Superconductors
While superconductors are fascinating materials to study , they are very practical ,
too ; think of the Magnetic Resonance Imaging (MRI) machines in hospitals , so
invaluable in medical diagnostics . MRIs have large coils of a superconducting
intermetallic compound made of niobium and titanium (Nb0.6Ti0.4 ; Tc = 9.8 K) , or of
niobium and tin (Nb3Sn ; Tc = 18 K) , immersed in a bath of ultracold (4.2 K) liquid
helium . These superconducting coils generate the intense magnetic fields required to
completely permeate the human body .
The preparation of superconductors is done by solid state chemists , who also try to
devise new chemical compounds that might have that property . That's where the
problem arises . There are no chemical theories or models of superconductivity , as it's
considered to be a physical and not a chemical phenomenon . The long-reigning BCS
theory (from Bardeen , Cooper , and Schrieffer) , is a lengthy mathematical treatise
that makes no mention of chemistry or of any chemical substances (the references are
listed at the end of this web page . Underlined blue hyperlinks can be clicked when
online to download the PDF or HTML file , which will open in a new window) .
However , all superconductors – and “ordinary” electrical conductors , of course – are
elements and chemical compounds which can be described in chemistry terms . How
can we associate the physical phenomenon of superconductivity with the chemical
description of the materials in which it occurs ?
The A15 (beta-tungsten) crystal structure for an M3X intermetallic compound . Red
spheres : M atoms ; blue spheres : X atoms . Examples : Nb3Sn (see above) , Nb3Ge ,
V3Si . This molecular model is based on the sketch of the A15 structure in Simon and
Smith's book .
Matthias observed that the higher Tc A15 superconductors always had a Transition
metal element as the M atom (d shell valence electrons were involved) , and the
optimum average number of valence electrons per atom per formula unit was a
maximum of five or seven . In later years and decades researchers refined and
broadened Matthias's Rules , but never succeeded in extending them to ternary and
quaternary compounds (the high Tc cuprate superconductors , for example) . The
highest Tc ~ 22 K for an M3X A15 intermetallic compound (and for superconductors
generally) was achieved for Nb3Ge films in 1973 , and that record stood until 1986–87
with the discovery of the cuprate family of superconductors .
“The rule that superconductivity is only possible if there exists at least one space
direction not intersected by plane or conical nodal surfaces can only be verified for a
limited number of superconductors . On the other hand , in no case does anything
point against the validity of this rule . In those cases in which the condition of the rule
is fulfilled , superconductivity is found with very few exceptions . We can thus
assume that the principle condition for the occurrence of superconductivity is in fact
the absence of these nodal surfaces”.
Krebs seems to have been one of the few scientists to study the electronic structures of
nonmolecular solids and superconductors from an orbital point of view .
Unfortunately , his concepts apparently were ignored at the time and forgotten (except
by me) . Recently , his rule about nodes in metallic bond orbitals has been overturned
by the remarkable discovery of an ephemeral superconductivity in heavily-doped
(with boron) semiconductors such as diamond , silicon (PDF , 507 KB) , and silicon
carbide (PDF , 1480 KB) . However , his nodal principle still remains valid for
metallic solids and electrical conduction in general ; I refer to it as Krebs's Theorem ,
and have restated it for the metallic bond this way :
“True metals have a metallic bond consisting of a nodeless crystal orbital along at
least one crystal axis , while in pseudometals the metallic bond consists of a crystal
orbital that is periodically intersected by nodes”.
I think it's safe to say that up to now , all of the known “synthetic” (chemical
compounds , not elements , which are “natural”) superconductors have been
discovered in a serendipitous manner . Serendipity is a lucky or unexpected
discovery , and it often plays an important role in scientific research . Someone will
produce a material that has an extraordinary property that makes it of great interest .
That material is then widely studied , and usually many of its analogues are prepared
and examined . I believe this is true for every new type of superconductor discovered
so far . None were designed and synthesized from first principles , simply because
there are no first principles , in the chemical sense , for superconductors . In scientific
philosopic terms , Matthias's Rules and Krebs's Theorem are inductive (deriving a
general law from specific examples) ; they followed from a study and classification of
existing materials , which were obtained from serendipitous discoveries . What is
needed is a deductive model (a predictive law , from which specific examples are
derived) , one that is based on a broader approach to understanding the phenomenon .
Combining basic physical and chemical concepts , an entirely new model is
constructed , from which novel superconductor candidate compounds can be designed
, synthesized , and tested . The results from these predictions can then be used to
refine and extend the model , or to refute it . If the model is successful , scientists will
no longer have to rely on serendipity to obtain a fresh supply of new superconducting
materials for their research . The objective of this web page is to bring forward such a
deductive model of high temperature superconductors and from it make several
predictions for the design and synthesis of new high Tc compounds .
I began studying superconductors in 1990 after reading about the new high Tc cuprates
in the popular press , but quickly became frustrated with the total lack of any sort of
chemical explanation for them . What chemistry there was of the cuprate materials
merely involved chemical “cooking”, without any significant theoretical input from
chemists . As mentioned above , the dominant BCS theory was purely mathematical
and completely divorced from the actual chemical materials (elements and
compounds) comprising the various superconductors .
