to appear in Supercond. Sci. Technol.

18 (2005) R1-R8 1
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TOPICAL REVIEW

Assembling the puzzle of superconducting

elements: A Review
Cristina Buzea 1,2 * and Kevin Robbie 1,2
1
Physics Department, Queen's University, Kingston K7L 3N6, Canada
2
Centre for Manufacturing of Advanced Ceramics & Nanomaterials, Queen's University

ABSTRACT: Superconductivity in the simple elements is of both technological

relevance and fundamental scientific interest in the investigation of superconductivity
phenomena. Recent advances in the instrumentation of physics under pressure have
enabled the observation of superconductivity in many elements not previously known to
superconduct, and at steadily increasing temperatures. This article offers a review of the
state of the art in the superconductivity of elements, highlighting underlying correlations
and general trends.

PACS: 74.70.Ad, 74.62.-c, 74.62.Fj, 74.62.Yb

(Some figures in this article are in colour only in the electronic version)
__________________________________________________________________________________________

1. Introduction Superconductivity is a collective state occurring in the

electron population of a material, and its study is an
After two decades of focused research on important discipline of condensed matter physics. The
superconductivity in copper oxides or cuprates, interest has occurrence of superconductivity is not restricted to
recently veered toward simpler materials, such as conventional materials, however, but is believed to be a
magnesium diboride and basic elements. Simple materials universal phenomenon, arising at all scales from
were recently reported to superconduct at, surprisingly high superconducting cosmic strings generated as topological
critical temperatures (Tc), 40 K for MgB2 - a binary defects in the early universe [9] or superconducting cores
compound [1], and 20 K for lithium under pressure - the in neutron stars [10], down to the fascinating phenomenon
highest Tc for a simple element [2]. During the last few of nuclear size superconductivity [11].
years, the physics community has been delighted with
observation of superconductivity in many new elements,
some of them under pressure, such as sulphur 17 K [3],
oxygen 0.5 K [4], carbon in nanotube 15 K [5] and
diamond forms 4K [6], a non-magnetic state of iron 1 K
[7], and the light elements lithium 20 K [2] and boron 11 K
[8]. While we will soon celebrate a century of
superconductivity (Figure 1), these recent discoveries
highlight answers to fundamental questions that the
elements of the periodic table still conceal. Though
thousands of papers have been published on the topic, a
general predictive model of superconductivity has eluded
us.
__________
* electronic mail: cristi@physics.queensu.ca Figure 1. Historical development of the critical temperature of
simple elements
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Figure 2. Periodic table of superconducting elements
Recently experiments and theories on atomic condensation
[12] and superconductivity in a two-dimensional electron
gas [13] have demonstrated a great variety of correlated
states related to superconductivity. First observed in
mercury almost a century ago [14], condensed-matter
superconductivity remains among the most studied
subfields of physics.
This review is organized as a systematic summary of
the superconducting behaviour of the chemical elements,
referencing the periodic table of Fig. 2. Beginning from
hydrogen, ending with iodine, the discussion surveys the
table, grouping elements by electronic structure to shed
light on the puzzle of superconductivity.
2. Inducing Superconductivity
Once thought a rare anomaly, it now appears that
superconducting states can be formed in most materials,
including thousands of inorganic compounds, most of the
natural elements, alloys, oxides, and even organic materials
and, significantly, the double-stranded molecules of DNA
[15].
2
If a given element is not superconducting at normal
pressure, there are several ways of causing it to
superconduct, illustrated schematically in Fig. 3. Transport
of electron pairs from a superconductor in close proximity
creates a small superconducting interface layer in some
materials, a phenomenon called proximity induced
superconductivity. Crystal strain or non-equilibrium crystal
textures can also induce superconductivity, through applied
pressure, quenched growth on a cold substrate, or epitaxial
templating in the form of thin films. Chemical doping that
affects electron occupancy (charge doping) produces
superconductivity in many materials, including diamond.
Finally, irradiation induced lattice disorder can also lead to
superconductivity through the suppression of spin
fluctuations.
The atomic structure of a material determines its
superconducting characteristics with superconductivity
