Superconductors
Superconductors
Superconductors
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The first widely-accepted theoretical
understanding of superconductivity was advanced
in 1957 by American physicists John Bardeen,
Leon Cooper, and John Schrieffer (above). Their
Theories of Superconductivity became know as the
BCS theory - derived from the first letter of each
man's last name - and won them a Nobel prize in
1972. The mathematically-complex BCS theory
explained superconductivity at temperatures close to absolute zero for elements and simple alloys.
However, at higher temperatures and with different superconductor systems, the BCS theory has
subsequently become inadequate to fully explain how superconductivity is occurring.
The 1980's were a decade of unrivaled discovery in the field of superconductivity. In 1964
Bill Little of Stanford University had suggested the possibility of organic (carbon-based)
superconductors. The first of these theoretical superconductors was successfully synthesized in
1980 by Danish researcher Klaus Bechgaard of the University of Copenhagen and 3 French team
members. (TMTSF)2PF6 had to be cooled to an incredibly cold 1.2K transition temperature (known
as Tc) and subjected to high pressure to superconduct. But, its mere existence proved the possibility
of "designer" molecules - molecules fashioned to perform in a predictable way.
Müller and Bednorz' discovery triggered a flurry of activity in the field of superconductivity.
Researchers around the world began "cooking" up ceramics of every imaginable combination in a
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quest for higher and higher Tc's. In January of 1987 a research team at the University of Alabama-
Huntsville substituted Yttrium for Lanthanum in the Müller and Bednorz molecule and achieved an
incredible 92 K Tc. For the first time a material (today referred to as YBCO) had been found that
would superconduct at temperatures warmer than liquid nitrogen - a commonly available coolant.
Additional milestones have since been achieved using exotic - and often toxic - elements in the base
perovskite ceramic. The current class (or "system") of ceramic superconductors with the highest
transition temperatures are the mercuric-cuprates. The first synthesis of one of these compounds
was achieved in 1993 at the University of Colorado and by the team of A. Schilling, M. Cantoni, J.
D. Guo, and H. R. Ott of Zurich, Switzerland. The world record Tc of 138 °K is now held by a
thallium-doped, mercuric-cuprate comprised of the elements Mercury, Thallium, Barium, Calcium,
Copper and Oxygen. The Tc of this ceramic superconductor was confirmed by Dr. Ron Goldfarb at
the National Institute of Standards and Technology-Colorado in February of 1994. Under extreme
pressure its Tc can be coaxed up even higher - approximately 25 to 30 degrees more at 300,000
atmospheres. The world record Tc of 138 °K
In recent years, many discoveries regarding the novel nature of superconductivity have been
made. In 1997 researchers found that at a temperature very near absolute zero an alloy of gold and
indium was both a superconductor and a natural magnet. Conventional wisdom held that a material
with such properties could not exist! Since then, over a half-dozen such compounds have been
found. Recent years have also seen the discovery of the first high-temperature superconductor that
does NOT contain any copper (2000), and the first all-metal perovskite superconductor (2001).
Also in 2001 a material that had been sitting on laboratory shelves for decades was found to
be an extraordinary new superconductor. Japanese researchers measured the transition temperature
of magnesium diboride at 39 °Kelvin - far above the highest Tc of any of the elemental or binary
alloy superconductors. While 39 K is still well below the Tc's of the "warm" ceramic
superconductors, subsequent refinements in the way MgB2 is fabricated have paved the way for its
use in industrial applications. Laboratory testing has found MgB2 will outperform NbTi and Nb3Sn
wires in high magnetic field applications like MRI.
The most recent "family" of superconductors to be discovered is the "pnictides". These iron-
based superconductors were first observed by a group of Japanese researchers in 2006. Like the
high-Tc copper-oxides, the exact mechanism that facilitates superconductivity in them is a mystery.
However, with Tc's over 50K, a great deal of excitement has resulted from their discovery.
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SUPERCONDUCTOR TERMINOLOGY
AND THE NAMING SCHEME
Anti-ferromagnetism: A state of
matter where adjacent ions in a material are aligned in opposite or "anti-parallel" arrays. Such
materials display almost no response to an external magnetic field at low temperatures and only a
weak attaction at higher temperatures. There is evidence that anti-ferromagnetism in the copper
oxides plays a role in the formation of Cooper pairs and, thus, in facilitating a superconductive state
in some compounds.
BCS Theory: The first widely-accepted theory to explain superconductivity put forth in
1957 by John Bardeen, Leon Cooper, and John Schreiffer. The theory asserts that, as electrons pass
through a crystal lattice, the lattice deforms inward towards the electrons generating sound packets
known as "phonons". These phonons produce a trough of positive charge in the area of deformation
that assists subsequent electrons in passing through the same region in a process known as phonon-
mediated coupling. This is analogous to rolling a bowling ball up the middle of a bed. 2 people, one
lying on each side of the bed, will tend to roll toward the center of the bed, once the ball has created
a depression in the mattress. And, a 2nd bowling ball, placed at the foot of the bed, will now, quite
easily, roll toward the middle.
Charge Reservoirs: In superconductors, charge reservoirs are the layers that may control the
oxidation state of adjacent superconducting planes (even though they themselves are not
superconducting). In the layered cuprates, these consist of copper-oxide chains.