The high Tc cuprates provided two important clues about their physical and chemical
natures , and how they could be linked together . The first clue was the
antiferromagnetism in the copper oxide precursors . The key ingredient in
synthesizing all of the cuprates is copper(II) oxide , CuO , a jet black , refractory (m.p.
1326 ºC) solid which is known to be antiferromagnetic (TN = 230 K , – 43 ºC) . This
antiferromagnetism was often retained when CuO was chemically combined with one
or more other compounds to form more complex cuprates , such as La2CuO4 .
The copper(II) in La2CuO4 is 3d9 electronically , so it will have at least one unpaired
singlet valence electron . According to the simple equation for calculating the spin-
only magnetic moment µ for n unpaired electrons , µ = [n (n+2)] ½ , the ninth singlet
electron in La2CuO4 should produce in it a magnetic moment of 1.73 BM (Bohr
magnetons) . However , Arjomand and Machin measured a much lower magnetic
moment for the compound : 0.69 BM at room temperature (300 K) , and 0.34 BM at
liquid nitrogen temperature (80 K) . These results suggested that La2CuO4 is indeed
strongly antiferromagnetic , even at room temperature . Many subsequent studies of it
confirmed these early findings and provided much more information about La2CuO4 .
In the Spring of 1987 the combined Chu and Wu research teams announced their
synthesis and study of YBCO , the first liquid nitrogen range cuprate superconductor
(Tc ~ 93 K) . Their discovery began a frantic search for more high temperature
superconducting cuprates with even higher transition temperatures . YBCO is also a
copper(II)–copper(III) mixed-valent compound with the ideal empirical formula
YBa2Cu3O7 . Its Cu(II)–Cu(III) can be quickly seen by displaying YBCO's “valence
counting formula” : (Y3+ Ba2+ Ba2+)(Cu2+ Cu3+ Cu2+)(O2-)7 . It's interesting to note in
this regard that Arjomand and Machin prepared the two pure , homovalent precursors
to YBCO , BaCuO2 and YCuO3 , back in 1975 . They found the former compound to
be – astonishingly ! – ferromagnetic , and the latter material had high spin octahedral
Cu3+, that while paramagnetic , became mildly antiferromagnetic when cooled to 80 K
. However , YBCO has a completely different crystal structure than either BaCuO2
and YCuO3 , with radically different magnetic and electrical properties than them .
All of the high Tc superconductors were found to have mixed-valent metal cations
(mostly Cu2+ and Cu3+) , and that provided the second important clue – the
“chemistry” one – about high temperature superconductivity . Before reviewing the
role of mixed-valent chemistry , though , I'll first outline the significance of the
“physics” clue , that of antiferromagnetism .
The Transition metals and their compounds display a wide range of magnetic
properties such as Curie paramagnetism , Pauli paramagnetism , ferromagnetism ,
ferrimagnetism , and antiferromagnetism , to name five of the commoner magnetic
ordering states in the solids . Such conditions are produced by the valence shell d
orbital electrons in the metal atoms and their cations . The second type of magnetism ,
Pauli paramagnetism , is produced by the spins of the mobile , free electrons above
the Fermi level EF in the metallic bond . Strong ferromagnetism in metals such as
iron , cobalt , and nickel is associated with the magnets of everyday experience ,
although a weaker ferromagnetism can also be found in certain Transition metal
compounds such as chromium dioxide .
All electrical conductors and superconductors are metallic solids , having a metallic
bond (or conduction band , for the physicists) throughout their lattice . In any one
given sample of a metallic solid there is a single metallic bond , comprised of
continuously overlapping atomic orbitals , which form one single lattice-wide crystal
orbital , XO , containing the valence shell electrons associated with the metallic bond .
The Fermi-Dirac distribution assigns these electrons to a vast number of energy levels
corresponding to the number of participating metal atoms , pairing them two by two
according to the Pauli exclusion principle . In most common metals , about 99% of the
electrons in the metallic bond are thus spin-paired at room temperature , while about
1% of them remain as unpaired singlets in higher energy levels . The boundary
between the paired and unpaired electrons in the XO is the Fermi level , EF . The
unpaired electrons above EF are the free , mobile electrons that are responsible for all
the properties so typical of the metallic solids : electrical conduction and
superconduction , high thermal conduction , metallic luster (high reflectivity) ,
metallic colours , opacity , and Pauli paramagnetism , as noted above .
While it's the mobile singlet electrons above EF that are the electrical charge and
energy carriers in ordinary conductors , it's pairs of electrons – the famous Cooper
pairs – that are the electrical carriers in superconductors . The electrons in the Cooper
pairs are spin-paired , that is , their magnetic spins have an antiparallel orientation , in
a manner similar to the spin-paired electrons in the atomic kernels and in the covalent
bond , for example . At first glance , it would seem that the static electric field around
the electrons would cause them to be repelled from one another . However , a simple
calculation involving High School physics (Coulomb's Laws of Electric Force and
Magnetic Force) shows that the magnetic field around the electrons , derived from
their spins , is much stronger than the corresponding electric field :
Coulomb's Law of Electric Force is simple and straightforward , and is in all of the
physics textbooks I reviewed on the subject . However , Coulomb's Law of Magnetic
Force is by comparison little known . It turns out that the force relationship between
two (macroscopic) magnets is rather complex , and the equation for the magnetic
force used above is a simplification , as explained in the competent Wikipedia article ,
“Magnetic Field” :
“The force between two magnets is quite complicated and depends on the orientation
of both magnets and the distance of the magnets relative to each other . The force is
particularly sensitive to rotations of the magnets due to magnetic torque .