arising as a collective transport behavior through the
electronic potential of the crystal. An illustration of this is
the existence of different critical temperature values for
polymorphic forms of certain elements, such as lanthanum,
which superconducts at Tc = 4.8 K when double hexagonal
closed packed, dhcp, compared to Tc = 6 K when face
centered cubic, fcc [16].
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Figure 3. Techniques used to transform normal elements into superconductors
3. Superconductivity under Pressure
Applying pressure is often the simplest way of modifying
the crystalline structure of a material, where the material
can undergo structural phase transitions, each structure
being characterized by a unique electronic configuration.
Phase transformations occur in many elements under
compression and some high-pressure phases exhibit
superconductivity.
The renaissance in high-pressure research on
superconductivity is primarily the result of recent
development of high-pressure diamond anvil cells [17].
While the highest attainable pressure in 1968 was
approximately 25 GPa employing Bridgman type anvils at
liquid helium temperatures [18], today measurements can
be performed to a maximum pressure of 260 GPa [8]. This
made possible the surprise observation of higher-pressure
emergent phases of simple elements that exhibit
superconducting properties. Of particular interest is the
research of the light elements, as they are predicted to
superconduct at record high temperatures [19].
Superconductivity under pressure is seen in many
elements, as is summarized in the periodic table of Fig. 2.
Some elements transformed to a metallic state without
showing signs of superconductivity, e.g. xenon [20], others
to semiconductors, e.g. nitrogen [21].
4. Superconducting elements
4.1. Hydrogen
As the first element in the periodic table, hydrogen attracts
much attention, especially due to the predictions of its
high-pressure superconductivity at very high temperatures
[19]. At moderate pressures and temperatures, H occurs in
an insulating molecular phase. Almost seven decades ago
hydrogen was predicted to transform under extreme
3
pressure into a monoatomic metallic solid [22], then that
metallic H will superconduct in the atomic phase [19], with
critical temperatures reaching high values, perhaps to room
temperature. The main technological problem encountered
in the study of H, the smallest of atoms, is its high
diffusivity and chemical reactivity, which make it the most
difficult material to contain at high pressure, tending to
embrittle and weaken gaskets and anvils. Despite these
difficulties, the study of H has generated several interesting
results, among which is its transformation into a metallic
fluid at 140 GPa [23], and the modification of its optical
properties (darkening) at higher pressures [24]. All
attempts at demonstrating its superconductivity, however,
have had negative results.
4.2. Alkali and alkaline metals
Among the alkali metals (Li, Na, K, Rb, Cs, Fr) only Li
and Cs were found to superconduct under pressure.
Calculations predicted superconductivity of Li at high
pressure [25] with a Tc of up to 80 K [26]. Early
measurements of Li resistivity under pressure revealed a
phase transition accompanied by a sudden drop of
resistivity around 7 K, attributed to possible
superconductivity [27]. A clear demonstration of Li
superconductivity was recently published [2, 28], with Tc
increasing with pressure and reaching an unprecedented 20
K for a simple element, under 50 GPa [2]. A plot of its
critical temperature dependence on pressure is shown in
Fig. 4 together with the behavior of superconducting
alkaline earth metals. The experimental behavior of Li is
not adequately resolved, and agreement has not been
reached on its Tc dependence on pressure [2, 28, 29]. Data
measured under almost hydrostatic pressures [29]
(compressed in an anvil while surrounded by helium to
provide uniform pressure without shear) shows an increase
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Figure 4. Critical temperature dependence on pressure for alkali
and alkaline metals, Li [2, 28, 29], Ca [36], Ba [37-43], Sr [37].
then decrease of Tc with pressure, evidence that
superconductivity competes with symmetry breaking
structural phase transitions.
Cesium under pressure (not shown in Fig. 4) has a
much lower critical temperature than Li, with Tc decreasing
monotonically from 1.66 K for increasing pressure [30].
For the other alkalis, preliminary calculations suggest that
Na might become superconducting under pressure [31], but
has yet to be experimentally observed.
Among alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra)
several superconduct: Be, Ca, Sr, and Ba. Beryllium, has a
modest Tc of 26 mK in bulk form [32], but attains a Tc of
9.95 K when deposited as a quenched-condensed film [33].