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Chevrel (phases): A class of molybdenum chalcogenides (compounds containing Group VI
elements S, Se or Te along with molybdenum and a positively charged metal ion) - named for
Roger Chevrel of the University of Rennes, whose research brought them to the attention of the
scientific community in the early 1970's. Recently, the Superconductivity Group at the University
of Durham (UK) reported a novel fabrication technique that increases Bc2 (upper critical field) in
the chevrel PbMo6S8 from 50 T in bulk materials up to > 100 T. Click HERE to read a [technical]
writeup on this (as a PDF file). Or click HERE to see a short list of some of these compounds
alongside their Tc's.
Coherence Length: The size of a cooper pair - representing the shortest distance over which
superconductivity can be established in a material. This is typically on the order of 1000Å; although
it can be as small as 30Å in the copper oxides.
Cooper Pair: Two electrons that appear to "team up" in accordance with theory - BCS or
other - despite the fact that they both have a negative charge and normally repel each other. (Named
for Leon Cooper.) Below the superconducting transition temperature, paired electrons form a
condensate - a macroscopically occupied single quantum state - which flows without resistance.
However, since only a small fraction of the electrons are paired, the bulk does not qualify as being a
"bose-einstein condensate". Click here to see an animation of a cooper pair.
DAC: An acronym for "diamond anvil cell". Often the Tc of a superconductor can be
coaxed upward with the application of high pressure. The DAC is used to accomplish this in the
laboratory. A DAC is composed of 2 specially-cut diamonds and a stainless steel gasket. The gasket
goes between the diamonds and seals a small chamber in which a fluid is placed. Since neither the
diamonds nor the liquid will compress, hydrostatic forces in excess of a million atmospheres can be
brought to bear on a sample suspended within the fluid. Click here to see a graphic of a DAC.
D-Wave: A form of electron pairing in which the electrons travel together in orbits
resembling a four-leaf clover. Wave functions help theoreticians describe (and predict) electron
behavior. The d-wave models have gained substantial support recently over s-wave pairing as the
mechanism by which high-temperature superconductivity might be explained
Energy Gap: This is the energy required to break up a pair of electrons. According to BCS
theory, the formula for determining the energy gap (in meV) is Eg=7/2 KTc. Where K =
Boltzmann's constant (8.62e-5 eV/K). And where Tc is the critical transition temperature in Kelvin.
Since electron-pairing is universally agreed to be the method by which superconductivity occurs,
this is the amount of energy required to disrupt the superconducting state.
ESR: An acronym for "Electron Spin Resonance" (also EPR: Electron Paramagnetic
Resonance). This is another mechanism by which superconductivity might be explained in some
materials. Simply put, ESR is the response of electrons to electromagnetic radiation or magnetic
fields at discrete frequencies. Electrons, as they move, create tiny magnetic moments. Nearby
electrons are influenced either beneficially or adversely. When the moments are complementary, the
electrons become paired and can help each other move through a crystal lattice.
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Ferrite: Ferrites are ceramics with magnetic properties. They are included on this page
because many of the same elements used in ferrites (e.g. Ba, Sr, Tm, O) are also key constituents in
ceramic superconductors. This may be an important clue in understanding high-temperature
superconductivity.
Flux-Lattice: A configuration created when flux lines from a strong magnetic field try to
penetrate the surface of a Type 2 superconductor. The tiny magnetic moments within each resulting
vortex repel each other and a periodic lattice results as they array themselves in an orderly fashion.
Fluxon: The smallest magnetic flux (flux quantum) that exists in nature. Just as electrons
are quantized charge, fluxons are a quantized flux. The term is used in association with vortices,
which result from magnetic fields penetrating Type 2 superconductors in single fluxon quanta.
Click here to view a hollographic depiction of waves of fluxons on the surface of superconducting
Niobium.
lux-Pinning: The phenomenon where a magnet's lines of force (called flux) become trapped
or "pinned" inside a superconducting material. This pinning binds the superconductor to the magnet
at a fixed distance. Flux-pinning is only possible when there are defects in the crystalline structure
of the superconductor (usually resulting from grain boundaries or impurities). Flux-pinning is
desirable in high-temperature ceramic superconductors in order to prevent "flux-creep", which can
create a pseudo-resistance and depress Jc and Hc. Click here to see a superconductor suspended in
air by flux-pinning.
Hall Effect: When a magnetic field is applied perpendicularly to a thin metal film or
semiconductor film that is conducting an electric current, a small voltage will appear perpendicular
to the axis of both the film and the magnetic field. This voltage is proportional to the strength of the
applied field. However, the output is typically not linear. The Hall resistance (the ratio of the Hall
voltage to the current) changes in steps, pursuant to the laws of quantum mechanics. This is known
as the Integral Quantum Hall Effect or just Quantum Hall Effect. Discovered in 1879, the Hall
effect was named for its discoverer Edwin H. Hall, a graduate student at Johns Hopkins University.
Hc: The scientific notation representing the "critical field" or maximum magnetic field that
a superconductor can endure before it is "quenched" and returns to a non-superconducting state.
Usually a higher Tc also brings a higher Hc.
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known as a low "Fermi energy" and makes them unlikely - and unusual - superconductors. Research
suggests cooper-pairing in heavy fermion systems arises from the magnetic interactions of the
electron spins.
Hole: A positively-charged vacancy within a crystal lattice resulting from the shortage of an
electron in that region. Holes are typically induced by doping a material with an impurity. However,
they can also be synthesized electronically with devices like the field-effect transistor (FET).