In many cases , the force and the torque on a magnet can be modeled quite well by
assuming a “magnetic charge” at the poles of each magnet and using a magnetic
equivalent to Coulomb's law . In this model , each magnetic pole is a source of an H-
field that is stronger near the pole . An external H-field exerts a force in the direction
of H on a north pole and opposite to H on a south pole . In a nonuniform magnetic
field , each pole sees a different field and is subject to a different force . The
difference in the two forces moves the magnet in the direction of increasing magnetic
field and may also cause a net torque .
Unfortunately, the idea of “poles” does not accurately reflect what happens inside a
magnet (see ferromagnetism) . For instance , a small magnet placed inside of a larger
magnet feels a force in the opposite direction . The more physically correct
description of magnetism involves atomic sized loops of current distributed
throughout the magnet” .
The critical requirement is that the two electrons are in an antiparallel orientation to
each other in order for the magnetic field force to surpass that of the electric field .
That being the case , the two electrons can associate with each other in the Cooper
pair . In fact , the Fm / Fe ratio may be double that indicated in the calculation above ,
which applies to a single set of magnetic poles :
I'm speculating here , but possibly the Fm / Fe ~ 2400 case might apply to Cooper pairs
below Tc , while at Tc the magnetic spins reorient to the weaker Fm / Fe ~ 1200 case .
Then , as the Cooper pairs scatter off lattice atoms , their magnetic spins interact with
those of neighbouring lattice atom electrons , and the pairs are torn apart :
Another possibility might be the thermal promotion by energy packets (kT) of the
antiparallel electrons into singlet electrons with a parallel orientation , which forces
them apart and breaks up the Cooper pairs :
The pairing of electrons participating in the metallic bond occurs both in physical
space (across the lattice dimensions) and in energy space ; that is , each pair of
electrons is at the same energy level . However , they may be very widely separated
physically , at opposite ends of the crystal , or they may be near to each other , maybe
even on neighbouring atoms . This applies to both the electron pairs below EF , and to
the Cooper pairs that form above EF . Because the Fermi-Dirac distribution limits the
population of mobile , free electrons above EF to roughly 1% of the entire population
of metallic bond electrons , they are widely distributed , statistically , across the
crystal lattice . Thus , their coherence lengths tend to be very long . The absolute
value of the magnetic force between any two sets of antiparallel electrons above EF ,
which might otherwise be able to couple them , must be virtually nil . The pairing
mechanism in such superconductors will therefore be that of phonon mediation , as
described in the BCS theory . Once the phonons have pushed the electron pairs
together , the magnetic coupling force can then link them together into Cooper pairs .
“These new pairs [in the high Tc cuprates] differ from BCS pairs [in the low Tc
classical superconductors] in one respect at least : the distance between the charge
carriers of each pair in the new superconductors is much shorter , by a factor of
around 100” (G. Vidali , p. 137) .
A striking example of how non-metal atoms can provide their electron pairs to the
metallic bond is that of rhenium trioxide , ReO3 , whose electrical conductivity is a
remarkable 149,300 ohm-1cm1 (ambient) , comparable to that of many common
metallurgical metals . Its parent element rhenium , with a hexagonal close-packed
(hcp) crystal structure , has a much lower electrical conductivity , 58,140 ohm-1cm1
(ambient) . Rhenium trioxide has a very simple cubic crystal structure :
Metallic solids with direct metal–metal bonds , such as all the metallurgical metals of
common experience , their alloys and intermetallic compounds , and synthetic metals ,
will thus be adversely affected by the Fermi-Dirac distribution in the sense of being
unable to superconduct at higher temperatures (or at all) . Twenty-nine metal elements
are known to superconduct at ambient pressure (several more , and a few non-metal
elements as well , can superconduct when highly compressed) , but only at a few
kelvins above Absolute Zero . On the other hand , all of the genuine high temperature
superconductors (the cuprates) have a bilayer Cu–O metallic bond . I've discussed
several examples of compounds with a bilayer metallic bond , including that of YBCO
, in another web page , “A New Classification of Metallic Solids”, to which the
interested reader is referred .
The third prominent feature of all high Tc superconductors is that they have mixed-
valent cations as the electronically-active components of the materials , i.e. they
participate in the metallic bond . There are four recognized types of mixed-valent
compounds , which are now universally referred to as the Robin-Day classes , named
for the most prominent researchers in that field , M. Robin and P. Day , whose wide-
ranging survey of mixed-valent compounds , published in 1967 , is still the definitive
review of the topic .
Net reaction : Cu2+A + Cu2+B -------------> Cu3+A + Cu1+B ........... E0T = – 2.247 V
The very large negative cell potential for this reaction – the disproportionation of
copper(II) to copper(I) and copper(III) – indicates that it is highly unfavourable
thermodynamically at STP and is essentially impossible . The copper(II) 3d9 valence
electrons are strongly pinned on their respective kernels , and thus homovalent
copper(II) oxide compounds are insulators (or poor semiconductors) .
