Superconductivity of BaLi4 under pressure

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Superconductivity of BaLi4 under pressure
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2013 J. Phys.: Condens. Matter 25 375701
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J.Phys.:Condens.Matter 25 (2013) 375701 (6pp) doi:10.1088/0953-8984/25/37/375701
Superconductivity of BaLi
Anne Marie J Schaeffer
,Matthew C DeLong
,Zachary WAnderson
WilliamB Talmadge
,Sivaraman Guruswamy
and Shanti Deemyad
Department of Physics and Astronomy,University of Utah,Salt Lake City,UT 84112,USA
Department of Physics,Cornell University,Ithaca,NY 14853,USA
Metallurgical Engineering,University of Utah,Salt Lake City,UT 84112,USA
Received 29 April 2013,in final form31 July 2013
Published 21 August 2013
Online at
We studied the pressure-induced superconductivity of BaLi
up to 53 GPa by means of
electrical resistivity in a diamond anvil cell.Superconductivity in BaLi
is first observed at a
pressure of 5.4 GPa with a superconducting critical temperature (T
) of 4.5 K.Below 2 GPa,
superconductivity is not observed above the minimumtemperature achievable in the current
study,2 K.Between 5.4 and 12 GPa,the T
increases steeply to its maximumvalue of 7 K.
Above 12 GPa,the pressure dependence of T
is complex and the sign of dT
=dP changes
several times in going up to the maximumpressure studied,of 53 GPa.
(Some figures may appear in colour only in the online journal)
Enhancement of the properties of metals by alloying them
with other metals is a technique that has been used from
the earliest stages of human history.Prior to the discovery
of superconductivity in MgB
,with T
D 40 K [1],it was
widely thought that the maximum superconducting transition
temperature from electron–phonon coupling was 30 K [2].
Superconductivity in MgB
,which was confirmed to be
a phonon-mediated superconducting system [3],restored
interest in compounds of low atomic number (Z) elements.
Lithium is the lightest metallic and superconducting
element.Due to its light mass and metallic behavior,several
compounds of lithium have been predicted and subsequently
studied for superconducting properties (e.g.[4–7]).At
ambient pressure,lithium becomes a superconductor below
0.4 mK [8].This value is orders of magnitude lower than
the theoretically predicted T
of 1 K by ab initio electronic
structure calculations and the McMillan expression [9].
This low T
is attributed to several factors such as the
reduced electronic density of states at the Fermi surface
in the 9R phase of lithium [10] or the suppression of
superconductivity due to spin fluctuations [11].Under high
pressure,lithium reaches one of the highest transition
temperatures of elemental superconductors [12–14];T
14–20 K.Alternatively,by chemical modification,it may
be possible to synthesize a lithium-rich compound in
which a high superconducting transition temperature is
achieved through electronic enhancement.Studying the
superconducting phase diagram of lithium-rich compounds
can provide insight to finding ways which enhance the
superconductivity by chemical modification.
None of the alkali earth metals that are miscible
with lithium at ambient pressure (Ca,Sr,and Ba) are
superconducting at one atmosphere,however,all become
superconductors under high pressure [15–17].While calcium
reaches the highest T
(29 K at 216 GPa [17]) of any
elemental superconductor,bariumhas a lower critical pressure
of superconductivity than either calcium or strontium.
Barium has complex pressure dependent structures [18–21]
and becomes a superconductor above 3.7 GPa with T
60 mK [15,16,22].The transition temperature of barium
increases to about 5.3 K at 18 GPa and then smoothly
decreases to 4:5 K at 43 GPa,which is the highest pressure
at which its superconductivity has been studied.
