Chapter 1
Overview of High-Temperature Superconductivity Theory, Surfaces, Interfaces, and Bulk Systems 1
1
1
D. Sahu, A. Langner, Thomas F. George, J. H. Weaver, H. M. Meyer,III ,David L. Nelson, and Aaron Wold 2
2
3
4
1
Departments of Chemistry and Physics, 239 Fronczak Hall, State University of New York at Buffalo, Buffalo, NY 14260 2Department of Chemical Engineering and Materials Science, University 3
of Minnesota, Minneapolis, MN 55455 Chemistry Division, Office of Naval Research, Arlington, V A 22217-5000 Department of Chemistry, Brown University, Providence, RI 02912 4
An overview of the theoretical and experimental aspects of the recently-discovered superconducting compounds is presented. This overview is divided into three sections. In the first section a review of some of the theoretical and computational works is presented under the subsections entitled pairing mechanisms, electronic structure calculations and thermophysical properties. In the second section surface and interface chemistry issues related to the fabrication and use of high-temperature superconductors for high-performance applications are presented. Specific issues that are discussed include metallization and the formation of stable ohmic contacts, and chemically-stable overlayers that are suitable for passivation, protection and encapsulation of superconducting material structures that can then be used under a wide range of environmental conditions. Lastly, issues are discussed that are related to each of the bulk high-temperature superconducting ceramic oxides which have received so much attention the past two years. These include Tl Ba Ca Cu O with a critical temperature of 125 K, which is the current record. 2
2
2
3
10
0097-6156/88AB77-0001$06.00/0 • 1988 American Chemical Society
2
CHEMISTRY OF HIGH-TEMPERATURE SUPERCONDUCTORS II
Theory Since the discovery of high-temperature superconductivity i n the CuO ceramics i n the year 1986, there has been an explosion of t h e o r e t i c a l works r e l a t i n g to these systems. I t i s not possible, i n a short review of t h e o r e t i c a l work l i k e t h i s , to examine the e s s e n t i a l ideas of even a small f r a c t i o n of t h i s large body of literature. We select, quite a r b i t r a r i l y , some of the work we are aware of and discuss the e s s e n t i a l ideas of these. We apologize, i n advance, to a l l the research workers whose work we have not reviewed. This t h e o r e t i c a l overview i s divided into three sections: (1) p a i r i n g mechanism, (2) electronic structure calculations and finally, (3) thermophysical properties. In the section on p a i r i n g mechanism we review the basic microscopic mechanisms that might be responsible for producing superconducting states. This i s a fundamental question and the success of any t h e o r e t i c a l model addressing i t should be judged i n r e l a t i o n to the experiments i t explains and the phenomena i t predicts. The second part, dealing with e l e c t r o n i c structure calculations, i s quite important i n that such calculations give d e t a i l e d information about conduction processes, density of states and anisotropics i n k-space. F i n a l l y , i n the section on thermophysical properties we review works r e l a t i n g to phonon dispersion and soft modes, dynamics of tetragonal-toorthorhombic phase t r a n s i t i o n s and the temperature and concentration dependence of the s t a b i l i t y of these phases. (1) Pairing Mechanism In the conventional superconductors a p a i r of electrons of opposite spin and momentum form a bound state which leads to a coherent and highly correlated many-body superconducting state. The a t t r a c t i v e i n t e r a c t i o n between the electrons of the p a i r i s mediated by l a t t i c e vibrations (phonons) and the electrons overcome t h e i r strong Coulomb repulsion by staying away from each other i n time (retardation). The basic question i n the new superconductors i s What i s the p a i r i n g mechanism? For a review of some of the early p a i r i n g models proposed for the high-T materials we r e f e r the reader to the work by Rice [1]. One of the leading theories for the high-T superconductors i s the resonating-valence-band (RVB) model proposed by Anderson [2] and h i s coworkers [3]. According to this model, the p a i r i n g mechanism i s magnetic i n o r i g i n and not of the conventional BCS type. The s t a r t i n g point of the RVB theory i s a two-dimensional Hubbard model at h a l f - f i l l i n g with strong on-site Coulomb repulsion U and an a t t r a c t i v e i n t e r - s i t e hopping energy t. Without oxygen doping ( i . e . , dopant concentration 5 - 0 ) , the ground state of the above model i s expected to be a long-range anti-ferromagnetic (AF) state [4], but Anderson argues that f r u s t r a t i o n might favor a RVB state over an AF ground state. The basic idea of the RVB theory i s that strong electron-electron correlations r e s u l t i n a separation of charge degrees of freedom from spin degrees of freedom. At low doping (6 0) and temperature, the quasi-particle excitations are believed to be "holons" ( i . e . , charge-carrying spinless p a r t i c l e s ) and "spinons" (i.e., spin-** chargeless particles). C