We see from this simple redox analysis that there is no thermodynamic barrier to the
electron resonance in Robin-Day Class II (Class 3) mixed-valent compounds . That's
why they have such extraordinary optical , electrical , and magnetic properties ,
compared to their corresponding homovalent parent compounds , in which the valence
electrons are pinned on their atomic kernels . This extremely fast electron resonance
permits the free electrons in the metallic bond to closely approach other nearby free
electrons ; and , if the two electrons have an antiparallel orientation with respect to
each other , they can magnetically couple together , as discussed above .
The same situation occurred again with YBCO not long after . The compound
YBa2Cu3O6.5 with homovalent copper(II) was partially oxidized in an atmosphere of
pure oxygen to YBa2Cu3O7 , which is a Robin-Day Class II mixed-valent compound .
YBCO is a true metal , with an inverse temperature–electrical conductivity
relationship (its ambient electrical conductivity is around 500 ohm-1cm-1 ) . It has a
bilayer metallic bond , with the linear oxygen linking atoms providing their 2pz
electron pairs to the pi XO . The copper(II) oxide matrix in which the metallic bond is
located in YBCO is strongly antiferromagnetic over a wide temperature range ; thus ,
a strong antiparallel spin orientation was induced in the mobile , free electrons above
EF in the XO . Since virtually all the Cu2+ 3d9 valence electrons were above EF
(because of the bilayer XO) , they were on neighbouring copper atoms and so their
coherence lengths were extraordinarily short . The magnetic coupling force was
therefore quite strong , and the resulting Cooper pairs were remarkably stable . As a
result of all these converging factors , YBCO proved to have a record (at the time , in
early 1987) transition temperature , Tc ~ 93 K , well into the liquid nitrogen (>77 K)
range .
* Second , the material must have a bilayer metallic bond , so that all the valence
electrons concerned from the electronically active metal atoms will be located above
EF . They will then be located on neighbouring metal atoms and will have very short
coherence lengths , and can strongly couple together magnetically to form reasonably
stable Cooper pairs .
Any theory is of little value unless it can be tested by various experimental methods ,
by which it is verified , or refined , or refuted . In the following section of this web
page I'll outline the syntheses of several new types of potential high temperature
superconductors , which may provide some evidence to support the antiferromagnetic
induction model described above .
In the Iron web page I proposed the mixed-valent Fe1+–Fe2+–Fe1+ triad , for example in
the novel compounds Fe3OX (X = a chalcogenide anion , i.e. sulfide , disulfide ,
selenide , and telluride) , for incorporation into new superconductor candidates . If the
base of iron(II) cations , 3d6 , can be kept in a low-spin condition (the chalcogenide
anions should ensure that this happens) , the “extra” 3d7 valence electrons on the
iron(I) cations can form the Cooper pairs : Fe2+sp Fe2+sp Fe2+sp e22- . The FeO matrix of
this system is antiferromagnetic [TN = 198 K (–75 ºC)] , so there is a good chance of it
being superconducting at a reasonably high Tc . On the other hand , iron(III) cations ,
3d5 , are permanently paramagnetic because of their odd number of valence electrons ,
so they can never be used as the electronically-active cations in the metallic bond ,
where they would prevent the formation of Cooper pairs . Thus , while the compound
LaFeO3 is antiferromagnetic with an extraordinarily high TN = 750 K (477 ºC) , its
iron(III) cations disqualify it from consideration as an antiferromagnetic precursor
compound .
In actual practice , there are few usable triads that can be derived from the elements
whose antiferromagnetic compounds are listed in the above Table (copper is , of
course , the outstanding exception) . The concept of chemically creating a metallic
bond within an existing antiferromagnetic compound thus turns out to be of rather
limited scope . A more practical approach – and one with a much wider scope – would
be to combine an existing diamagnetic mixed-valent triad with an external
antiferromagnetic induction compound . While most elements have multiple valence
states (especially the Transition metals) and so could theoretically provide us with
many mixed-valence triads – refer to Robin and Day's comprehensive review of
mixed-valence chemistry – I'll discuss only several of the better known ones , because
of the limited available length of this web page .
The first one is the bismuth triad , which is found in the high Tc superconductor
BSCCO-2212 (bismuth strontium calcium copper oxide , Bi2Sr2Ca2Cu3O10+y ; Tc ~ 110
K) :
This molecular model was based on the sketch of BSCCO-2212 by G.-H. Gweon .
It's generally thought that superconduction in BSCCO is in the copper oxide layers :
“The present work on the Bi compounds , as well as similar work on the high-Tc
thallium phases , whose structures also do not contain Cu–O chains , indicates that
superconductivity resides in the CuO2 planes” (Tarascon et al. , p. 8891) .
This might not be correct , as the following simple redox analysis shows . First , here's
a Table of common oxidizing metal species and their standard reduction potentials :
The standard reduction potentials , E0red , for the metal species are all versus the SHE
at STP . However , they were derived either from measurements in aqueous media or
from thermodynamic calculations , so we should be cautious about applying them in a
solid state environment . Nevertheless , they can provide some useful guidance to the
chemist in the design of new superconductor candidates .