The heavier alkaline earth metals, Ca, Ba, and Sr transform
into superconductors only under pressure, explained as an
s-d electron transition arising from ion core orthogonality
requirements [34]. Calcium [35, 36] and strontium [37]
have a positive dTc/dp curve, while the critical temperature
of Ba increases and then decreases [37-42], as seen in Fig.
4. From electronic band structure calculations for Ba [43] it
was concluded that the 5d component in the conduction-
electron wave function increases strongly under pressure,
transforming Ba into a 5d transition metal through s-d
hybridization at the Fermi level.
4.3. s2d1 transition metals
Yttrium [30] and its related s2d1 transition metals Sc, La,
and Lu [44], have a positive dTc/dp slope, as shown in Fig.
5. Lanthanum has two superconducting phases at normal
pressure, dhcp at 4.8 K and fcc at 6 K [16].
4
Figure 5. Critical temperature dependence on pressure for s2d1
transition metals, La [16], Lu [44], Sc [44], Y [30].
4.4. Transition metals
Most of the transition metals [27 metals from the area
cornered by Ti, Hf, Hg, and Zn) are superconducting at
normal pressure, the highest critical temperatures being for
elements in the fifth group: Nb at 9.25 K [45], V at 5.4 K
[46], and Ta at 4.4 K [47]. Niobium also holds the record
for the highest critical temperature of an element at normal
pressure. No structural phase transitions are observed in Nb
and Ta, so changes in Tc are thought to be the result of
changes in electronic structure alone, creating a Tc(p) that
is nearly constant in Nb from 10 Gpa to 70 GPa, and from
ambient to 45 GPa in Ta [45], as seen in Fig. 6. Unlike
niobium and tantalum, vanadium has a large positive
pressure coefficient of the critical temperature [48], its
critical temperature under pressure reaching 17.2 K at 120
GPa, among the highest for simple elements [49]. The
increase of Tc is thought to be due to suppression of
electron spin fluctuations through broadening of the d-band
width [50].
A material less studied since its superconductivity
discovery [51, 52], is zirconium, with two superconducting
phases, hcp and bcc (body center cubic), reaching a critical
temperature of 11 K at 30 GPa in its bcc form [53].
Chromium superconducts at 3 K in an fcc phase
fabricated by epitaxially sandwiching Cr between gold
layers [54].
Palladium is a metal with particularly interesting
properties. From its high electronic density of states at the
Fermi surface and its phonon spectrum, one would expect
strong electron-phonon coupling, and therefore a
reasonable high superconducting transition temperature.
Experimentally, however, superconductivity does not occur
down to 1.7 mK [55] due to spin fluctuations, though
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Figure 6. Critical temperature dependence on pressure for
transition metals, Zr [52, 53], V [48-50], Nb [45], Ta [45, 67], and
Fe [7].
palladium can be transformed into a superconductor with a
Tc of 3.2 K through the introduction of lattice disorder via
low-temperature irradiation with He+ ions [56], in
qualitative agreement with theoretical predictions for
superconductivity in palladium without spin fluctuations
[56].
4.5. Superconductivity and magnetism
The correlation between superconductivity and magnetism
makes the study of ferromagnetic metals (Fe, Co, Ni, Gd)
particularly important. Iron is the classic magnetic metal,
being strongly ferromagnetic at standard conditions in its
bcc phase. In this ferromagnetic form iron does not
superconduct to the lowest temperatures attainable. At
pressures above 10 GPa iron assumes an hcp structure,
believed to be non-magnetic. The superconductivity of the
iron hcp phase was predicted [57] and was recently
confirmed experimentally [7]. As illustrated in Fig. 6, the
Tc(p) diagram for iron has a specific bell-shaped curve.
Interestingly, this phase diagram for iron [7] shows a
striking resemblance to the critical temperature versus
doping or carrier concentration of superconductors with
antiferromagnetic parent compounds - La2-xSrxCu2O4 [58],
or UGe2 [59], as illustrated in Fig. 7. While their
relationship is not fully understood, it was believed that
ferromagnetism and superconductivity were competing
mechanisms, and the superconductivity of iron came as a
surprise. Perhaps the explanation lies in theoretical model
of magnetism mediated superconductivity [59]. The
validity of this model was questioned until recently, when
5
Figure 7. Normalized critical temperature variation with
pressure and doping level for materials with ferromagnetic or
antiferromagnetic behavior. Data are taken from references [59],
[58] and [7] for UGe2, La-Sr-Cu-O, and Fe, respectively.
superconductivity was observed in UGe2, on the border of
ferromagnetism within the same electrons that produce
band magnetism [59]. These recent discoveries of
