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Physica B 296 (2001) 112}119

The other high-temperature superconductors


W.E. Pickett*
Department of Physics, University of California, Davis, CA 95616, USA

Abstract

Since the discovery of the high-temperature superconducting cuprates in 1986, there have been four classes of
superconductors discovered that have members with critical temperature higher than the highest known in 1986. These
classes are typi"ed by (in chronological order) the representatives: Ba K BiO , Cs C , YPd B C, and Na HfNCl,
\V V      V
with maximum critical temperatures, respectively, of 35, 40, 23, and 25 K. These new superconductors are mostly di!erent
from the older superconductors, and certainly di!erent from the layered cuprates. For several characteristics that are
possibly important for superconductivity, two or three of the classes share similarities. There seems, however, to be
almost no feature that is shared by all four classes. However, the three for which there is isotope shift data clearly qualify
as phonon-coupled superconductors.  2001 Elsevier Science B.V. All rights reserved.

Keywords: Superconductivity; Intermetallics; Quaternary compounds; Isotope e!ect

1. Motivation for this overview E Stay away from oxygen.


E Stay away from magnetism.
From the early 1970s until 1986 when the high- E Stay away from insulating phases.
temperature superconductors based on CuO
 Here N(E ) is the density of states at the Fermi level
layers were discovered, [1] the highest supercon- $
E . It has been abundantly clear that many of these
ducting critical temperature ¹ was 23 K in the
 $
A15 pseudobinary system Nb Al Ge [2,3]. `rulesa have been broken by the cuprate high-
 \V V temperature superconductors (HTS), which are in
Two decades of intense study had increased ¹ in
 a class by themselves when considering supercon-
the A15s from &15 to 23 K, and the prevailing
understanding of producing high-temperature ductivity.
superconductors at that time was encoded in a The purpose of this paper is to provide an over-
loosely formulated set of `Matthias's rulesa: view and a comparison of four classes of materials
that have been discovered since the discovery of the
E Transition metals are better than simple metals. HTS, all of which have maximum values of ¹

E There are favorable electron/atom ratios [N(E ) equal to or higher than 23 K critical temperature in
$
peaks]. the A15 superconductors. Representatives of these
E High symmetry is good; cubic symmetry is best. classes are listed in Table 1, with the year of dis-
covery of that class, the maximum ¹ , and a rough

characterization of the value of N(E ). What will
$
* Tel.: #1-530-752-0926; fax: #1-530-752-4717. become clear is that at least three of these classes of
E-mail address: pickett@physics.ucdavis.edu (W.E. Pickett). superconductors are quite di!erent from those that

0921-4526/01/$ - see front matter  2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 4 5 2 6 ( 0 0 ) 0 0 7 8 7 - 0
W.E. Pickett / Physica B 296 (2001) 112}119 113

Table 1 Coulomb repulsion is neglected, and more gener-


Classes of superconductors, with representative member, with ally adds to a number less than but of the order of
¹ '20 K, excluding the cuprate superconductors. The date of
 . The picture arising from the isotope shift data is
discovery, and rough characterization of their Fermi level den- 
sity of states N(E ) is given summarized in Table 2.
$
Year ¹  (K) Representative N(E )
 $
2. The barium bismuthate system
1973 23 Nb Ge Large

1988 35 Ba K BiO Small
\V V  This system is the only high ¹ system whose
1991 40 Cs C
 
Large 
1994 23 YPd B C Large discovery was strongly in#uenced by theory.
 
1997 25 Na HfNCl
V
Small Building on knowledge of the electronic structure
of the Ba(Pb, Bi)O (BPBO) system, whose

¹ peaks around 13 K, Mattheiss et al. [5] reduced
Table 2

the carrier concentration by substituting K on the
Classes of superconductors, with representative member, the Ba site rather than Pb on the Bi site, and produced
Maximum ¹ in the class, and indication of the measured value
 ¹ '20 K in the Ba K BiO (BKBO) system, a
of the isotope shift of ¹ for certain elements
  \V V 
value which was then raised to 30 K by Cava et al.
¹  (K) Representative  [6,7] and "nally to 35 K. Doping with Rb also
 H
works [6] but that system has been studied very
23 Nb Ge
 little.
}
35 Ba K BiO  "0.2; 0.4
\V V  - Superconductivity in BKBO emerges from a dis-
40 Cs C  &0.3}0.4
  ! torted perovskite structure (space group C2/m [8],
23 YPd B C  &"0.25
 