The presence of a minimumin a melting curve,indicative
of lattice instabilities and the presence of soft phonon
modes,in many cases is correlated with an enhancement
2013 IOP Publishing Ltd Printed in the UK &the USA
J.Phys.:Condens.Matter 25 (2013) 375701 A MJ Schaeffer et al
Figure 1.Unit cell of BaLi
,P6=mcc (192)—hexagonal,
a D 9:1875.5/
A;c D 9:1875.7/
A;c=a D 1:0000;V D
;Z D 2.
of superconductivity [23].The melting curve of barium
reaches the lowest melting temperature of all alkali earth
metals in all studied pressure ranges (T
 400 K) [24]
and its melting temperature decreases in the pressure
range of 1.5–8 GPa,which coincides with the onset of
pressure-induced superconductivity.Lithium itself has a
very unusual melting curve,which also exhibits a drastic
decrease in its melting temperature under pressure [25–28],
as well as a sequence of symmetry-breaking structural phase
transitions under pressure [29,30].The minimum of the
melting curve of lithium occurs at the phase boundary
of fcc-hR1-cl16.This structural phase boundary at low
temperature coincides with the maximum temperature of
lithium’s superconductivity [12–14].
Lithium forms two binary compounds with barium,
and Ba
;both are rich in lithium [31–33].These
compounds have large unit cells and complex structures
at ambient pressure.In BaLi
,the compound crystallizes
in the hexagonal space group,P6
=mmc with 24 lithium
and 6 barium atoms per unit cell (figure 1).Lithium
atoms form Li [12] icosahedral cages centered on another
lithium atom.The cages are connected with additional
lithium atoms.Each is surrounded by 6 barium atoms,all
together forming a hexagonal pattern [32].The band structure
and electronic properties of such a structure are complex,
thus superconductivity can have a non-intuitive pressure
In this paper we have experimentally investigated the
superconductivity of BaLi
from ambient pressure to 53 GPa
in a diamond anvil cell apparatus and pursued the possibility
of an enhancement of lithium’s superconducting properties by
chemical modification with barium.
2.Experimental details
has been previously synthesized and its structures
have been refined by x-ray studies [32,33].We used the
synthesis procedure from the latest studies [32],summarized
here.Stoichiometric proportions of lithium (99.9% purity,
Alfa Aesar,Na main impurity) and barium(99%purity,Sigma
Aldrich,Sr main impurity) were measured with better than
1%precision by weight ratio of the components inside a high
purity argon glove box and were mixed together.The mixture
was placed in a molybdenum crucible and sealed under a low
pressure argon atmosphere inside a Pyrex ampule by using
an oxy-acetylene torch.The Ba–Li phase diagram shows a
peritectic reaction (solid phase 1 C liquid phase!solid
phase 2 on cooling) at 429 K at Ba–80%Li and a eutectic
reaction at 416 K and 89.5% Li.Stoichiometric BaLi
kept at the liquid region (T D 623 K=350 C) in a Thermolyne
30 400 oven for ten days and cooled down slowly at rate of
1 K h
to a temperature of 421 K just below 429 K and
above the eutectic temperature of 416 K.The sample was
allowed to stay at this temperature for over 11 days.The
reaction temperature of 421 K is 97% of the melting point
of BaLi
).Sufficiently fast diffusion across
is expected at this temperature and over 10 days of
heat treatment was expected to allow the peritectic reaction
to go to completion based on the high homologous reaction
temperature (T=T
) and the reference paper by Smetana and
Simon [32].The ampule was transferred to the argon-filled
glove box.The appearance of BaLi
was consistent with
the description given in previously published work [32].The
resultant compound is a polycrystalline sample which is brittle
and xenomorphic in appearance.This is in stark contrast to
pure lithium and barium,both of which are soft,very pliable
The sample was ground in a tantalumcrucible to fine size
particles for several hours and was sealed in a 1 cm
with 2 m Mylar film on top of a glass slide.X-ray powder
diffraction studies at ambient pressure were performed in a
Philips X’Pert x-ray Diffractometer with Cu K radiation
( D 1:540 60
A).The diffraction pattern collected over 1.5 h
was consistent with the diffraction pattern of BaLi
from the
refined crystal structure of BaLi
by Smetana and Simon [32].
has several overlapping diffraction peaks with Ba.
However,analysis of the XRDprofile and the absence of some
of the intense peaks of barium,such as Ba (310),conclude
that the amount of bcc barium present,and consequently
lithium-rich regions,in our sample,if any,is below 5%.