Copper(III) , with the highest E0red , is the most powerfully oxidizing metal cation
known . YBCO , with mixed-valent Cu(II)–Cu(III) , is a strong oxidizer , and when
exposed to atmospheric humidity it can oxidize water to oxygen gas and hydroxide
anions . The bismuth triad is Bi(V)–Bi(III)–Bi(V) [Bi(4.33+)] , which is 6s0–6s2–6s0
electronically . The Bi(V) component of the triad is a remarkably powerful oxidizer ,
with E0red ~ 1.8 V ; the mixed-valent triad Bi(4.33+) would have a somewhat lesser
E0red . Consider the unoxidized parent precursor to BSCCO , Bi2Sr2Ca2Cu3O10 . By
valence-counting we see that all of its metal atom components are homovalent :
(Bi3+)2(Sr2+)2(Ca2+)2(Cu2+)3O1020- . Using oxidizing conditions in its preparation (such as
a flowing atmosphere of pure oxygen gas) a small mole fraction , y , of oxide can be
added to the precursor material to obtain BSCCO , Bi2Sr2Ca2Cu3O10+y ; the actual
value of y has never been specified , to the best of my knowledge . This added
increment of oxygen removes some of the valence electrons from the metal atom
components . Will the electron donor be the bismuth(III) or the copper(II) ? Redox
considerations suggest that bismuth(III) is easier to oxidize to Bi(V) than copper(II) is
to oxidize to copper(III) . So the superconductor triad in BSCCO is Bi(V)–Bi(III)–
Bi(V) , not the copper triad .
The electron exchange equilibrium is expected to lie well to the left in the above
equation . The absolute difference between the two E0red values for Bi(V) and Cu(III)
is roughly 0.6 V , written between vertical bars to indicate that it is neither a positive
nor negative value . In this picture , the homovalent copper(II) cations have been
redox-activated by the bismuth(V) components , and so superconductivity would
indeed occur in the CuO2 planes , as claimed by Tarascon and co-workers .
“Direct through-space magnetic dipole interaction of spins is far too small to account
for most magnetic-ordering phenomena” (p. 148) .
The electron spin orientations of the cations are mediated by the p orbital electron
pairs of the intervening anions , as shown below for the Cu–O–Bi atoms in BSCCO ,
for example :
Superexchange in this particular case may be facilitated by the pπ –pπ overlap of the
Cu 5pz –O 2pz –Bi 7pz orbitals to form a linear nodeless Cu–O–Bi pi XO . The spin
orientations of the Cu and Bi valence electrons will be synchronized by
superexchange , with bismuths' free electrons copying the antiparallel orientations of
their copper 3d9 partners , which are pinned in the Cu–O lattice .
Generally , the free electrons' spins will mimic those of any sort of magnetic ordering
in the adjacent induction layers . For example , if the induction agent was
ferromagnetic , the spin ordering in the free electrons above EF would be identical ,
i.e. parallel . This is reminiscent of their precise reflection of incident light
wavelengths , which is the physical basis of mirrors .
0.6 BaO + 0.4 KO2 + ½ Bi2O3 --------- (1) heat at 675 ºC , 3 days ---------
As mentioned above , Arjomand and Machin prepared La2CuO4 and thought it might
be antiferromagnetic :
“La2CuO4 has a very low magnetic susceptibility ........ which remains relatively
constant over the temperature range 8–300 K . It is not clear why this behaviour
occurs , unless there is a very strong antiferromagnetic interaction” (p. 1064) .
They also prepared La2NiO4 in another study of ternary nickel oxides , and similarly
found it to be antiferromagnetic . For typical high spin Ni2+, µ eff ~ 3.1 BM ; at 300 K ,
they found µ eff = 1.70 BM ; at 80 K , they found µ eff = 1.09 BM (Table 3 , p. 1057) .
Bednorz and Müller's success with Ba- and Sr-doped La2CuO4 resulted in it being
extensively studied from the late 1980s onward . La2CuO4 , La2NiO4 , and La2CoO4
are now recognized as being quite strongly antiferromagnetic , with Néel temperatures
of around 350 K , 330 K , and 270 K respectively (mentioned by Blundell et al. ,
PDF , 116 KB ; but see the refs. in Several investigations for various different TN
values . Magnetic susceptibilty and TN are very sensitive to the sample preparation
history and to the compound's stoichiometry) .
Several investigations of how partially oxidizing La2CuO4 and La2NiO4 affects their
magnetic susceptibilty and TN are very pertinent to this present report . It was
generally found that partial oxidation of the copper(II) and nickel(II) in the
compounds substantially degraded their antiferromagnetism , flattening their magnetic
susceptibility curves and lowering their TNs . This should come as no surprise in light
of the above discussion of mixed-valent compounds . Partial oxidation is chemically
creating mixed-valent Cu(II)–Cu(III) and Ni(II)–Ni(III) ; the 3d valence electrons in
the Cu(II) and Ni(II) , previously pinned in the homovalent compounds , are now
resonating in the mixed-valent materials . This electron resonance is degrading the
antiferromagnetic ordering of the 3d electrons in the lattice .
We can now clearly see the dilemma of high temperature superconductivity : on the
one hand , we need the Robin-Day Class II (Class 3) mixed-valent resonance to unpin
the valence electrons in the homovalent insulators and create a bilayer metallic bond
in them ; but on the other hand , such a resonance destroys the antiferromagnetism we
need to ensure the free electrons have the antiparallel orientation they require for
magnetic coupling into Cooper pairs . Chemists trying to synthesize such
superconductors must therefore find the precise balance between optimizing the
mixed-valency and yet retaining sufficient antiferromagnetism in the modified
material . We will always be confronted by this dilemma as long as we try to design a
superconductor by creating a Robin-Day Class II mixed-valent metallic compound
within an antiferromagnetic homovalent precursor .