Modern electronic devices rely heavily on holes (as p-type semiconductors) to function. There is
evidence that the holes of hypocharged oxygen in charge-reservoirs are, in fact, what makes
possible high-temperature superconductivity in the layered cuprates.
Infinite layer: Infinite layer compounds have no clear separation between molecules. Rather
than electrostatic bonding between discrete molecules to form a bulk crystalline aggregate, all the
atoms are bound together by covalent or co-ionic bonding to form the equivalent of one huge
molecule. (Ba,Sr)CuO2 and Na2Ba6Si46 are examples of "infinite layer" or "infinite network"
superconductor compounds.
Isotope Effect: The influence atomic mass contributes to the critical transition temperature
of a superconductor. For example, 203.4Hg has a Tc of 4.126K. While 198Hg has a Tc of 4.177K.
Since both forms of mercury have the same lattice structure, this difference in Tc can be attributed
solely to the difference in mass. To learn more, click here.
Jc: The scientific notation representing the "critical current density" or maximum current
that a superconductor can carry. Also note that, as the current flowing through a superconductor
increases, the Tc will usually decrease.
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is the voltage that appears, and h is Planck's constant] Sidebar: This oscillation frequency has, in
fact, resulted in an upward revision of Planck's constant from 6.62559e-34 to 6.626196e-34.
Kelvin: A scale of temperature measurement that starts at "absolute zero", the coldest
theoretical temperature attainable. (Named for Lord William Thomson Kelvin.)
Meissner Effect: Exhibiting diamagnetic properties to the total exclusion of all magnetic
fields. (Named for Walther Meissner.) This is a classic hallmark of superconductivity and can
actually be used to levitate a strong rare-earth magnet. To see a movie of a magnet being levitated
by a superconductor, click here.
Mott Transition: The Mott transition is the shift from an insulating to a metallic state in a
material. The high- temperature copper oxides are composed of CuO2 planes that are separated
from each other by ionic "blocking layers". Although it has one conduction electron (or hole) per
Cu site, each CuO2 plane is originally insulating because of the large electron correlation. That
behavior is typical of the Mott insulator state, in which all the conduction electrons are tied to the
atomic sites. The superconducting state emerges when holes from the blocking layers dope the
CuO2 layers in a way that alters the number of conduction electrons and triggers the Mott transition.
Researchers believe that the strong antiferromagnetic correlation, which originates in the Mott-
insulating CuO2 sheets and persists into the metallic state, could be a possible mechanism of high-
temperature superconductivity. (courtesy Science Week)
Penetration Depth (also London Penetration Depth): This term relates to how deeply a
magnetic field will penetrate the surface of a superconductor. An external magnetic field impinged
upon a Type 2 superconductor will decay exponentially into the surface based on the paired electron
density within the superconductor (only a small fraction of the electrons are in a superconductive
state). The "London" name comes from brothers F. London and H. London, who in 1935 created a
theoretical model of superconductivity. For a more technical explanation and the actual formula to
calculate penetration depth, click here.
Perovskites: A large family of crystalline ceramics that derive their name from a mineral
known as a perovskite. They are the most abundant minerals on earth and have a metal-to-oxygen
ratio of approximately 2-to-3. Copper-oxide superconductors are layered perovskites. The
perovskite name comes from Russian mineralogist Count Lev Aleksevich von Perovski.
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consequence of phase slip is a lower current-carrying state. A similar phenomenon occurs in
Josephson Junctions.
Planar Weight Disparity (PWD): A term referring to the method by which Tc can often be
increased by adjusting the relative weights of alternating layers in copper-oxide superconductors.
The greatest improvements usually occur when making the insulating layers heavy/light OR the Cu-
O2 planes heavy/light - but not both. Click HERE to read more about this discovery.
P-Wave: A rare form of electron pairing in which two electrons travel together in spherical
orbits; with both having the same direction of rotation. (See "D-Wave" explanation above.)
Re-entrant (behavior): A condition where a material retreats from its superconductive state
and then re-enters it. This can be caused by a strong external magnetic field that dynamically
exceeds the Hc of the material and/or is mis-aligned (in the case of some organic superconductors),
a discordant temperature below Tc (in the case of some borocarbides), or by Jc hysteresis
(momentarily exceeding the critical current density, causing the Tc to shift downward).
Resistance: The opposition of a material to the flow of electrical current through it. Energy
lost due to resistance is a result of vibrations at the molecular level and manifests itself as heat in
proportion to the square of the current flow. In a superconductor all resistance disappears below a
certain temperature. However, this applies only to direct current (DC) electricity. Other types of
losses result when transporting alternating current (AC). Examples of this include hysteresis,
reactive-coupling and radiational losses. In the new high-temperature ceramic superconductors, the
power loss in applications like transmission lines is inversely proportional to the critical current
density for low magnetic field applications. This limitation can be compensated for to some degree
by increasing the ratio of voltage to current. In Type 2 superconductors carrying high-frequency
alternating current, "skin effect" losses also result as the energy tends to migrate to the surface
where the conductive medium is incontiguous, producing a pseudo-resistance. In some materials the
amount of resistance may also depend on the direction of current flow (anisotropic resistivity)
and/or presence of an external magnetic field (hall effect).
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However, having one-dimensional geometry, this wire does not exhibit the Meissner effect, except
when configured as a closed loop.