25 Na HfNCl
V
? possibly P2/m at the lowest temperatures [9]) of
semiconducting BaBiO . This monoclinic structure

is very low symmetry (four operations) but contains
followed Matthias's rules, and certainly di!erent the inversion operation, hence it is not ferroelectric.
from each other. Electronic structure calculations of the (unstable)
The discussion will proceed system-by-system, in cubic perovskite structure of BaBiO indicate a

order of their discovery. Since the Cs C systems metallic system } in fact, a half-"lled band system
 
has been well reviewed elsewhere, the discussion } with a strongly nested Fermi surface that drives
here will be particularly selective. The discussion a Peierls-like, charge density wave doubling of the
here is not focussed on the coupling mechanism per cell [10,11]. The Bi ions in the doubled cell become
se, but since there is some isotope e!ect information inequivalent, but the charge disproportionation
on all but one of these systems, we will include has been found both experimentally and theoret-
discussion and references on this data. The isotope ically to be small. In addition, the BiO octahedra

shift coe$cient  due to isotope replacement rotate, again doubing the unit cell and complicat-
H
of element j with mass M in the compound is ing both the experimental characterization and the
H
de"ned by theoretical description.
Doping with K at a concentration x*0.3 leads
d log ¹ to a cubic metal and ¹ up to 35 K. For most
 "!  (1) 
H d log M purposes this system behaves in a rigid band way
H
based on cubic BaBiO band structure. The

and a value of  that is de"nitely nonzero (greater relevant energy range is dominated by a broad
H
than 0.1, say) is normally regarded as clear evidence antibonding Bi 6s}O 2p band crossing the Fermi
of participation of phonons in the superconducting level [12].
pairing (see Carbotte's review [4]). In a harmonic Although there have been questions about the
phonon-coupled system, the sum of the (positive) possible in#uence of residual electron}electron in-
isotope shifts from each of the elements adds to  if teractions in explaining the normal state properties

114 W.E. Pickett / Physica B 296 (2001) 112}119

and high value of ¹ in BKBO, nearly all studies [21}26] that there is little to add here except to put

have concentrated on electron}phonon (E}P) them into the context of these classes of supercon-
coupling, and particularly the coupling to the high- ductors. Gunnarsson has given a detailed review
frequency oxygen modes. This view is justi"ed by [22] of the various theoretical considerations that
the isotope shift of ¹ , where reported values are enter into the superconductivity of the fullerides.

 "0.22 [13],  "0.41 [14], and  "0.35 [15]. Superconductivity was discovered "rst in the tri-
- - -
Rigid-ion-type models of the coupling indicate alkali-fullerides such as K C [27,28] in the area
 
dominant coupling to oxygen [11,16]. A tight- of ¹ &20 K, but there are now several combina-

binding parametrization of electronic structure and tions of alkali or alkaline earth metal atoms that
E}P matrix elements [17] also led to strong coup- can produce superconductivity when placed in in-
ling, with E}P coupling strength &1.1 for the terstitial sites in the fullerene lattice. The highest
maximum ¹ , and ¹ values of over 30 K could be value reported is 40 K for Cs C under pressure
   
accounted for. Tunneling measurements [18,19] [29].
also indicate strong coupling to high-frequency These fullerides are simply unique, not only in
phonons in BKBO, and overall features consistent the world of superconductivity but in crystalline
with an E}P mechanism with relatively strong solids in general. Structurally, the solids consist of a
coupling. A very interesting loose end in this pic- lattice determined mostly by the highly symmetri-
ture is the recent result of Meregalli and Savrasov cal, closed shell C molecules. Electronically, the

[20] who have carried through the only fully "rst fullerene molecule can be viewed almost as a nearly
principles calculation of the phonon spectrum and spherical &superatom', supplying superatom or-
E}P coupling strength for BKBO. Their results bitals that have a more angular structure than a
correspond only to a coupling strength of "0.3, transition metal's d suborbitals have, but otherwise
insu$cient to account for ¹ in the 30}35 K range. are orbitals with small overlap with neighboring