Wells has pointed out the similarity of the K2NiF4 crystal structure with that of the
perovskites :
Referring to the Table of Oxidizers above , we note that cobalt(II) oxide can't be
oxidized by Bi(V) , so La2CoO4 could also be tried as an antiferromagnetic induction
agent with Ba0.6K0.4BiO3 . Yamada and co-workers measured TN = 275 K for
La2CoO4 .
Normally , researchers would carefully avoid the inclusion of high spin cations with
any superconductor material or candidate . However , they should remember that high
spin copper(II) is found in BSCCO-2212 , for example . I pointed out in the Doping
web page that in the YBCO series of cuprates , MBa2Cu3O7 , superconductivity was
still observed even when M was a paramagnetic Rare Earth cation such as Dy3+, 4f9 ;
Gd3+, 4f7 ; Sm3+, 4f5 ; and Nd3+, 4f3 . These are all inert spectator cations , nested
between the electronically active CuO2 sheets and CuO3 pyramids . The Rare Earth
cations in the YBCO series are off to the side and don't participate in the Cu–O
bilayer metallic bond in them . Their f electron Curie paramagnetism is undoubtedly
much weaker than the d electron antiferromagnetism in the copper(II) cations . They
therefore don't disrupt the formation of the Cooper pairs and are quite innocuous .
Similarly , the layers of La2CuO4 intercalated between the bismuthate layers – in
which the electronic activity actually occurs – shouldn't interfere with the Bi–O
superconductivity , so long as their Cu2+ doesn't mix into the bismuth layers . The two
different layers are somewhat like “oil and water”, and probably would remain cleanly
separated , like the complex layers in BSCCO-2212 .
The titanium triad would be present in this system in the composition La0.67Sr0.33TiO3 ,
although that might not be the optimum formula . The optimized LaxSr1-xTiO3 would
then be combined with an equimolar quantity of stoichiometric La2NiO4 to obtain the
layered La/Sr–Ti–Ni–O structure , which hopefully would have a significantly
enhanced superconducting transition temperature relative to the original LaxSr1-xTiO3 .
N. Bergeal and co-workers recently reported that epitaxial films of LaxSr1-xTiO3 they
prepared had a Tc ~ 0.3 K (PDF , 1592 KB) .
The tungsten (and other) bronzes are brightly coloured with a metallic luster , and
they can have high electrical conductivities . For example , the cubic bronze
Na0.85WO3 has an ambient conductivity of around 70,000 ohm-1cm-1 . Despite these
remarkably high conductivities , few of the tungsten (or other) bronzes become
superconducting , even near Absolute Zero . Matthias and co-workers studied the
electrical conductivity near Absolute Zero of a dark blue sample of tungsten bronze
having the approximate composition Na0.3WO3 , whose Tc ~ 0.57 K (onset) .
Rubidium tungsten bronzes have the highest transition temperatures of the alkali
metal tungsten bronzes , with the Tc = 1.98 K for RbxWO3 (x = 0.27–0.29) reported in
1965 . An efficient synthesis of rubidium tungsten bronzes in a microwave furnace
was recently described by J. Guo and co-workers . All the conductive bronzes display
Pauli paramagnetism , with no evidence of any antiferromagnetism .
Tungsten bronzes were first prepared in 1823 by the prominent German chemist
Friedrich Wöhler (1800–1882) , and several synthesis routes to them have been
developed since then . In a typical procedure described in detail in Inorganic
Syntheses , W(0) and W(VI) are reproportionated to mixed-valent W(V,VI) using a
mixture of tungsten metal powder , tungsten trioxide , and sodium tungstate salt . This
classical method was recently modernized by carrying it out in a microwave furnace .
Another interesting preparation of a barium tungsten bronze was published by Conroy
and Yokokawa :
x BaCl2 + x WO2 + WO3 ---- (900 ºC , 15 hrs , in vacuo) ------> BaxWO3 + x WO2Cl2
(g) .
The by-product WO2Cl2 was sublimed from the mixture , thus driving the reaction to
completion . However , this resulted in a deplorable loss of valuable metal reagent
from the system . Here's a suggestion for a simple route to sodium tungsten bronzes ,
also involving the evolution of a gaseous by-product – but an expendable one – and
using only relatively inexpensive reagents :
x NaH + WO3 ---- (warm in a stream of pure flowing nitrogen) ------> NaxWO3 + ½ x
H2 (g) ; and ,
x NaBH4 + WO3 ---- (pure flowing nitrogen) ------> NaxWO3 + ½ x H2 (g) + ½ x B2H6
(g) .
Both sodium hydride and sodium borohydride are well-known reagents in organic
chemistry , the former as a strong but non-nucleophilic base , and the latter as a mild
reducer of numerous organic functional groups . The corresponding lithium and
potassium compounds are also known and are commercially available , but are less
frequently used than the sodium chemicals . Hydride is a remarkably strong reducing
agent , and it should readily transfer one of its 1s2 valence electrons to the mildly-
oxidizing W(VI) in the WO3 :
The substantial E0T suggests that the NaH–WO3 reaction could be strongly exoergic ,
so the two compounds should not be compressed into a pellet , but rather gently
mixed together as loose powders . Caution : please take the appropriate safety
precautions if attempting these reactions ! Use of eye protection (safety glasses , with
goggles or a visor) is obligatory , and a safety screen and leather gloves are strongly
advised . Only semi-micro quantities of the reagents (no more than a gram or two)
should be combined in exploratory work , until the researcher is confident that the
reaction – if successful , of course – can be safely scaled up to a preparative level .