Sinter: The process of heating a material to just below its melting point. An extended period
of sintering is the method by which the constituent components of a ceramic superconductor are
combined in a solid-state reaction. Since ceramic superconductors are inherently brittle, sintering
helps promote intergranular bonding and hardness.
Stripes: Stripes are microscopic rivers of charge that flow across the surface of a Type 2
superconductor. It is theorized that stripes encourage "holes" to pair up and, as such, may play a
role in facilitating charge transfer. Recently, at the Stripes 2000 conference in Rome, Italy, it was
shown that there exists a critical value of micro-strain that must be exerted upon the CuO2 planes
for stripes to form. Click here to learn more.
S-Wave: A form of electron pairing in which the electrons travel together in spherical orbits,
but in opposite directions. (See "D-Wave" explanation above.)
Tc: The scientific notation representing the critical transition temperature below which a
material begins to superconduct. The sudden loss of resistance in a superconductive medium may
occur across a range as small as 20 millionths of a degree or, in the case of some stoichiometrically
imperfect compounds, tens of degrees. Click here to see a graphic example. ("Tc" is not to be
confused with the atomic symbol for Technetium.)
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desired Tc. This can involve Pulsed-Laser Deposition (PLD) or Pulsed-Electron Deposition (PED)
of the material. A variation of this technique can be used to increase the Tc of a superconductor by
growing it on a supporting material with a smaller interatomic spacing. The supporting material acts
as a molecular "girdle" to compress the atomic lattice of the superconductor, thereby raising its
transition temperature. Superconductive tape is made using thin film deposition technology.
Undressing: The process by which a quasiparticle becomes more like a bare (normal)
particle. It is theorized this may be a driving force behind superconductivity, as undressed electrons
are significantly lighter and can, thus, conduct current more readily. To learn more, click here.
Unit Cell: A unit cell is the smallest assemblage of atoms, ions, or molecules in a solid,
beyond which the structure repeats to form the 3-dimensional crystal lattice.
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With the discovery of the ceramic superconductors, came a need for
a classification system to describe structure types. The cuprate
superconductors all have blocks of conducting CuO2 planes, alternating
with insulating, spacing and separating layers. This makes possible a
systematic Naming Scheme that allows for identification and comparison.
The scheme chosen uses four numbers. The first denotes the number of
insulating layers between adjacent conducting blocks. The second
represents the number of spacing layers between identical CuO2 blocks.
The third gives the number of layers that separate adjacent CuO2 planes
within the conducting block. And, the fourth is the number of CuO2planes
within a conducting block.
There are also occasionally letters of the alphabet in the 5th and 6th positions. Suffixes like
"T*", "C", and "F" describe to researchers structure detail in the oxygen positions.
To further complicate matters, several of the more popular structures have names that do
NOT follow the 4-number scheme. For example, the compound Y1Ba2Cu3O7 is often referred to by
the 3-number name "123". This delineates the number of metal atoms (the stoichiometry) - without
regard to atom location - within the structure. Using the 4-number scheme, it would be classified a
"1212".
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A TYPICAL SUPERCONDUCTORS
AND THE FUTURE
Fullerenes, like ceramic superconductors, are a fairly recent discovery. In 1985, professors
Robert F. Curl, Jr. and Richard E. Smalley of Rice University in Houston and Professor Sir Harold
W. Kroto of the University of Sussex in Brighton, England, accidentally stumbled upon them. The
discovery of superconducting alkali metal fullerides came in 1991 when Robert Haddon and Bell
Labs announced that K3C60 had been found to superconduct at 18 K.
Larger, non-spherical pure carbon fullerenes that will superconduct have only recently been
discovered. In April of 2001, Chinese researchers at Hong Kong University found 1-dimensional
superconductivity in single-walled carbon nanotubes at around 15 Kelvin. And in February 2006,
Physicists in Japan showed non-aligned, multi-walled carbon nanotubes were superconductive at
temperatures as high as 12 K. Silicon-based fullerides like Na2Ba6Si46 will also superconduct.
However, they are structured as infinite networks, rather than discrete molecules. Fullerenes are
technically part of a larger family of organic conductors which are described below.
Organic superconductors are composed of an electron donor (the planar organic molecule)
and an electron acceptor (a non-organic anion). Below are a few more examples of organic
superconductors.
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(TMTSF)2ClO4
[tetramethyltetraselenafulvalene + acceptor]
(BETS)2GaCl4
[bis(ethylenedithio)tetraselenafulvalene + acceptor]
(BEDO-TTF)2ReO4H2O
[bis(ethylenedioxy)tetrathiafulvalene + acceptor]
YPd2B2C 23.0 K
LuNi2B2C 16.6 K
YNi2B2C 15.5 K
TmNi2B2C 11.0 K (resistance increases below Tc)
ErNi2B2C 10.5 K (ferromagnetic)
HoNi2B2C 07.5 K (see above graphic)
NOTE: Other elements that exhibit ferromagnetism have been - by one means or another -
integrated into superconducting compounds. See the below section on
Heavy Fermions.
The "Heavy Fermions" sound like a family of overweight circus
performers. But, they are yet another example of atypical
superconductors. Heavy fermions are compounds containing rare-earth
elements such as Ce or Yb, or actinide elements such as U. Their (inner
shell) conduction electrons often have effective masses (known as
Note: UGe2 and URhGe2 exhibit simultaneous ferromagnetism and superconductivity. Read more
about this phenomenon in the below section on Ruthenates.