Some of the basics of the BKBO system perhaps orbitals [30}32].
may be considered to be understood. But why it so The alkali (or alkaline earth) ions go into the
much better a superconductor than, say, the oxide interstitial sites in the solid, and change the struc-
LiTi O , or more to the point, the very similar ture somewhat, but the primary e!ect is to donate
 
compound BPBO? It is dangerous to make a seri- their valence electrons to the narrow ((1 eV wide)
ous comparision to LiTi O (¹ "13 K), as it is C -derived bands. The hopping is however large
   
one of only two out of many oxide spinels that is enough compared to the intra-molecular Coulomb
metallic and thus may be curious itself. (The other repulsion that metallic behavior results, and in
conducting spinel is LiV O , an even more curious many cases superconductivity arises. Superconduc-
 
heavy fermion compound.) At present, there may tivity was discovered [27] around 20 K in K C
 
be no better information on the strong di!erence almost as soon as metallicity was obtained.
between BKBO and BPBO than that which guided The many considerations that arise in evaluating
Mattheiss et al. [5]: altering the Fermi level toward whether superconductivity in fullerides arises for
half "lling (and strongest coupling to the oxygen E}P coupling has been reviewed by Gunnarsson
bond stretch vibrations) by BiPPb induced charge [22]. A similarity to BKBO is that the coupling
ordering waves on the Pb}Bi sublattice; varying the results mainly from the high frequency phonons. In
electron count by BaPK leaves the Bi sublattice the fullerides these modes are those that modulate
intact. As a result the system retains structural the C}C bonds most strongly, which are primarily
stability further into the strong coupling regime. those in which the C atoms move tangentially to
the surface of a C molecule.

Several isotope shift experiments have been re-
3. The fullerides ported, and are referenced and discussed in pre-
vious reviews [21,22]. The accepted value is
The fullerene (C )-based solids have been around  &0.35, which is a normal value for
 !
studied so heavily and reviewed so thoroughly a conventional superconductor. (Much larger
W.E. Pickett / Physica B 296 (2001) 112}119 115

values have been reported in two cases but appar- discovered by Mazumdar, Hagarajan, and collab-
ently do not represent intrinsic shifts.) An experi- orators in the Y}Ni}B ternary system [35] and in
ment by Chen and Lieber [33] is particularly the Y}Ni}B}C quaternary system [36] at 12 K.
noteworthy. They realized that a (say, 50%) mix- Cava et al. [37] obtained superconductivity in the
ture of C and C can be achieved in a fulleride in LnNi B C system for Ln"Y and for the lanthan-
 
two distinctly di!erent ways: each buckyball can ides Ln"Tm, Er, Ho, and Lu. For the Lu
contain half of each (statistically, of course), with compound ¹ was above 16 K. The phase was

the solid made of these similar buckyballs, or, identi"ed as a layered structure of the modi"ed
buckyballs can be made separately of each isotope, ThCr Si type [38]. This system can be made with
 
and the solid made of a 50% mixture of each type. most of the lanthanides, and after the initial excite-
Optical measurements on the solids con"rmed that ment over the relatively high ¹ in this system, the

substitution occurred as expected } in the "rst case strong subsequent activity has centered largely on
the infrared-active phonons were mass-averaged, the competing and sometimes coexisting magnetic
while in the second case the phonons were mass- and superconducting order parameters [39]. Some
di!erentiatied. In the "rst case,  +0.3 was ob- overviews are available [40,41], but an extensive
!
tained, consistent with the value quoted above (this review is yet to be undertaken.
is the standard way of doing the isotope replace- Rather early on, ¹ +23 K was reported in the

ment). In the second case, the anomalously large Y}Pd}B}C system [42,43] and was naturally sus-
value of  &1.3 was obtained. This result still has pected to be YPd B C with the same crystal struc-
!  
no satisfactory explanation. Since the change of ture, but it has proven to be very di$cult to isolate
mass is 8%, it is possible } but not likely } that the a large enough fraction of the phase to determine
linear aproximation assumed in Eq. (1) breaks the structure unambiguously. There have been dis-
down. Another possibility is a large anharmonicity agreements in the literature about whether the 23
of strongly coupled phonon modes. The most K superconducting phase has the same structure as
strongly coupled are the H symmetry modes of the the other borocarbides [44}46], but the majority of

