Superconducting properties of Zr1+xNi2-xGa

and Zr1-xNi2+xGa Heusler compounds

Cite as: AIP Advances 7, 055706 (2017); https://doi.org/10.1063/1.4974279
Submitted: 23 September 2016 . Accepted: 27 October 2016 . Published Online: 11 January 2017

Saad Alzahrani, and Mahmud Khan

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AIP Advances 7, 055706 (2017); https://doi.org/10.1063/1.4974279 7, 055706

© 2017 Author(s).
 AIP ADVANCES 7, 055706 (2017)

Superconducting properties of Zr1+x Ni2-x Ga

and Zr1-x Ni2+x Ga Heusler compounds
Saad Alzahrani and Mahmud Khana
Department of Physics, Miami University, Oxford, Ohio 45056, USA
(Presented 3 November 2016; received 23 September 2016; accepted 27 October 2016;
published online 11 January 2017)

The superconducting properties of a series of Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga

compounds have been investigated by x-ray diffraction, electrical resistivity, dc
magnetization, and ac susceptibility measurements. While the parent compound,
ZrNi2 Ga, exhibited the cubic L21 Heusler structure, multiple non-cubic structures
formed in the Zr and Ni rich doped materials. For x ≤ 0.3, all Zr1-x Ni2+x Ga
compounds demonstrated superconducting behavior, but no superconductivity was
observed in the Zr1+x Ni2-x Ga alloys for x > 0.2. The magnetization data revealed
that all materials in both Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga series exhibited type-II
superconductivity. With increasing doping concentration x, the paramagnetic order-
ing were enhanced in both systems while the superconducting properties were
found to weaken. The observations are discussed considering the structural dis-
orders in the systems. © 2017 Author(s). All article content, except where oth-
erwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/). [http://dx.doi.org/10.1063/1.4974279]

INTRODUCTION
Ni based Heusler alloys with the cubic L21 structure are well known to exhibit exciting phenom-
ena including martensitic phase transitions,1–3 magnetocaloric effects,4,5 shape memory effects.6,7 and
superconductivity.8–10 Considering the fact that elemental Ni is ferromagnetic, Ni-rich intermetallic
alloys are expected to order magnetically instead of demonstrating superconductivity. Therefore, from
fundamental science point of view, the observation of superconductivity in Ni based Heusler alloys are
of great interest. ZrNi2 Ga is one of these alloys that show superconductivity with a superconducting
(SC) transition temperature of TC ≈ 2.9 K.9
Including ZrNi2 Ga there are nearly 19 Heusler superconductors that have 27 valence electrons
per formula unit with an average of 6.75 electrons per atom.11 In common, superconductivity in
these materials are explained considering the van Hove singularities, which refers to a saddle point in
the energy dispersion curves of the electronic structure of the respective material.12 Among these 19
superconductors, several are rare-earth metal based, like YbPd2 Sn and ErPd2 Sn, where superconduc-
tivity and antiferromagnetic interactions co-exist.13–15 ZrNi2 Ga was shown to be a weakly coupled
BCS type-II superconductor, with a paramagnetic state above TC .9 It was also shown that partial
replacement of Zr by Nb resulted in the broadening of the Van Hove singularity and introduced a
high degree of disorder in Zr1-x Nbx Ni2 Ga, causing a suppression of TC of the system.
Here, we have experimentally studied the magnetic and SC properties of Zr1+x Ni2-x Ga and
Zr1-x Ni2+x Ga (0 ≤ x ≤ 0.3) systems. The number of average of electrons per atom is less than 6.5
in Zr1+x Ni2-x Ga while greater than 6.5 in Zr1-x Ni2+x Ga compounds. Therefore, it is interesting to
explore the SC properties of these two systems.

EXPERIMENTAL TECHNIQUES
The Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga (0 ≤ x ≤ 0.3) samples (2 g each) were prepared by
arc-melting the constituent elements (of more than 3N purity) in high purity argon atmosphere.

a
Author to whom correspondence should be addressed: khanm2@MiamiOH.edu

2158-3226/2017/7(5)/055706/6 7, 055706-1 © Author(s) 2017

055706-2 S. Alzahrani and M. Khan AIP Advances 7, 055706 (2017)