When the crystalline structure of some of these materials is broken apart, its surface
becomes increasingly ferromagnetic at low temperatures. This phenomenon flies in the face of
condensed matter theory. So much so, that researchers have characterized them as an analog to
superfluid Helium-3. And, when copper is added to the mix, even stranger things happen. In June
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1999 New Zealand researcher Dr. Jefferey Tallon and his German colleague Dr. Christian Bernard
discovered a ruthenium-cuprate** whose bulk is both a superconductor and a magnet. Although it
was not the first compound discovered that exhibits coexisting ferromagnetism and
superconductivity, it's remarkably high Tc of 58 K makes it truly distinct in the world of
superconductors. Unlike "normal" superconductors, this compound becomes diamagnetic at about
one-half Tc.
While no one can predict what future discoveries will be made in the field of
superconductivity, some recent developments in the tungsten-bronze system suggest a new vista
may be emerging. In July of 1999 researchers Y. Tsabba and S. Reich of the Weizmann Institute in
Israel reported possible superconductivity near 91 °K in the sodium-doped tungsten-bronze
Na0.05WO3. This would be the first known HTS that is not a cuprate. Most tungsten-bronze
compounds that are known to superconduct have Tc's below 4K - making this a truly tantalizing
find.
Other categories of materials that theory suggests may produce superconductors are the
higher silver fluorides and complex fluorides - known as fluoroargentates. Fluoroargentates bear a
strong similarity to oxocuprates, compounds that currently have the highest transition temperatures
of all known superconductors. In October 2003 researchers Wojciech Grochala, Adrian Porch and
Peter P. Edwards reported sudden drops in magnetic susceptibility within a large number of samples
of Be-Ag-F. They attribute this to possible spherical regions of superconductivity – with a Tc up to
64 °K - couched inside a ferromagnetic host.
With few exceptions (e.g. polysulphur-nitrides), most polymers resist being coaxed into a
superconductive state. However, some organic polymers exhibit electrical resistance many orders of
magnitude lower than the best metallic conductors. And, they do this at room temperature! These
ultraconductors™, materials such as oxidized atactic polypropylene (OAPP), do not have zero
resistance. But, their enhanced conductivity at ambient temperatures and pressures may actually
allow them to compete with superconductors in certain fields. Polypropylene, for example, is
normally an insulator. In 1985, however, researchers at the Russian Academy of Sciences
discovered that as an oxidized thin-film, polypropylene can have a conductivity 105 to 106 higher
than the best refined metals. The Meissner effect - the classic criterion for superconductivity -
cannot be observed, as the critical transition temperature appears to be above the point at which the
polymer breaks down (>700K). However, strong (giant) diamagnetism has been confirmed
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TYPE 1 SUPERCONDUCTORS:
AND A PERIODIC CHART COMPARISON
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Hafnium (Hf) 0.128 K HEX
Iridium (Ir) 0.1125 K FCC
Beryllium (Be) 0.023 K (SRM 768) HEX
Tungsten (W) 0.0154 K BCC
Platinum (Pt)* 0.0019 K (see note 1)
Lithium (Li) 0.0004 K BCC
Rhodium (Rh) 0.000325 K FCC
*Note 1: Tc's given are for bulk (alpha form), except for Palladium, which has been irradiated with.
He+ ions, Chromium as a thin film, and Platinum as a compacted powder.
Many additional elements can be coaxed into a superconductive state with the application of
high pressure. For example, phosphorus appears to be the Type 1 element with the highest Tc. But,
it requires compression pressures of 2.5 Mbar to reach a Tc of 14-22 K. The above list is for
elements at normal (ambient) atmospheric pressure. See the periodic table below for all known
elemental superconductors (including Niobium, Technetium and Vanadium which are technically
Type 2).
**Note 2: Normally bulk carbon (amorphous, diamond, graphite, white) will not superconduct at
any temperature. However, a Tc of 15K has been reported for elemental carbon when the atoms are
configured as highly-aligned, single-walled nanotubes. And non-aligned, multi-walled nanotubes
have shown superconductivity near 12K. Since the penetration depth is much larger than the
coherence length, nanotubes would be characterized as "Type 2" superconductors.
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TYPE 2 SUPERCONDUCTORS:
The first superconducting Type 2 compound, an alloy of lead and bismuth, was fabricated in
1930 by W. de Haas and J. Voogd. But, was not recognized as such until later, after the Meissner
effect had been discovered. This new category of superconductors was identified by L.V.
Shubnikov at the Kharkov Institute of Science and Technology in the Ukraine in 1936(1) when he
found two distinct critical magnetic fields (known as Hc1 and Hc2) in PbTl2. The first of the oxide
superconductors was created in 1973 by DuPont researcher Art Sleight when Ba(Pb,Bi)O3 was
found to have a Tc of 13K. The superconducting oxocuprates followed in 1986.
Type 2 superconductors - also known as the "hard" superconductors - differ from Type 1 in
that their transition from a normal to a superconducting state is gradual across a region of "mixed
state" behavior. Since a Type 2 will allow some penetration by an external magnetic field into its
surface, this creates some rather novel mesoscopic phenomena like superconducting "stripes" and
"flux-lattice vortices". While there are far too many to list in totality, some of the more interesting
Type 2 superconductors are listed below by similarity and with descending Tc's. Where available,
the lattice structure of the system is also noted.
