This article briefly reviews ceramic superconductors from historical and materials perspectives. It describes the factors that distinguish high-temperature cuprate superconductors from most electronic ceramics and places them in the context of other families of superconducting materials. Finally, it describes some of the scientific issues presently being actively pursued in the search for the mechanism for high-temperature superconductivity and the directions of research into new superconducting ceramics in recent years.
I. Introduction
DURING the long history of electronic oxide ceramics before
1986, even the most astute observer would have found few
clues predicting the revolution in materials science and physics
that those materials would eventually unleash. Oxide ceramics are
an important part of electronics technologies because of their
electrically insulating, optical, and dielectric properties, but very
rarely for their ability to conduct electrical current. Insulators
such as steatite, dielectrics such as SiO2 and Ta2 O5 , piezoelectrics such
as lead zirconate titanate (PZT), optical materials such as LiNbO3
,and the transparent semiconductor indium tin oxide (ITO) can be
considered as representative of the large class of metal oxides with
real and potential applications in electronics technologies. Al-though
such materials are sophisticated and complex when con-sidered
from any point of view, their technological usefulness in
electronics generally results (with the exception of ITO and a
handful of other materials) from their ability to block or highly
resist the passage of electrical current and, as an important
consequence in some cases, their transparency at optical wave-lengths.
These important characteristics of most oxides are related to a
fundamental chemical difference between the metallic elements
and oxygen: the difference in their electronegativities. These
differences in electronegativity result in semiconducting or insu-lating
materials, with forbidden energy gaps between the highest
occupied orbitals in the solid derived from oxygen electronic states
and the lowest unoccupied orbitals derived from the metal elec-tronic
states. The technical applications of electronic ceramics
depend very highly on the materials scientist's manipulations of
these energies, the introduction or elimination of defects that alter
the distribution of energy states and/or their occupancy by charge
carriers, and other factors such as the polarizabilities of the
component atoms.
Not all metal oxides are transparent. Transition-metal oxides
have been used since ancient times as pigments because of strong
optical-frequency localized electronic absorptions between differ-ent
excited states of the electrons in the transition-metal d orbitals,
which lead to color. As electronic conductors, however, i.e., as
competitors for copper wire, with few exceptions, they have never
been of significant technological interest. Their principal consid-eration
as electrical conductors has come primarily from their
stability under high temperature, chemically extreme conditions
where metals are not expected to be thermodynamically stable, as,
for example, is found in electrodes for magneto-hydrodynamic
generators.
This whole picture was stood up side down in late 1986 with the
discovery of superconductivity at surprisingly high temperatures in
an electronically conducting oxide based on lanthanum, barium,
copper, and oxygen. Superconductivity is the passage of electrical
current with zero resistance below a certain critical temperature
(Tc). The best superconductors known at the time, to be described
below, were metallic compounds, not ceramics, as one might
expect as a consequence of the (no longer obvious) general fact
that metals are good electrical conductors and oxides are not. Good
superconductors do not have to be good metallic conductors above
their superconducting transition temperature, however, and the
fundamental characteristics that result in superconductivity at high
temperatures in the copper oxides have little to do with any type of
conventional understanding of the electronic properties of materials.
In fact, more than a decade after their discovery, there
continues to be no universally accepted theory for why these
materials are superconductors. No one working in the field in the
early days could possibly have foreseen that this would be the case
after so much work and thought had been devoted to the problem.