buckyball, but anharmonicity is not apparent in the evidence seems to indicate so. Very recently,
other data on these modes. Dezaneti et al. [47] claimed to have made the direct
It was emphasized by SchluK ter et al. [34] that identi"cation.
there is a monotonic relationship between the value The layered crystal structure of YNi B C
 
of ¹ and the shortest distance d between two C suggested that this was another quasi-two-dimen-

atoms on neighboring C molecules, with ¹ in- sional system, as the cuprates had been found
 
creasing with d. This e!ect is generally explained to be. Electronic structure studies indicated this
(see Ref. [22]) as resulting from the expression should not be the case [48}50] but that the
electronic structure should be only weakly anisot-
"N(E )<. (2)
$ ropic. This prediction has been substantiated
The Fermi surface averaged pairing potential < is by the extensive experimental data that has
insensitive to spacing, being largely a molecular prop- appeared due to the availability of clean, large
erty. The bandwidth decreases, however, as the inter- single crystals [39].
molecular spacing } and hence hopping } decreases, There is nothing so remarkable in the band
and N(E ) increases. This trend will "nally be halted structure, of either LuNi B C (¹ "16.6 K) or
$   
by correlation e!ects; however, it seems to hold for all the isostructural, isovalent YPd B C (apparently
 
fullerides superconductors fabricated so far. the ¹ "23 K compound) to indicate that it

should be an unusually good superconductor. In
a general sense it might be said that it is an
4. The rare earth}transition metal}borocarbides intermetallic (or -metalloid) compound that is
comparable to Nb Ge, but there are other such

The "rst discoveries in this system were reported intermetallic compounds with a rather high value
in 1994. Superconductivity in this system was of N(E ) that are not good superconductors.
$
116 W.E. Pickett / Physica B 296 (2001) 112}119

One obvious and suggestive feature is a band


that is quite #at near the (/a, /a, 0) part of the
Brillouin zone. This band has not had any simple
interpretation in terms of a tight-binding picture. It
has a majority of Ni d character, but is split o! from
the main Ni d band region and is hybridized with
both B and C, and interactions with the rare earth
atom also seem to have some importance for this
band [51]. It is this band that produces the peak in
the density of states very close to E , a peak that is
$
clearly central to the high value of ¹ . A simpler

guess, however, based on the band structure and
Fig. 1. Structure of the Na-doped HfNCl structure. Left: ar-
the strong Ni character, would be that magnetism, rangement of the Na, Cl, and HfN layers. A full monolayer of Na
not superconductivity, would arise. is pictured. Right: bonding con"guration of the (HfN) bilayer.

An estimate of the relative coupling strength of Note that Hn and N are bonded to each other across the bilayer
the four atoms in LuNi B C [52] gave the ratios as well as within it.
 
B : C : Ni"50% : 30% : 20%, i.e. these atoms may
have contributions that are comparable in magni-
tude. Mattheiss et al. pointed out [53] a strong by Cl ions, and in the undoped compounds this six
dependence of the position of the #at band to the layer slab is van der Waals bonded to neighboring
position z of the B atom, translating into strong slabs. Electronic structure studies [65}67] obtain a
coupling to the B atom. Laurie and Franck [54] gap of 1.5}2 eV, similar to the experimental value.
reported an isotope shift of  "0.27, indicating The system is consistent with a formal ionic de-
that B motion is very strongly involved in enhanc- scription Hf>N\Cl\, with the Hf d shell empty.
ing ¹ . Further study indicates however that an ionic pic-

On the experimental side, strong coupling e!ects ture is limited, because there is a strong covalent
have been seen through neutron spectroscopy of component to the bonding involving N p and Hf
the phonons of these compounds by Kawano et al. d states that shows up in the band character and in
[55], by Stassis et al. [56], and by Gompf et al. the valence charge distribution.
[57], leaving no doubt of the strong d}p coupling Virtual crystal calculations indicate [65,66] that
in this system. The overview by Drechsler et al. [58] the doped-in Na atom gives up its valence electron
should be consulted for further information and to a Hf d}N p band within the layer, in line with
references. expectations. This band is comprised of in-plane
orbitals (d , d   and p , p ), which being above
VW V \W V W
the "lled N p bands and at the bottom of the
5. The transition metal chloronitrides Hf d bands, is probably best characterized as
non-bonding. Since there are two such layers,
The layered compounds ZrNCl and HfNCl have a bonding combination and an antibonding combi-
been known for some time, [59,60] but it was nation forms, split by &1.5 eV. It is the layer-
reported only in 1996 that they could be doped symmetric d}p band that the additional electrons
} intercalated } with Li or Na to become metallic occupy. This situation can be seen in the left panel
and superconducting [61}64]. An impressive of Fig. 2.
value of ¹ "25 K was reached by Yamanaka It is not easy to ascertain accurately the fraction