The tungsten triad would be represented in the bronze [Na1+]2 [W(V)O3 –W(VI)O3 –
W(V)O3] ; dividing by 3 , we have Na0.67WO3 , which is in the “mid-range” of
sodium-doped WO3 . This may or may not represent the optimum doping level for
superconductor candidates , so I would suggest adding a less doped bronze , say
Na0.35WO3 , and a more highly doped one , say the conductive cubic bronze Na0.85WO3
mentioned above , to the research study of these materials . These three sodium
tungsten bronzes would then be combined with an equimolar quantity of La2NiO4 to
produce the composites La2NaxNiWO7 (x = 0.35 , 0.67 , and 0.85) for physical
testing . A “shake-'n-bake” technique , with an inert atmosphere of pure , dry argon ,
and moderate baking temperatures (~ 800–900 ºC) , would be used in their
preparation . Chemical bonding in La2NiO4 is entirely ionic in nature , while the W–O
bonds in the bronzes are covalent , so hopefully the W–O and Ni–O layers would
remain completely separated in the new W–O–Ni composites .
Molybdenum trioxide , a pale green powder , m.p. 795 ºC , could similarly be reacted
with NaH and/or NaBH4 to produce the corresponding sodium molybdenum bronzes .
The molybdenum triad is 4d1– 4d0– 4d1 for Mo(V)–Mo(VI)–Mo(V) , and the exact
triad would be present in the bronze Na0.67MoO3 [tetragonal K0.5MoO3 has an
unusually high Tc = 4.2 K (Sleight and co-workers)] . MoO3 is somewhat more
strongly oxidizing [Mo(VI) / Mo(V) ~ 0.7 V] than WO3 . It might therefore be
possible to try the more oxidizing La2CuO4 , as well as La2NiO4 and La2CoO4 , as
antiferromagnetic induction agents with the NaxMoO3 bronzes .
Rhenium trioxide , briefly discussed above , would also provide an excellent test of
the antiferromagnetic induction theory . As mentioned earlier , although it has a
remarkably high ambient electrical conductivity , it never becomes superconducting .
It's really a type of bronze , with a cubic crystal structure similar to the tungsten
bronze perovskites [hexagonal K0.3ReO3 has a Tc = 3.6 K (Sleight and co-workers)] .
Its Re(VI) is 5d1 electronically . Rhenium trioxide has a bilayer Re–O metallic bond ,
but it displays Pauli paramagnetism and isn't antiferromagnetic at all . ReO3 could be
layered with an equimolar quantity of La2NiO4 to form the composite La2NiReO7 ,
whose electrical properties would be carefully studied and compared with those of the
parent compound .
(1–x) BaCO3 + ½ x La2O3 + ½x SnO + (1– ½x) SnO2 --------- (flowing argon)
--------->
Ba1-x Lax SnO3 + (1–x) CO2 (g) [or ¼x Sn0 + (1– ¼x) SnO2] , where x = 0 to 1 ,
and their electrical conductivities determined . The composite Ba0.33 La0.67 SnO3 [i.e.
3–4–3 , which is equivalent to 4–2–4] would represent the tin triad , although it might
not be optimized with respect to electrical conductivity and superconductivity (if
any) . Tin(II) is very easily oxidized to tin(IV) [0.151 V] , so all of the synthesis
procedures should be carried out in an inert (argon) atmosphere . The optimum Ba1-x
Lax SnO3 composite would then be intercalated with stoichiometric La2NiO4 and/or
La2CoO4 (but not with the oxidizing La2CuO4) to obtain Ba/La–Sn–O–Ni/Co layered
structures for further electrical testing .
Another example is titanium disulfide , TiS2 , which I've discussed in the Layered web
page . It has a lamellar morphology like that of graphite , with a golden-yellow colour
and a metallic luster . Its ambient electrical conductivity is about 1400 ohm-1cm-1 , and
while it has an inverse temperature–conductivity relationship , TiS2 apparently never
becomes superconducting , although many of its intercalation products do (but only
close to Absolute Zero) . Suppose a layer of an antiferromagnetic induction agent was
intercalated between each layer of TiS2 ; would the composite then become
superconducting at an appreciable Tc ? Here's a suggestion : equimolar quantities of
TiS2 and the compound tetrakis(triethylphosphite)nickel(0) , [(EtO)3P]4Ni , both of
which are commercially available , could be reacted together . After distillation of the
complexing (EtO)3P ligands from the solid , the nickel atoms would bond with the
sulfurs to form a coating of NiS over the TiS2 layers . Nickel(II) sulfide is known to be
a fairly strong antiferromagnetic material [TN = 263 K (–10 ºC) , Table above] , so
possibly the nickel-intercalated product TiS2Ni might prove to be a superconductor ,
with a Tc well above Absolute Zero .
The study of AFM induction in layers of metallic solids continues in the web page ,
“New Layered Compounds for High Temperature Superconductivity”, with more
examples of metallic–AFM composites .
was achieved : J.R. Gavaler , “Superconductivity in Nb–Ge Films Above 22 K”, Appl.
