiSn 6.09 1.0 1.0 Quasi HMF 99
found to agree with Slater-Pauling rule.57–59 CoFeTiSb 6.08 2.0 2.0 HMF 101
NiFeTiSi 5.84 2.0 2.0 HMF 103
G. Other equiatomic quaternary Heusler alloys NiFeTiGe 5.93 1.77 2.0 HMF 103
NiFeTiP 5.78 1.0 1.0 HMF 103
The spin-polarized band structure and DoS calculations
NiFeTiAs 5.83 1.39 1.0 FM 103
were performed in some other EQHAs, i.e., CoFeMnZ CoFeScP 5.789 1.0 1.0 HMF 104
(Z ¼ As and Sb) by Elahmar et al.,102 NiFeTiZ (Z ¼ Si, P, CoFeScAs 5.942 1.01–1.0 1.0 HMF 104
Ge, and As) by Karimian et al.,103 CoFeScZ (Z ¼ P, As, and CoFeScSb 6.198 1.02 1.0 HMF 104
Sb) by Gao et al.,104 CoMnTiZ (Z ¼ P, As, and Sb) by CoMnTiP 5.69 1.0 1.0 HMF 105
Khodami and Ahmadian,105 NiCoCrGa by G€okhan et al.,106 CoMnTiAs 5.83 1.0 1.0 HMF 105
VCoHfGa and CrFeHfGa by Yang et al.,107 and FeCrMnSb CoMnTiSb 6.07 1.0 1.0 HMF 105
by Singh et al.108 The results of these calculations are sum- NiCoCrGa 5.781 4.01 4.0 HMF 106
€
marized in Table IV. Ozdogan et al.,31 also performed ab- VCoHfGa 6.261 3.02 3.0 SGS 107
CrFeHfGa 6.261 3.0 3.0 SGS 107
initio calculations on various EQHA systems in order to
FeCrMnSb 6.067 2.0 2.0 HMF 108
understand their HMF and/or SGS properties. Table IV sum-
marized the results of theoretical calculations on different
EQHA systems.
structural order and distribution of the atoms in the crystal lat-
VII. SUMMARY AND CONCLUSIONS
tice. Tunability of the electronic structure and thereby the
Equiatomic quaternary Heusler alloys with Y-type crystal magnetic and electrical properties is another advantage of
structure show interesting properties useful for applications in EQHAs. Therefore, these alloys constitute one of the most
spintronic devices. They have been subjected to a large num- important material systems that belong to the half-metallic
ber of experimental and theoretical investigations in view of ferromagnetic family. A special class of HMF materials,
their fundamental and applied interests. Possibilities of known as spin gapless semiconductors, is also drawing a lot
achieving high Curie temperature and large spin polarization of attention from researchers currently. One can expect very
are the most crucial aspects of these alloys, in general. They interesting materials from this category as well in the very
also have the advantage of larger spin diffusion length over near future.
pseudo-ternary Heusler alloys such as X2Y1aY0 aZ, since the Various studies reported so far indicate that achieving a
random distribution of Y and Y0 in the latter gives additional fully ordered crystal structure in EQHAs is very difficult. It
disorder scattering. The electronic structure and hence the was found that even a small amount of atomic disorder could
physical properties of these alloys strongly depend on the cause changes in their electronic structure and their magnetic
031101-20 L. Bainsla and K. G. Suresh Appl. Phys. Rev. 3, 031101 (2016)

9
and transport properties. Therefore, the role of disorder in L. Bainsla, A. I. Mallick, A. A. Coelho, A. K. Nigam, B. S. D. Ch., S.
Varaprasad, Y. K. Takahashi, A. Alam, K. G. Suresh, and K. Hono,
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investigating its application potential. Experimental tools 10
L. Bainsla, A. I. Mallick, M. Manivel Raja, A. A. Coelho, A. K. Nigam,
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L. Bainsla, M. Manivel Raja, A. K. Nigam, and K. G. Suresh, J. Alloys
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Y. Du, B. S. D. Ch. S. Varaprasad, Y. K. Takahashi, T. Furubayashi, and
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