All high pressure data were taken inside a diamond
anvil cell (DAC).Superconductivity was determined by the
sudden drop in resistivity,measured by means of an AC
resistivity technique by either quasi-four probe or exact
four probe,built on an insulating gasket (figure 2).A
further test of superconductivity in the sample,to exclude
filamentary superconductivity paths,was also done by the
AC magnetic susceptibility method at 12 GPa where the
maximum T
was observed in the resistivity experiment.
A strong signal from magnetic susceptibility measurements
allows excluding the possibility of the presence of a small
filamentary superconducting path,but does not exclude the
possibility of surface effects.It was assumed that BaLi
react with diamonds in a similar manner to pure lithium,
and the DAC was prepared as outlined in previous high
pressure studies on lithium [25].In order to better compare
the superconducting versus pressure curve of BaLi
to that of
barium (see results),the T
of barium was measured with the
same setup.
J.Phys.:Condens.Matter 25 (2013) 375701 A MJ Schaeffer et al
Figure 2.AC resistivity measurement setup.Inset shows the
arrangement of the leads in quasi-four probe measurement.
All data were taken in six isobaric runs inside a
temperature controlled liquid
He cryostat (Janis SVT-200).
Pressure was determined from fluorescence of several ruby
spheres distributed across the sample chamber,measured
before and after each cooling cycle.Temperature was
measured using a diode thermometer,thermally anchored to
the DAC close to the sample.
Superconductivity was measured in BaLi
from ambient
pressure to 53 GPa.The resistance as a function of
temperature was recorded for both cooling and heating.Due
to better temperature control,the onset of T
is determined
fromthe heating curves in all cases (figure 3).In high pressure
experiments,especially non-hydrostatic experiments which
are an inherent part of resistivity experiments,large pressure
gradients in the sample chamber are unavoidable;thus a
broadening of the superconducting transition is present.In the
pressure regions where the T
is monotonically increasing,
the onset of the transition is a good representative of the
of the sample at maximum pressure.In the pressure
regions of monotonically decreasing T
,the scenario is just
the opposite.We have shown in all data the onset and the end
Figure 3.Resistivity as a function of temperature for selected data points.The size of the transition in different runs depends on sample
size.In the graphs above,all data have been scaled to show the same size transition for comparison.Arrows indicate the onset of T
Resistivity curves (a),(b) are for BaLi
,the asterisk near the 2 GPa curve is a possible onset of a superconducting transition near 2.5–2 K.
The resistivity curves in (c) are for bariumat 35 and 43 GPa.Red and blue bars indicate the upper or lower bounds of T
as defined by [16].
The curve in (d) is the data point taken at 12 GPa by the AC magnetic susceptibility method.The ratio of the residual resistivities at ambient
pressure is R.297 K/=R.5 K/ 14 and samples were showing metallic behaviour throughout all pressure runs.
J.Phys.:Condens.Matter 25 (2013) 375701 A MJ Schaeffer et al
Figure 4.Superconducting phase diagramof BaLi
.The data point
at 53 GPa,marked by a star,remains unconfirmed due to the
diamond failing before the pressure was confirmed after heating.
The data point in run 6 (12 GPa,6.9 K) is taken by the AC magnetic
susceptibility method.
of each transition.In all cases,the accuracy in temperature
determination is 0.1 K.Superconductivity down to the
lowest temperature accessible in our setup (2 K) was not
observed at ambient pressure nor at 2 GPa.
Superconductivity first appears at 5.4 GPa,with a T
4.5 K,then monotonically increases to a maximum of 7 K at
12 GPa.The onset of the pressure-induced superconductivity,
determined by extrapolation,is shifted to lower pressures than
barium and the maximum T
in BaLi
is higher by 2 K
(there is a weak indication of possible superconductivity in
near or under 2.5 K at 2 GPa shown by an asterisk in
figure 3(a)).After reaching the maximum,the T
at a shallower slope,to 4.7 K at 37.5 GPa.At higher
pressures,a second increase in T
was observed,reaching a
second maximum of 5.5 K at 45 GPa,after which the T
begins to decrease once more up to 49 GPa.A third,very
slight increase in T
under pressure from 49 to 53 GPa was
observed,however,the diamond failed before the pressure
could be confirmed after warming up the sample and this
data point is not conclusive.The resistivity curve of bariumat
35 GPa and the resistivity of BaLi
at 8 and possibly 29 GPa
showed double step like drops in resistivity at T
(figure 3).