superconductivity in iron [7], as well as in cobalt
compounds [60, 61], re-focuses attention on magnetic
mediated superconductivity as an alternative to phonon
mediated.
4.6. Metals
Metals from groups 13-15 (Al, Ga, In, Tl, Sn, Pb, Bi)
situated on the right edge of the transition metals in the
periodic table show several common characteristics. First,
they all superconduct at normal pressure, except bismuth,
which is almost a semi-metal. Second, the Tcs of the
elements decrease with increasing pressure, as shown in
Fig. 8 for Al [62], Sn [63], Pb [40, 64-67] and Bi [39, 40],
the derivative dTc/dp having similar values. In addition, the
critical temperature seems to increase from group 13 to 15.
Aluminum superconducts below 1.18 K [62], and when
in mesoscopic wire form shows a peculiar resistance peak
in the superconducting state near Tc, attributed to thermal
fluctuations producing phase slips of the superconducting
order parameter [68].
Gallium has a critical temperature of 1.08 K in bulk
form, and in amorphous film form, quench-condensed on
liquid-helium cooled substrates, attains 8.6 K [69].
Bismuth is an example of those elements that do not
display superconductivity under ordinary circumstances,
but undergo superconducting phase transitions in a fcc
phase [70] after being subjected to hydrostatic pressure. Bi
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Figure 8. Critical temperature dependence on pressure for
metals, Al [62], Sn [63], Pb [40, 64-67], Bi [39, 40].
superconducts with a Tc of 8.7 K at 9 GPa [40], with a Tc =
4 K [70] in thin film form on Ni substrates, and with Tc =
6.2 K [71] when amorphous.
4.7. Semi-metals
A general characteristic of semi-metals is that they do not
show superconductivity at normal pressure, but
superconduct when compressed. Most of them have
structural phase transitions within the studied pressure
range, and exhibit different Tcs for different phases. As a
common feature of Si [72-74], As [75, 76], and Te [77-79],
the critical temperature increases with pressure, followed
by saturation and a decline (Fig. 9). The recent research of
superconductivity in the lightest semi-metal - boron,
probably triggered by the announcement of MgB2
superconductivity at nearly 40 K [1], spurred interest in
superconducting physics on boron-related compounds [80].
Boron superconductivity was observed with a maximum Tc
of 11.2 K at 250 GPa [8], as shown in Fig. 9.
4.8. Non-metals
Among non-metals, carbon (in the form of diamond and
nanotubes), oxygen, bromine, and iodine have recently
been transformed into superconductors, while the
superconductivity under pressure of phosphorus, sulfur,
and selenium was observed much earlier (Fig. 10).
Nitrogen was transformed into a semiconductor under
pressure without exhibiting superconductivity [21].
6
Figure 9. Critical temperature dependence on pressure for semi-
metals, B [8], Si [72-74], As [75, 76], Te [77-79].
Carbon likely occurs in the widest variety of elemental
forms, the most known allotropes being graphite, diamond,
C60 carbon spheres (Buckminster-fullerenes), and carbon
nanotubes derived from curved graphene sheets. The
possibility of superconductivity in carbon nanotubes was
predicted in 1995 with Tc expected to be inversely
proportional to the nanowire diameter, an effect related to
electron-phonon interactions [81]. In 2001 Kociak et al.
[82] reported superconductivity below 0.55 K in ropes of
single-walled carbon nanotubes with low-resistance
contacts to non-superconducting metallic pads. Later the
same year Tang et al. [5] succeeded in observing
superconductivity in one-dimensional 0.4 nm diameter
single-walled carbon nanotubes encapsulated in channels
of zeolite crystals with a record high Tc of 15 K. The latest
surprise from superconductivity in carbon-based materials
came from boron doped diamond [6]. The discovery of
superconductivity in a diamond-type structure suggests that
Si and Ge, also having a diamond crystal structure, might
superconduct under appropriate doping conditions.
Since the discovery of superconductivity in
phosphorous [83] at 5.8 K under 17 GPa its critical
temperature was increased under 30 GPa pressure to 18 K
[84]. The superconducting transition temperature of
phosphorus under pressure depends on the path in the
pressure-temperature diagram [84-86]. Black insulating
phosphorous with an orthorhombic structure is the most
stable form at ambient conditions. When pressure is
increased at liquid-helium temperature black phosphorus
transforms to a metallic phase with a simple cubic structure
with a Tc up to 10.5 K [85]. If red phosphorus is used as the
starting material and pressurized at 4.2 K, the Tc increases
up to 13 K with the onset of transition at 18 K under 30
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Figure 10. Critical temperature dependence on pressure for non-