Phys. Lett. 23 (8) , pp. 480-482 (1973) . Matthias had also investigated Nb3Ge earlier :
B.T. Matthias et al. , “Superconductivity of Nb3Ge”, Phys. Rev. 139 (5A) , pp.
A1501-A1503 (1965) . They found that for a bulk sample of stoichiometric Nb3Ge the
Tc ~ 17 K (onset) .
frantic search : R.M. Hazen , The Breakthrough , The Race for the
Superconductor , Summit Books , New York , 1988 . See also : B. Schechter , The
Path of No Resistance , The Story of the Revolution in Superconductivity , Simon and
Schuster , New York , 1989 ; J.L. Mayo , Superconductivity , The Threshold of a New
Technology , TAB Books , Blue Ridge Summit (PA) , 1988 ; J. Langone ,
Superconductors , The New Alchemy , Contemporary Books , Chicago (IL) , 1989 ;
Simon and Smith (see above) also provide a good account (“Breakthrough” , Ch. 13 ,
pp. 247-265) of the world-wide research efforts in the high temperature
superconductivity of the cuprates around 1986–87 .
magnetite : The electronic situation in magnetite is quite complex , and there have
been many studies of it over the past decades . For reviews of the physics and
chemistry of magnetite , see the following two articles : F. Walz , “The Verwey
Transition – A Topical Review”, J. Phys. : Condens. Matter 14 (12) , pp. R285-R340
(2002) ; J. García and J. Subías , “The Verwey Transition – A New Perspective”, J.
Phys. : Condens. Matter 16 (7) , pp. R145-R178 (2004) .
oxidize water : M.F. Yan et al. , “Water Interaction with the Superconducting
YBa2Cu3O7 Phase”, Appl. Phys. Lett. 51 (7) , pp. 532-534 (1987) .
B.M. Klein et al. : B.M. Klein et al. , “Electronic Structure and High Critical
Temperature in Oxide Superconductors”, Ch. 3 , pp. 26-43 in Chemistry of High-
Temperature Superconductors II , D.L. Nelson and T.F. George (eds.) , ACS
Symposium Series 377 , American Chemical Society , Washington , DC , 1988 ;
Figure 1 , p. 28 ; ibid. , J. DiCarlo et al. , “Determination of the Homogeneity Range
of La2CuO4”, Ch. 11 , pp. 140-144 ; Figure 2 , p. 144 . The La2CuO4 structure was
also sketched by J.B. Goodenough , “Ceramic Superconductors , Single-Valent versus
Mixed-Valent Oxides”, Ch. 16 , pp. 287-321 in Electron Transfer Biology and the
Solid State , Inorganic Compounds with Unusual Properties , M.K. Johnson et al.
(eds.) , Adv. Chem. Series 226 , American Chemical Society , Washington , D.C. ,
1990 ; Fig. 15 , p. 318 .
Wells : A.F. Wells , Structural Inorganic Chemistry , 3rd edition , Clarendon Press ,
Oxford (UK) , 1962 . The K2NiF4 structure is sketched in Fig. 166 , p. 499 .
Verwey : E.J.W. Verwey , “Valence Induite”, Bull. Soc. Chim. France , mises au
point D122 (1949) [“Induced Valence”, Chem. Abs. 43 , 6015g (1949)] .
tungsten bronzes : P.G. Dickens and M.S. Whittingham , “The Tungsten Bronzes and
Related Compounds”, Quart. Rev. 22 (1) , pp. 30-44 (1968) ; H.R. Shanks , P.H.
Sidles , and G.C. Danielson , “Electrical Properties of the Tungsten Bronzes”, Ch. 22 ,
pp. 237-245 in Nonstoichiometric Compounds , R. Ward (ed.) , Adv. Chem. Series 39
, American Chemical Society , Washington , D.C. 1963 ; M.J. Sienko , “Electric and
Magnetic Properties of the Tungsten and Vanadium Bronzes”, Ch. 21 , pp. 224-236 in
Nonstoichiometric Compounds ; C.T. Hauck , A. Wold , and E. Banks , “Sodium
Tungsten Bronzes”, pp. 153-158 in Inorg. Synth. 12 , R.W. Parry (ed.) , McGraw-
Hill , New York , 1970 [republished by R.E. Krieger , Huntington , NY] .
Rubidium tungsten bronzes : A.R. Sweedler , Ch. J. Raub , and B.T. Matthias ,
“Superconductivity of the Alkali Tungsten Bronzes”, Phys. Lett. 15 (2) , pp. 108-109
(1965) ; R.K. Stanley , R.C. Morris , and W.G. Moulton , “Conduction Properties of
the Hexagonal Tungsten Bronze , RbxWO3”, Phys. Rev. B20 (5) , pp. 1903-1914
(1979) .
Conroy and Yokokawa : L.E. Conroy and T. Yokokawa , “The Preparation and
Properties of a Barium Tungsten Bronze”, Inorg. Chem. 4 (7) , pp. 994-996 (1965) .
Sleight and co-workers : A.W. Sleight , T.A. Bither , and P.E. Bierstedt ,
“Superconducting Oxides of Rhenium and Molybdenum with Tungsten Bronze Type
Structures”, Solid State Commun. 7 (2) , pp. 299-300 (1969) .