This double step transition is sharp and is different from
pressure broadening effects and can be due to structural phase
transitions occurring in the given pressure ranges.Different
coexisting phases near the structural phase transitions can
exhibit different superconducting critical temperatures which
lead to a double transition.
The superconducting phase diagramof BaLi
varies from
that of elemental lithium [12–14].BaLi
does not reach a
maximum T
close to that of lithium,14–20 K,however,it
begins to superconduct at a much lower pressure,5.4 GPa
versus 20 GPa.It also reaches a maximum T
at a lower
pressure,12 versus 30 GPa.The superconducting phase
diagram of barium [16,34],is more similar to that of BaLi
Figure 5.Superconducting phase diagramof BaLi
(this study) in
comparison to elemental lithium[12] and barium[16,34].The
dashed lines mark the structural phase boundaries of barium[21].
Black squares show the superconductivity of bariumthat was
measured in the current study for better comparison of the
superconductivity of bariumand BaLi
The overall similarity of the shape of the T
versus pressure
graph of BaLi
to elemental bariumprompted a closer look at
the T
of bariumat high pressure.The T
of BaLi
and barium
differ most distinctly in the lower pressure range,where BaLi
first becomes a superconductor (figure 4).However,in the
pressure range above 32 GPa,the two appear to become
more similar,from 32 to 38 GPa,the T
are within error of
each other.To elucidate the comparison between BaLi
barium,two data points for barium were taken at pressures
of 35 and 43 GPa.We found no inconsistencies with previous
studies [16].We slightly extended the known superconducting
phase diagram of barium,analyzing in the same manner as
Dunn and Bundy [16].
While BaLi
shows a distinct enhancement of super-
conductivity in a small pressure range above 40 GPa,any
evidence of a enhanced superconducting phase in barium is
not conclusive.Barium overall shows a rather flat decline
in T
[16] from 5.3 K at 18 GPa to 4.2 K at 38 GPa,at
43 GPa,the T
increases slightly to 4.4 K.However,due to
the differences in the definition of T
,this evidence is hardly
compelling.When defining the upper limit according to Dunn
and Bundy [16],the T
of Ba decreases from5.3 K at 18 GPa
to 4.7 K at 35 GPa,then increases again to 4.9 K at 38 GPa
and decreases to 4.6 Kat 43 GPa.From35 to 43 GPa,all these
data are within error of each other.The presence of a second
superconducting phase is not ruled out,the data are within
error bounds and there is not a strong enough indication to
draw a conclusion.
The similarities in the pressure dependence of supercon-
ductivity in BaLi
and pure barium may suggest the
possibility of the presence of non-reacted barium forming a
J.Phys.:Condens.Matter 25 (2013) 375701 A MJ Schaeffer et al
percolated superconducting path (figure 5).This possibility
is examined and excluded based on the following tests and
analysis:the fraction of volume at percolation threshold in a
random 3D network for the formation of a complete barium
superconducting path is 16% [35–38].The resistivity of
the sample at its superconducting transition drops to less
than 15% of its value right before the transition in all cases.
Including the small pieces of platinum electrode present in
the path,the large drop in the resistivity is consistent with
the presence of a complete superconducting path present
in the sample.This implies the presence of over 16% of
non-reacted barium in the sample,this is only possible at
the cost of a large amount of non-reacted lithium,with much
higher superconducting T
;which was not observed here.To
exclude the possibility of the presence of a large amount
of non-reacted barium in a single grain,we have used six
different pieces of samples in different runs and confirmed
similar superconducting behavior for all of them (figure 4).