For homogenization, the samples were sealed in partially evacuated and partially argon filled quartz
tubes and annealed at 1073 K for two weeks followed by quenching in cold water. The phase purity
and the crystal structure of the alloys were investigated by x-ray diffraction (XRD) measurements per-
formed on a Scintag Pad X-ray powder diffractometer that employed Cu-Kα radiation. The diffraction
patterns were indexed using a computer program known as PowderCell.16 The electrical resistivity
(by a four probe technique), dc magnetization and ac susceptibility measurements were performed on
a Physical Propriety Measurement System (PPMS) made by Quantum Design Inc. Before obtaining
the zero field cooled (ZFC) magnetization versus temperature, M(T), data, the samples were cooled
from 10 K to 2 K in a zero magnetic field. When the temperature stabilized at 2 K, a magnetic field
of 25 Oe was applied, and the ZFC M(T) data were recorded as a function of increasing temperature.
The field cooled cooling (FCC) M(T) data were obtained while sweeping down the temperature from
10 K to 2 K in the presence of the 25 Oe field. The ac magnetic susceptibility (ACMS) measurements
were performed in an ac field of 10 Oe and frequencies of 100 Hz, 1000 Hz, 5000 Hz, and 10000 Hz.

RESULTS AND DISCUSSION

The XRD patterns of ZrNi2 Ga are shown in FIG. 1. In agreement with the literature, the material
exhibits the L21 cubic structure with a lattice parameter of 6.0874 Å.9 It is interesting to note that
even a minor variation in the stoichiometry significantly changes the crystal structures of both the
Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga systems. As shown in the insets of FIG. 1, both the Ni and Zr rich
materials exhibit multiple structural phases. The structural phase of the Ni rich material with x = 0.1

FIG. 1. Room temperature XRD patterns for ZrNi2 Ga. The insets show the XRD patterns of selected Zr1+x Ni2-x Ga and
Zr1-x Ni2+x Ga compounds.

FIG. 2. Temperature dependence of the normalized resistivity of ZrNi2 Ga, Zr0.8 Ni2.2 Ga, and Zr1.2 Ni1.8 Ga, measured at a
zero magnetic field.
055706-3 S. Alzahrani and M. Khan AIP Advances 7, 055706 (2017)

(Zr0.9 Ni2.1 Ga) consists of the L21 phase (approximately 64 %) and the Ni7 Zr2 -type monoclinic phase
(∼36 %). For the compound with x = 0.2 (Zr0.8 Ni2.2 Ga), the L21 phase reduces to ∼45 %, while the
monoclinic phase increases to ∼41 %. In addition, a ∼14 % of ZrNi2 -type tetragonal phase also exists
in the Zr0.8 Ni2.2 Ga compound. For x = 0.1, the Zr rich alloy (Zr1.1 Ni1.9 Ga) exhibits ∼40 % of the
L21 phase, ∼35 % of Ni7 Zr2 -type phase, and ∼25 % of a NiZr2 -type tetragonal phase. For the alloy
with x = 0.2 (Zr1.2 Ni1.8 Ga) the L21 phase reduces to ∼14 % while the Ni7 Zr2 -type phase increases to
∼64%. The NiZr2 -type tetragonal phase marginally reduces to ∼22%. The structural variations and
the multiple phases formations in the Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga compounds may be attributed
to the large difference in the metallic radii of Ni (1.246 Å) and Zr (1.602 Å).17
FIG. 2 shows the temperature dependence of normalized resistivity, ρ(T ), data for the
Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga (x = 0 and 0.2) alloys. The SC transitions (represented by the
sharp drops of resistivity near 2 K) are apparent in all three materials. The parent compound,
ZrNi2 Ga, exhibits a TC of ∼2.8 K, which is consistent with earlier reports.9 The Ni-rich alloy,
Zr0 .8 Ni2.2 Ga, demonstrates a TC of ∼2.6 K while the Zr rich compound, Zr1.2 Ni1.8 Ga, exhibits a TC
of ∼2.5 K. In addition to the sharp drop of resistivity at TC , the Zr and Ni doped off-stoichiometric
compounds exhibit slope-change-like anomalies before TC (at ∼5.5 K for Zr0 .8 Ni2.2 Ga and at

FIG. 3. Temperature dependence of the dc magnetization of (a) ZrNi2 Ga, (b) Zr0.8 Ni2.2 Ga, and (c) Zr1.2 Ni1.8 Ga, measured
at a magnetic field of 25 Oe.
055706-4 S. Alzahrani and M. Khan AIP Advances 7, 055706 (2017)