metals, P [86], S [3, 93], Se [77], Br [93], I [92].
Gpa. The resistance transition versus temperature exhibits a
drop with a finite temperature width, with onset at 18 K
and zero resistance at 8 K. A new simple bcc structure has
been observed above 262 GPa [87], giving hope that a
similar or higher Tc could be achieved in this phase. It was
suggested that this bcc phase of phosphorous might be
stabilized at ambient conditions using suitable templates
such as V(100), Fe(100), or Cr(100) substrates [88]. This
could lead to a breakthrough in technological spintronic
applications, where the combined spin and superconducting
degrees of freedom will provide a new level of
functionality for microelectronic devices.
The first studies of superconductivity of sulfur were
performed in 1978 with reports of transitions into the
superconducting state at 5.7 K [89] and 9.8 K [90]. Recent
studies of compressed sulfur [3, 91] show that the element
transforms to a superconductor with Tc increasing with
pressure to 17 K at 160 Gpa (Fig. 10). This is the third
highest reported transition temperature for an elemental
solid. This behavior contrasts with the negative dTc/dp
observed at much lower pressures in the heavier
superconducting chalcogens Se and Te [77].
The successful searches for superconductivity in the
halogen group were iodine [92] and bromine [93]. In the
case of bromine under pressure, a molecular to
monoatomic phase transition takes place at 80 GPa. At
pressures higher than 90 GPa bromine becomes a
superconductor [93].
Oxygen is known to show magnetic properties at low
temperatures, so was not expected to superconduct. At
pressures exceeding 95 GPa, solid molecular oxygen
undergoes a phase transition and becomes metallic. At
around 100 GPa solid oxygen becomes superconducting
7
Figure 11. Highest critical temperature of simple elements as a
function of the atomic number.
below 0.6 K, as revealed by resistive and magnetic
measurements [4]. It seems that the oxygen
superconductivity is present even in the molecular metallic
state, in contrast with iodine and bromine. The transition
temperature of oxygen is rather low compared to other
elements in the 16th series: S, Se, and Te which
superconduct at 17, 7, and 7.4 K, respectively, in spite of
all expectations from both the structural sequence and the
increase of Tc for this group.
None of the noble gases (He, Ne, Ar, Kr, Xe, Rn) are
known to superconduct. A report on xenon indicates its
transforms into a metallic state but without showing signs
of superconductivity [20].
5. Critical temperature correlations
As a general trend, the maximum critical temperature of
simple elements scales with the atomic number Z, the
highest Tc's being achieved for low Z (Fig. 11), implying
that light elements are the best candidates for the utmost
critical temperatures. Other correlations of Tc with normal
state properties [97], such as bulk modulus, work function,
Hall coefficient, Debye temperature, etc. should be re-
evaluated in the light of the most recent findings in the
critical temperature of simple elements. An interesting path
would be a search for possible correlation of Tc with Hall
coefficient changes under pressure.
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6. Conclusions
As future directions, further theoretical and experimental
studies of superconductivity at pressures exceeding 50 GPa
for most of the elements are needed.
While applying pressure to a material is an established
way of exploring new crystalline structures, recent thin
film fabrication methods have shown great utility in
growing unique and non-equilibrium crystals through
sandwiched epitaxy [54] or control of geometrical effects
in vapor aggregation [94, 95]. These methods should be
further employed in the search for new superconducting
phases.
The study of elemental superconductors has an
enormous impact on our understanding of
superconductivity. Current work is laying the foundations
of elemental superconductor nanowires applications and
further elucidation of the low dimensionality effect on their
properties. Advances in materials and nanomaterials
fabrication and characterization will certainly lead to
observation of superconductivity in elements at higher
temperatures, creating new opportunities for applications
such as spintronics [88] or DNA integrated molecular
electronics [96]. As suggested by the fast pace of
discoveries in this field of superconductivity, it seems the
periodic table of superconducting elements will likely need
updating in the near future.
Acknowledgements
We thank I. Pacheco for stimulating discussions and
invaluable suggestions, and J. E. Hirsch, J. M. Fraser, M.
J. Stott, and K. Shimizu for helpful comments on the text.
This research was supported in part by the Natural
Sciences and Engineering Research Council of Canada
(NSERC).
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