In addition,we have used the technique of AC magnetic
susceptibility to exclude the filamentary superconductivity in
our sample at 12 GPa,where the maximum T
of 7 K was
observed in electrical resistivity measurements,and found
consistent results.According to the phase diagram here,it
is plausible to argue that a distorted barium sublattice is the
major contributor to the superconductivity in BaLi
up to
37 GPa.At ambient pressure,the Ba–Ba distance in BaLi
slightly increased compared to a pure barium lattice (4.35
in pure barium to 4:55–4:6
A in BaLi
lithium has higher electron affinity than barium at ambient
conditions,the enhancement of T
in BaLi
compared to
pure barium is likely a lattice effect caused by the presence
of lithium rather than an electronic effect.It is notable that
at ambient pressure,the bonding energy of barium 3d
peak in BaLi
is shown to be very close to metallic barium,
whereas lithium’s 1s emission is decreased by 1 eV in BaLi
compared to pure metallic lithium [39].This is attributed to
the electronic re-arrangement of lithium in the BaLi
while the electronic properties of barium in BaLi
similar to metallic bariumat ambient pressure.
Barium has a rich structural phase diagram from
ambient pressure to 90 GPa [18–21].Barium undergoes a
pressure-induced phase transition from bcc to hcp around
5.5 GPa [20],which is relatively near,yet somewhat above,
the onset of its superconducting phase transition.Barium has
an hcp structure from 5.9 to 11.4 GPa,phase II,then another
hcp phase from 45 to 90 GPa,phase V [20,21].The T
barium increases monotonically throughout the phase I to the
phase III region,until it reaches its maximum of 5.3 K at
18 GPa.This pressure,as well as the region in which barium
and BaLi
are the most similar,lies within the boundaries
of barium’s phase IV;which consists of a series of complex
host–guest structures (Ba-IVa,b,c,etc) and persists over a
wide pressure range from12.6 to 45 GPa [19,21].It has been
noted [19,21],that the host structure appears to be stable
over the wide pressure range while the guest changes.The
loose analogy to the structure of ambient pressure BaLi
would be the barium sublattice being the guest,and the
lithium sublattice being the host.Compared to barium,the
lithium sublattice has a complex structure in BaLi
and its
contribution to superconductivity may also lead to a complex
pressure dependence at higher pressures (figure 5).
The structures of BaLi
under pressure have not yet
been studied and the complex pressure dependence of
superconductivity in this material may be associated either
with a sequence of structural phase transitions of one or both
sublattices,or drastic changes in electronic structures under
compression.The absence of superconducting transition tem-
peratures above 7 K,in the superconducting phase diagramof
,however,excludes the possibility of a pressure-induced
phase separation of this compound to elemental barium and
lithiumin the pressure range of this study.
In summary,BaLi
is shown experimentally to exhibit
pressure-induced superconductivity above 5.4 GPa.The
complex pressure dependence of superconductivity in BaLi
suggests a sequence of changes in the structures,or the
electronic properties of this material.Detailed structural
analysis at high pressure will shed light on the supercon-
ductivity in BaLi
.Our experimental results show a close
relation between the superconductivity of barium and BaLi
and could provide insight for finding new superconducting
intermetallic materials with higher T
at ambient pressure.
Extending the present experiments to higher pressures may
result in the emergence of new enhanced superconducting
phases,in which lithiumplays a dominant role.
The authors thank Dr R Hennig for insightful discussions
on the electronic properties of BaLi
,Dr A Simon for
explanations regarding sample preparation and Dr A Efros
for kindly providing references on percolation theory.
Experimental support by S R Temple,J Jue,Z Xu,and
J Bishop in sample preparation and low temperature studies,
J Hansen in magnetic susceptibility measurements,and
analysis of the XRD spectrum by M Sygnatowicz in the
Materials Characterizations Lab of the University of Utah,
Material Science Department is acknowledged.WT would
like to acknowledge the financial support from University of
Utah UROP program.Initial sample synthesis was done with
great help from the late W Wingert.This research has been
partially supported by the National Science Foundation under
Grant No.DMR 11-21252.
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