(Tl4Ba)Ba2Ca2Cu7O13+
~254 K
(As a 9223 structure)
(Tl4Ba)Ba4Ca2Cu10Oy
~242 K
(As a 9212/2212C intergrowth.)
Tl5Ba4Ca2Cu10Oy
~233 K
(As a 9212/2212C intergrowth.)
(Sn5In)Ba4Ca2Cu11Oy
~218 K
(As a B212/2212C intergrowth.)
(Sn5In)Ba4Ca2Cu10Oy
~212 K
(As a B212/1212C intergrowth.)
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Sn6Ba4Ca2Cu10Oy
~200 K
(As a B212/1212C intergrowth.)
(Sn1.0Pb0.5In0.5)Ba4Tm6Cu8O22+
~195 K
(As a 1256/1212 intergrowth.)
(Sn1.0Pb0.5In0.5)Ba4Tm5Cu7O20+
~185 K
(As a 1245/1212 intergrowth.)
(Sn1.0Pb0.5In0.5)Ba4Tm4Cu6O18+
~163 K
(As a 1234/1212 intergrowth)
Sn3Ba4Ca2Cu7Oy
~160 K
(As a 5212/1212C intergrowth.)
(Hg0.8Tl0.2)Ba2Ca2Cu3O8.33 138 K*
HgBa2Ca2Cu3O8 133-135 K
HgBa2Ca3Cu4O10+ 125-126 K
HgBa2(Ca1-xSrx)Cu2O6+ 123-125 K
HgBa2CuO4+ 94-98 K
Lattice: TET
* Note: As a result of a topological "defect", Hg will also go into the Cu atomic sites. Thus, the
volume fraction of the intended structure type is considerably less than 100%.
Tl2Ba2Ca2Cu3O10 127-128 K
(Tl1.6Hg0.4)Ba2Ca2Cu3O10+ 126 K
TlBa2Ca2Cu3O9+ 123 K
(TlSn)Ba4TmCaCu4Ox ~121 K
(Tl0.5Pb0.5)Sr2Ca2Cu3O9 118-120 K
Tl2Ba2CaCu2O6 118 K
TlBa2Ca3Cu4O11 112 K
TlBa2CaCu2O7+ 103 K
Tl2Ba2CuO6 95 K
TlSnBa4Y2Cu4Ox 86 K
Lattice: TET
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Sn3Ba4Tm3Cu6Ox 109 K (Superconductors.ORG - 2007)
*** Though not always listed as a component, a small amount of Lead (x=.2-.26) is often used with
Bismuth compounds to help facilitate a higher-Tc crystalline phase.
(Ca1-xSrx)CuO2 110 K
YSrCa2Cu4O8+ 101 K (Superconductors.ORG - 2007)
(Ba,Sr)CuO2 90 K
BaSr2CaCu4O8+ 90 K (Superconductors.ORG - 2007)
(La,Sr)CuO2 42 K
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YBa3Cu4Ox (9223C structure) 177 K (Superconductors.ORG - 2009)
(Y0.5Lu0.5)Ba2Cu3O7 107 K (Superconductors.ORG - 2005)
(Y0.5Tm0.5)Ba2Cu3O7 105 K (Superconductors.ORG - 2005)
Y3Ba5Cu8Ox 105 K (Superconductors.ORG - 2008)
Y3CaBa4Cu8O18+ 99 K (Superconductors.ORG - 2010)
(Y0.5Gd0.5)Ba2Cu3O7 97 K (Superconductors.ORG - 2005)
Y2CaBa4Cu7O16 96 K (Superconductors.ORG - 2006)
Y3Ba4Cu7O16 96 K (Superconductors.ORG - 2005)
Y2Ba5Cu7Ox 96 K (Superconductors.ORG - 2008)
NdBa2Cu3O7 96 K
Y2Ba4Cu7O15 95 K
GdBa2Cu3O7 94 K
YBa2Cu3O7 92 K (See above graphic)
TmBa2Cu3O7 90 K
YbBa2Cu3O7 89 K
YSr2Cu3O7 62 K
Comment: "1-2-3" superconductors actually have the 1212C structure. Thus, the formula for YBCO
could be written CuBa2YCu2O7.
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(Eu,Ce)2(Ba,Eu)2Cu3O10+ 43 K
(La1.85Sr0.15)CuO4 40 K
****
SrNdCuO 40 K
(La,Ba)2CuO4 35-38 K
(Nd,Sr,Ce)2CuO4 35 K
Pb2(Sr,La)2Cu2O6 32 K
30 K (First HTS ceramic SC discovered -
(La1.85Ba.15)CuO4 1986)
Comment: All of the above are copper perovskites, even though their metal-to-oxygen ratios are not
exactly 2-to-3. The best performers are those compounds that contain one or more of the electron-
emitters BaO, SrO or CaO, along with a Period 6 heavy metal like Mercury, Thallium, Lead,
Bismuth, or Gold.
Comment: The above are members of the newly discovered iron pnictide family.
Comment: Among the binary alloys, these are some of the best performers; combining Group 5B
metals in a ratio of 3-to-1 with 4A or 3A elements.
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PuCoGa5 18.5 K (First SC transuranic compound)
NbN 16.1 K
Comment: After NbTi (below) NbN is the most widely used low-temperature superconductor.
(1.) "History of Physics Research in Ukraine", by Oleksandr Bakai and Yurij Raniuk, Kharkov
Institute of Science and Technology, 1993.