1. SAHU ET AL.
Overview ofHigh-Temperature Superconductivity
3
Superconductivity i s due to formation of a condensate consisting of holon pairs. Since Bose-Einstein condensation i s not possible i n a s t r i c t l y two-dimensional system, the interplanar couplings are important i n giving r i s e to superconductivity. The RVB theory has been amplified or modified i n several ways [5,6,7], the d e t a i l s of which we won't go into here. Rice and Wang [8] have proposed a model i n which superconductivity i s due to condensation of a pair of bosons which gives r i s e to quasi-particle e x c i t a t i o n energies which are similar to those of RVB theory, but d i f f e r e n t from BCS theory. Rice and Wang, however, favor a phonon interaction which mediates the a t t r a c t i o n between the boson p a i r i n question. Coffey and Cox [9] have given a nice summary of the essential points of the RVB theory i n Section II of t h e i r paper. Another theory that has been proposed i s the spin-bag mechanism of Schrieffer's group [10]. The s t a r t i n g point of t h e i r theory i s the strong AF spin order i n the neighborhood of the superconducting transition (T ) and two-dimensional spincorrelations over a length L (-200 Â) i n the neighborhood of the Neel t r a n s i t i o n (T^ » Τ ). Doping creates extra holes i n the system and these are assumed to be l o c a l i z e d over a length i ( « L ) . The spin of the hole couples to the spin density of the AF background through an exchange interaction. Within a given domain a hole produces an e f f e c t i v e potential well or bag i n i t s v i c i n i t y i n which the hole i s s e l f - c o n s i s t e n t l y trapped. The p a i r i n g i s due to an effective a t t r a c t i v e interaction between two holes which overcomes the short range Coulomb repulsion. The importance of spins i n producing a superconducting state has also been emphasized i n a model proposed by Emery [11]. He has proposed that oxygen doping In the 214-material creates holes at the oxygen s i t e s and that there i s a narrow band of oxygen holes which couple strongly to the l o c a l spin configuration of the Cu-sites. This strong coupling i s responsible for an a t t r a c t i v e interaction between the oxygen holes. We mention i n passing that other mechanisms such as plasmons [12] and excitons [13] have also been proposed as possible candidates for being the condensate of the superconducting state. Recently doubts have been expressed about the importance of the magnetic o r i g i n of the pairing interaction. The bismuth superconductors [14,15] (BaKBiO-) which are c l o s e l y related i n structure to the e a r l i e r superconductors and which are free of copper provide counter examples [16] to the magnetic o r i g i n of superconductivity. Another counter example [16] i s the 123-material i n which Cu i s substituted 100% by Ag bringing T down to 40 Κ. This has led some people to propose that l o c a l structure might play a role i n producing a superconducting state. A recent double-well model [17] of oxygen motion indicates trends i n t h i s d i r e c t i o n ; i t has been shown that a strong T-dependent electron-phonon coupling parameter could produce T « 100 K. q
c
(2)
Electronic Structure Calculations
The electronic structure [18-25] of the undoped compounds i s immense interest i n getting a clue to the o r i g i n superconductivity. These parent compounds are La CuO, (denoted 214), YBa Cu^0 (denoted by 123) and B i S r C a C u O (denoted ?
?
7
?
?