et al. [62] in Na HfNCl with an estimated value x of Na, and hence conduction electrons, in the
V
of x&0.3. superconducting parts of the samples, although
The structure of this system is shown in Fig. 1. x&0.3 has been quoted as the likely value. At this
(HfN) (or (ZrN) , but we take the Hf compound doping level, the Fermi energy still lies within the
 
for de"niteness) bilayers are cladded on either side lowest conduction band, which is a surprisingly low
W.E. Pickett / Physica B 296 (2001) 112}119 117

6. Comparisons and contrasts

There seems to be little mystery why the fuller-


ides, and the borocarbides are superconducting at
roughly the observed temperature. The transition
metal chloronitride system is newer and much less
e!ort has been expended on it. Even the chemical
composition of the superconducting phases are un-
certain, and there is reason to believe this value
may be crucial. The "rst three systems are E}P
coupled systems, and there is simply no clear in-
formation yet on the fourth system.
The "rst three systems are also comprised of type
II superconductors, and estimates of materials
Fig. 2. Virtual crystal band structure in symmetry direction of
Na HfNCl, for (left) x"0.25, (center) x"0.35, and (right)
parameters [65] indicate the chloronitrides are
V type II as well. This feature is of central interest in
x"0.45. The band structure becomes notably non-rigid-band-
like for x"0.45, and there are even important di!erences (be- the borocarbides, since many of the materials have
sides band "lling) between the x"0.25 and the x"0.35 bands. competition between magnetic ordering and super-
Note that it is right around x"0.35 where the #at bands conductivity.
(strongly Hf d  -like) begin to become occupied.
X As noted in the introduction, Matthias' rules are
profoundly violated by these new classes of super-
conductors with ¹ '20 K and by the HTS. One

mass (mH"0.6 m ) band that leads to a small can observe that there are characteristics that are
value of N(E ) and seems unlikely to encourage common to some of all of these newer classes:
$
either strong E}P coupling or large electron cor-
relation e!ects. This state of a!airs has presented 1. must be multicomponent } more than a binary;
a conundrum in trying to account for the pairing 2. at least one site should have variable occupancy
mechanism. No isotope shift data have been (`dopanta);
reported. 3. large electronegativity di!erence between con-
Recent analysis of the condition of samples, and stituents;
the middle and right panels of Fig. 2 suggests a pos- 4. proximity to a magnetic or insulating phase;
sible resolution of this puzzle. OroH -SoleH et al. [68] 5. mixed antibonding bands at the Fermi level;
have shown that samples are likely to more in- 6. there are favorable electron/ion ratios.
homogeneous than previously thought, and there-
fore the value of x in the superconducting regions Regarding new rule 1, A C is binary in the
 
may be di!erent than supposed. Fig. 2 indicates strict sense, but it is a much richer system than
that around x&0.35, the second conduction band standard binary compounds. The other systems
begins to become occupied. This band is quite #at have four elements. As for new rule 2, the borocarb-
over some regions of the Brillouin zone, due to its ides must be considered as stoichiometric. They can
strong d  character that couples primarily to be alloyed on certain sites, but that #exibility is not
X
N p orbitals with a dp overlap, which is typically central to their superconductivity. The fullerides
X
much smaller than the dp overlap that leads to the also tend strongly toward stoichiometry, where
low mass band. This #at band leads to a high value ¹ is highest. For the other two systems, BKBO

of N(E ), and possibly to correlation e!ects as well. and Na HfNCl, a variable concentration is crucial,
$ V
One should note in this regard that the electronic as it is in many HTS systems. The electronegativity
structure around the Fermi level is very strongly di!erence (3) is large in at least three of the systems.
two dimensional, a feature that may also play a In the borocarbides, there may be some ionic char-
part in the pairing mechanism. acter but it is di$cult to identify and quantify. In
118 W.E. Pickett / Physica B 296 (2001) 112}119

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