Page 24 of 31
APPLICATION OF SUPERCONDUCTORS:
Magnetic-levitation is an application
where superconductors perform extremely
well. Transport vehicles such as trains can be
made to "float" on strong superconducting
magnets, virtually eliminating friction
between the train and its tracks. Not only
would conventional electromagnets waste
much of the electrical energy as heat, they
The Yamanashi MLX01 Maglev train. would have to be physically much larger than
superconducting magnets. A landmark for the commercial use of MAGLEV technology occurred in
1990 when it gained the status of a nationally-funded project in Japan. The Minister of Transport
authorized construction of the Yamanashi Maglev Test Line which opened on April 3, 1997. In
December 2003, the MLX01 test vehicle (shown above) attained an incredible speed of 361 mph
(581 kph).
Although the technology has now been proven, the wider use of MAGLEV vehicles has
been constrained by political and environmental concerns (strong magnetic fields can create a bio-
hazard). The world's first MAGLEV train to be adopted into commercial service, a shuttle in
Birmingham, England, shut down in 1997 after operating for 11 years. A Sino-German maglev is
currently operating over a 30-km course at Pudong International Airport in Shanghai, China. The
U.S. plans to put its first (non-superconducting) Maglev train into operation on a Virginia college
campus. Click this link for a website that lists other uses for MAGLEV.
The Korean Superconductivity Group within KRISS has carried biomagnetic technology a
step further with the development of a double-relaxation oscillation SQUID (Superconducting
QUantum Interference Device) for use in Magnetoencephalography. SQUID's are capable of
sensing a change in a magnetic field over a billion times weaker than the force that moves the
needle on a compass (compass: 5e-5T, SQUID: e-14T.). With this technology, the body can be
probed to certain depths without the need for the strong magnetic fields associated with MRI's.
Electric generators made with superconducting wire are far more efficient than conventional
generators wound with copper wire. In fact, their efficiency is above 99% and their size about half
that of conventional generators. These facts make them very lucrative ventures for power utilities.
General Electric has estimated the potential worldwide market for superconducting generators in the
next decade at around $20-30 billion dollars. Late in 2002 GE Power Systems received $12.3
million in funding from the U.S. Department of Energy to move high-temperature superconducting
generator technology toward full commercialization.
Other commercial power projects in the works that employ superconductor technology
include energy storage to enhance power stability. American Superconductor Corp. received an
order from Alliant Energy in late March 2000 to install a Distributed Superconducting Magnetic
Energy Storage System (D-SMES) in Wisconsin. Just one of these 6 D-SMES units has a power
reserve of over 3 million watts, which can be retrieved whenever there is a need to stabilize line
voltage during a disturbance in the power grid. AMSC has also installed more than 22 of its D-VAR
systems to provide instantaneous reactive power support.
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electricity through HTS (high-temperature superconducting) material. That cable was only 30
meters long, but proved adequate for testing purposes. In the summer of 2001 Pirelli completed
installation of three 400-foot HTS cables for Detroit Edison at the Frisbie Substation capable of
delivering 100 million watts of power. This marked the first time commercial power has been
delivered to customers of a US power utility through superconducting wire. Intermagnetics General
has announced that its IGC-SuperPower subsidiary has joined with BOC and Sumitomo Electric in
a $26 million project to install an underground, HTS power cable in Albany, New York, in Niagara
Mohawk Power Corporation's power grid. Sumitomo Electric's DI-BSCCO cable was employed in
the first in-grid power cable demonstration project sponsored by the U.S. Department of Energy and
New York Energy Research & Development Authority. After connecting to the grid successfully on
July 2006, the DI-BSCCO cable has been supplying the power to approximately 70,000 households
without any problems. The long-term test will be completed in the 2007-2008 timeframe.
The National Science Foundation, along with NASA and DARPA and various universities
are currently researching "petaflop" computers. A petaflop is a thousand-trillion floating point
operations per second. Today's fastest computers have reached "petaflop" speeds - quadrillions of
operations per second. Currently the fastest is a U.S. Military Supercomputer call the "Road
Runner" operating at 1.026 petaflops per second (with multiple CPU's). The fastest single processor
is a Lenslet optical DSP running at 8 teraflops. It has been conjectured that devices on the order of
50 nanometers in size along with unconventional switching mechanisms, such as the Josephson
junctions associated with superconductors, will be necessary to achieve the next level of processing
speeds. TRW researchers (now Northrop Grumman) have quantified this further by predicting that
100 billion Josephson junctions on 4000 microprocessors will be necessary to reach 32 petabits per
second. These Josephson junctions are incorporated into field-effect transistors which then become
part of the logic circuits within the processors. Recently it was demonstrated at the Weizmann
Institute in Israel that the tiny magnetic fields that penetrate Type 2 superconductors can be used for
storing and retrieving digital information. It is, however, not a foregone conclusion that computers
of the future will be built around superconducting devices. Competing technologies, such as
quantum (DELTT) transistors, high-density molecule-scale processors, and DNA-based processing
also have the potential to achieve petaflop benchmarks.
In the electronics industry, ultra-high-performance filters are now being built. Since
superconducting wire has near zero resistance, even at high frequencies, many more filter stages can
be employed to achive a desired frequency response. This translates into an ability to pass desired
frequencies and block undesirable frequencies in high-congestion rf (radio frequency) applications
such as cellular telephone systems. ISCO International and Superconductor Technologies are
companies currently offering such filters.