2
g
of of by by
4
CHEMISTRY OF HIGH-TEMPERATURE SUPERCONDUCTORS Π
2212). The important question i s : Why i s the ground state of these compounds an antiferromagnetic (AF) insulator? The band structure calculations, so far performed within the local density approximation, give results which are i n contrast to the experimental s i t u a t i o n - they a l l produce a m e t a l l i c ground state. The reason f o r this discrepancy i s believed to be the strong electron correlations i n the CuO planes which are not adequately taken into account i n a band picture. I t would be i n t e r e s t i n g to have e l e c t r o n i c structure calculations which take these correlations into account. In this regard, spin-polarized band structure calculations are expected to yield improved results over conventional band structure calculations. However, the r e s u l t s [2325] of spin-polarized band structure calculations do not seem to be definitive. We would l i k e to conclude t h i s section by s t a t i n g some of the important conclusions that have emerged from the band structure calculations. In these calculations [18,19] the importance of the two-dimensional nature of the CuO planes was emphasized. The copper d(x -y ) o r b i t a l s and the neighboring oxygen p(x,y) orbitals interact to produce bonding σ and antibonding σ* o r b i t a l s . Similar r e s u l t s [20-22] were also obtained f o r 123- and 2212-compounds. Another important r e s u l t i s that the antibonding band was positioned closer to the Fermi energy E . In the new 2212-compounds, a p a i r of s l i g h t l y f i l l e d B i 6p bands provide additional c a r r i e r s i n the Bi-0 planes [21]. A remarkable feature i n these compounds i s the charge separation between the two Bi-0 planes [22]. f
(3)
Thermophysical Properties
In t h i s b r i e f discussion of the thermophysical properties of the high-T oxide superconductors we r e s t r i c t ourselves to t h e o r e t i c a l investigations of the l a t t i c e dynamics of these systems. In p a r t i c u l a r , we review the work on phonon modes and oxygen vacancy ordering and t h e i r influence on the s t r u c t u r a l transitions of the 214 and 123 superconductors. Knowledge of the phonon spectrum and i t s dependence on the oxygen d i s t r i b u t i o n may prove to be of prime importance in elucidating the mechanism of high-T superconductivity. Several scenerios of how electron-phonon interactions can lead to high t r a n s i t i o n temperatures have been proposed including oxygen motion i n double wells [17], i n t e r l a y e r coupling [26,27] and coupling to soft quasicyclic modes associated with underconstrained nearest-neighbor rearrangements [28]. There have been a l i m i t e d number of t h e o r e t i c a l investigations on phonon frequencies and eigenvectors of the La~ (Ba.Sr) CuO, [29-31] and Y B a g C u ^ - [32-35] superconductors. Unscreened l a t t i c e dynamical models [30,3D], y i e l d i n g only the bare phonon frequencies, gave f a i r agreement with experimentally determined t o t a l phonon density of states, mean square atomic v i b r a t i o n a l amplitudes and Debye temperatures. Weber [29] has shown that the e f f e c t of screening, spectrum renormalization, due to conduction electrons gives r i s e to large Kohn anomalies near the Brillouin-zone boundary involving oxygen breathing modes. I t was pointed out by Chaplot [35] that an additional e f f e c t of renormalization i s to hybridize the high-frequency modes, dominated by oxygen, with the mediumc
1. SAHU ET AL.
Overview ofHigh-Temperature Superconductivity
5
frequency, heavier-nuclei modes thus making necessary an e f f e c t i v e mass description f o r the analysis of the isotope e f f e c t . Cohen, e t a l . [31] employing the potential-induced breathing model were able to predict the tetragonal-to-orthorhombic phase t r a n s i t i o n i n La^CuO^ as a r i s i n g from an I n s t a b i l i t y , softening, i n the B~ t i l t i n g mode of the I4/mmm tetragonal structure. The onset o ^ g t h i i t r a n s i t i o n has been recently derived from symmetry p r i n c i p l e s . As i s now well established, Υ^Ά^ ^ -/.β undergoes a tetragonal-to-orthorhombic phase t r a n s i t i o n for 1 > δ > 0 which i s a consequence of oxygen vacancy ordering i n the Cu-0 basal plane. Several approaches have been undertaken to model t h i s t r a n s i t i o n and describe the phase diagram i n (Τ,δ)-space. Most treatments are of the 2-D l a t t i c e gas type, employing f i r s t and second nearestneighbor interactions f o r oxygen and vacancies and solved by mean f i e l d techniques [37-45], Another approach, which has been successful i n predicting the microstructure o f the multiphase region, u t i l i z e s the method of concentration waves [46]; here the oxide i s treated as an i n t e r s t i t i a l compound of ordered oxygen atoms and vacancies on a simple l a t t i c e [47]. The model of Mattis [48] deserves mention since i t s p e c i f i c a l l y accounts for the copperoxygen bonds and thus enables predictions to be made concerning the d i e l e c t r i c response of the various phases. The picture that emerges from these studies i s that at high temperatures, Τ > 750 Κ, and/or stoichiometries δ < 0.5 a tetragonal phase exists with random ordering of oxygen and vacancies i n the Cu-0 basal plane. For material with δ - 0 the superconducting orthorhombic phase i s stable with oxygen (atoms) and vacancies forming alternate chains along the crystal b-direction. At low temperatures and intermediate stoichiometries phase separation occurs with micro regions of tetragonal phase, orthorhombic phase and a second cell-doubled orthorhombic phase [45]. Phase transitions between the tetragonal and orthorhombic phases are of a second-order disorder-order type. As a f i n a l note we mention the work on establishing the temperature domain i n which thermal fluctuations and c r i t i c a l behavior dominate. Many of the theories described i n this review are based on mean field techniques which become i n v a l i d when fluctuations are important. Estimates of the c r i t i c a l region, Ginzburg c r i t e r i o n , are i n the range ζ s (Τ -T)/T - 0 . 1 - 0 . 7 [4951]. However, i t has been pointed out that &ie breakdown of meanf i e l d behavior i s progressive [51]; the a b i l i t y of mean-field theory to predict non-universal quantities Xprefactors, GL-parameters and Τ ) i s l o s t within a region ζ - (Ç ) , Brout c r i t e r i o n [52], which may cover most of the superconducting regime. χ1
0
Surfaces and Interfaces The f u l l integration of bulk and thin f i l m high-temperature superconductors into existing and new technologies of high commercial value appears limited by a number of surface and interface materials issues. Many of these issues can be stated i n general terms because they are shared by each type of ceramic superconductor (2-1-4, 1-2-3, or 2-1-2-2). Others are more s p e c i f i c to the material under study, e.g., the toxic character of the T l 21-2-2 compound. As new materials with even higher c r i t i c a l temperatures are developed, analogous problems w i l l be encountered.