∼4.2 K for Zr1.2 Ni1.8 Ga). Unlike the other materials, that exhibit zero resistivity below TC , the
Zr rich alloy exhibits a non-zero residual resistivity below TC . The slope-change-like anomalies
observed in the ρ(T ) data of the doped materials may indicate the presence of minority super-
conducting phases with higher Tc’s, as also indicated by the multi-phase nature of the samples.
The non-zero residual resistivity observed in Zr1.2 Ni1.8 Ga below TC may be attributed to the
fact that the material exhibit only 14 % of the L21 structure, as shown earlier in the XRD data
(FIG. 1).
The M (T ) data for Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga (x = 0 and 0.2) alloys measured at a magnetic
field of 25 Oe are shown in FIG.3. All samples exhibit zero magnetization above TC . The ZFC and
FCC M(T) data overlaps above TC , but below TC they demonstrate thermomagnetic irreversibility.
The FCC data stays nearly zero below TC , while the ZFC data sharply drops, demonstrating a
negative magnetization. These irreversible behaviors observed in the ZFC and FCC M(T) data are
typical for type-II superconductors.9 Although not shown here, the SC transitions and the associated
thermomagnetic irreversibility were also observed in the Ni rich alloy with x = 0.3. However, the
transition was not observed in the Zr rich alloy with x = 0.3. This behavior may be associated with
the relatively large amounts of the secondary phases present in the Zr rich compounds, as discussed
earlier.

FIG. 4. Field dependence of the magnetization of (a) ZrNi2 Ga, (b) Zr0.7 Ni2.3 Ga, and (c) Zr1.3 Ni1.7 Ga, measured at 2 K.
055706-5 S. Alzahrani and M. Khan AIP Advances 7, 055706 (2017)

FIG. 4 shows the M(H) data for Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga (x = 0 and 0.3) samples measured
at T = 2 K, where the samples are in SC states. During the measurements the field was varied from
-10 kOe to 10 kOe. For a better visualization of the hysteresis loops, the M(H) data for the lower field
regions are shown in the insets of FIG. 4. All samples, except for Zr1.3 Ni1.7 Ga, show the butterfly
loops typical for a type-II superconductor. The parent sample, ZrNi2 Ga, exhibits the largest hysteresis
loop and although fairly week, above a critical field the M(H) data show paramagnetic behavior. It
is interesting to note that the paramagnetic behavior enhances (while the SC behavior diminishes)
in both the Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga materials with increasing Ni and Zr concentrations (see
FIG. 4b and 4c). In case of Zr1.3 Ni1.7 Ga, no butterfly loop is observed and the M(H) data for the
sample demonstrate a superparamagnetic behavior. For all Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga samples
the M(H) data measured above TC at 5 K and 10 K show paramagnetic (in case of Ni rich sam-
ples) and superparamagnetic (in case of Zr rich samples) behaviors. It is likely that the enhanced
paramagnetic and superparamagnetic interactions are due to the secondary phases in the doped
samples.

FIG. 5. Real components of ac susceptibility of (a) ZrNi2 Ga, (b) Zr0.8 Ni2.2 Ga, and (c) Zr1.2 Ni1.8 Ga, measured at an ac field
of 10 Oe and various frequencies.
055706-6 S. Alzahrani and M. Khan AIP Advances 7, 055706 (2017)

FIG. 5 show the temperature dependence of the real components of ac susceptibility, χ 0 (T), of
Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga (x = 0 and 0.2). The SC transitions, represented by the sharp drop
of χ 0 near TC , are observed for all samples. Between 2.5 K an 2.9 K, the χ 0 (T) for the parent com-
pound show a noticeable frequency dependence (see FIG. 5a), where TC shifts to lower temperature
with increasing frequency. Such frequency dependence are usually associated with the flux-creep
of type II superconductors.18 The frequency dependence is vaguely observed in the doped alloys
(FIG. 5a and 5b), demonstrating the weakening of the SC properties of the doped systems.

CONCLUSIONS
In summary, we have studied the SC properties of Zr1+x Ni2-x Ga and Zr1-x Ni2+x Ga compounds.
For x < 0.3 all materials exhibit superconductivity and demonstrates paramagnetic ordering above TC .
Due to the large differences in the atomic radii of Zr and Ni, even a small variation in the stoichiometry
of the materials results in significant changes in their structural properties. The structural disorder
dramatically effects the SC properties and magnetic ordering of the systems.
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