Superconductors have also found widespread applications in the military. HTSC SQUIDS
are being used by the U.S. NAVY to detect mines and submarines. And, significantly smaller
motors are being built for NAVY ships using superconducting wire and "tape". In mid-July, 2001,
American Superconductor unveiled a 5000-horsepower motor made with superconducting wire
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(below). An even larger 36.5MW HTS ship propulsion motor was delivered to the U.S. Navy in late
2006. The US Air Force expects planes will be able to fire non-lethal microwave rays at enemy
ground troops with the help of a new superconducting generator system. The new generators are
about the size of a small beer keg and designed to produce five megawatts of power. The generators
will have lightweight metal foils coated with superconducting material that carry many times more
current and are more efficient, strong enough for microwave weapons and light enough for
airplanes.
The military is also looking at using superconductive tape as a means of reducing the length
of very low frequency antennas employed on submarines. Normally, the lower the frequency, the
longer an antenna must be. However, inserting a coil of wire ahead of the antenna will make it
function as if it were much longer. Unfortunately, this loading coil also increases system losses by
adding the resistance in the coil's wire. Using superconductive materials can significantly reduce
losses in this coil. The Electronic Materials and Devices Research Group at University of
Birmingham (UK) is credited with creating the first superconducting microwave antenna.
Applications engineers suggest that superconducting carbon nanotubes might be an ideal nano-
antenna for high-gigahertz and terahertz frequencies, once a method of achieving zero "on tube"
contact resistance is perfected.
The most ignominious military use of superconductors may come with the deployment of
"E-bombs". These are devices that make use of strong, superconductor-derived magnetic fields to
create a fast, high-intensity electro-magnetic pulse (EMP) to disable an enemy's electronic
equipment. Such a device saw its first use in wartime in March 2003 when US Forces attacked an
Iraqi broadcast facility.
Among emerging technologies are stabilizing momentum wheel (gyroscope) for earth-
orbiting satellites that employs the "flux-pinning" properties of imperfect superconductors to reduce
friction to near zero. Superconducting x-ray detectors and ultra-fast, superconducting light detectors
are being developed due to their inherent ability to detect extremely weak amounts of energy.
Already Scientists at the European Space Agency (ESA) have developed what's being called the S-
Cam, an optical camera of phenomenal sensitivity (see above photo). And, superconductors may
Page 28 of 31
even play a role in Internet communications soon. In late February, 2000, Irvine Sensors
Corporation received a $1 million contract to research and develop a superconducting digital router
for high-speed data communications up to 160 GHz. Since Internet traffic is increasing
exponentially, superconductor technology may be called upon to meet this super need. Irvine
Sensors speculates this router may see use in facilitating Internet2.
Another impetus to the wider use of superconductors is political in nature. The reduction of
green-house gas (GHG) emissions has becoming a topical issue due to the Kyoto Protocol which
requires the European Union (EU) to reduce its emissions by 8% from 1990 levels by 2012.
Physicists in Finland have calculated that the EU could reduce carbon dioxide emissions by up to 53
million tons if high-temperature superconductors were used in power plants.
The future melding of superconductors into our daily lives will also depend to a great degree
on advancements in the field of cryogenic cooling. New, high-efficiency magnetocaloric-effect
compounds such as gadolinium-silicon-germanium are expected to enter the marketplace soon.
Such materials should make possible compact, refrigeration units to facilitate additional HTS
applications.
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SUPERCONDUCTOR LINKS:
Below are various links to web sites dealing with
superconductors and/or related fields; some of which may already
be listed on the USES, NEWS or PLAY pages.
YBCO Molecule
Pictures/Graphics/Animations:
Tutorial/Research:
Superconductivity In Its Simplest Form | Oxford University
Superconductivity Concepts Link Map | Georgia State University
Lectures on Superconductivity | University of Cambridge
High-Temperature Superconductors | Kent State University
Condensed Matter Theory | University of Michigan
Advanced Explanation of Superconductivity | Futurescience
Flux Lines in Type 2 Superconductors | Univ. of California, Santa Barbara
Hole Theory of Superconductivity | Univ. of California, San Diego
Oxide Superconductors Tutorial | by Bob Cava of Princeton University for the American
Ceramic Society
Reference:
Physica C | Superconductivity Journal
NIST Superconducting Materials Database | National Institute of Standards and Technology
Iowa State High-Tc Searchable Database Archive | Iowa State/Ames Lab
KEIRIN Superconductivity Papers Database | Japan
Solid State Communications | Elsevier Science
Superconductor Science and Technology | Institute Of Physics
Home page for the 1913 Nobel speech by Heike Kamerlingh Onnes
Home page for the 1972 Nobel speeches | by John Bardeen, Leon Cooper, and John Schreiffer
Home page for the 1973 Nobel speech by Brian D. Josephsen
Home page for the 2003 Nobel speeches to Abrikosov, Ginzburg and Leggett
U.S., European and Japanese Patent Search | Refined Search
High School Teacher's Guide to Superconductivity | Oak Ridge National Laboratory
Books on Superconductivity | Geometry.NET Picks
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Books on Superconductivity | RBookShop Picks
Glossary of Superconductor Terms | Superconductors.ORG
Matter Glossary | University of Liverpool
Ionic Radii of the Elements | Environmentalchemistry.COM
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