6
CHEMISTRY OF HIGH-TEMPERATURE SUPERCONDUCTORS Π
Hence, the knowledge base developed f o r one class of ceramic material may also apply to others. F i r s t , there are issues related to materials synthesis so that structures can be fabricated with predetermined shapes, sizes, and current carrying ability. These range from macroscopic to microscopic. Second, there are challenges related to the fabrication of superconducting t h i n films on a v a r i e t y of substrates, with S i being an obvious choice from the perspective of microelectronic devices. Third, there are issues r e l a t e d to the formation of stable ohmic contacts, p a r t i c u l a r l y for small samples and thin films. Fourth, there are problems r e l a t e d to the passivation, protection or encapsulation of small structures such as f i b e r s or t h i n films, so that the superconducting oxides can be used under a wide range of environments. These and a great many other issues raise challenging chemical questions. Spectacular progress has been made i n the few months that the new superconductors have been i n existence, and we can anticipate that rapid progress w i l l be made i n the near future. These e f f o r t s that address fundamental issues w i l l bring us one step closer to r e a l i z i n g breakthroughs i n technologies of high commercial value. I t might be thought that surface and interface issues should be separated from those involved i n the synthesis of the superconductors themselves. This i s c e r t a i n l y not the case, however, because many of the most e x c i t i n g opportunities f o r these materials w i l l be i n high performance applications. In these applications, the s i z e of the superconducting elements w i l l be comparable to those of the other components. Scaling down or shrinking the s i z e of a structure exacerbates problems r e l a t e d to interfacial phenomena. Indeed, the challenges of forming, contacting, and protecting a superconducting s t r i p 1 μια wide and 0.1 /im thick point to the intermingling of a wide range of materials issues. To date, issues related to bulk synthesis and surface or interface characterization have also been intimately t i e d . This can be seen by noting that the s t a r t i n g point for surface or interface research i s a well-characterized bulk material. Unfortunately f o r the surface s c i e n t i s t , early samples d i d not spring completely characterized from the f i r i n g furnaces, to paraphrase the springingforth of Minerva completely armed from the head of Jupiter. Instead, early samples were sintered, were 70-90% dense, and i n d i v i d u a l grains were clad with other phases [53,54]. D i f f i c u l t i e s i n characterizing these interfaces and i d e n t i f y i n g t h e i r intrinsic properties are r e f l e c t e d i n the l i t e r a t u r e of the l a s t year for the 1-2-3 and 2-1-4 materials, and the l a s t few months f o r the 2-1-2-2 materials. Only recently have bulk samples of s u f f i c i e n t q u a l i t y been available so that f r a c t u r i n g could provide a clean surface [53]. Today, i t i s r e l a t i v e l y routine to f i n d single c r y s t a l s having dimensions of greater than 1 mm, and several small companies are preparing to s e l l single c r y s t a l s as large a 1 cm x 1 cm so that f u l l characterization can be achieved. Early studies indicated that p o l y c r y s t a l l i n e , sintered samples of the 1-2-3 and 2-1-4 materials degraded rapidly upon exposure to a range of environments, including H«0, CO, C0 , 0 and solvents [5557]. More recent work suggests that degradation Is much slower and that some of the early problems were related to the intergranular 2
2
1.
SAHU ET AL.
Overview of High-Temperature Superconductivity
7
phases (e.g. carbonates or cuprates). Early work also showed that exposure of the 1-2-3's to high-intensity u l t r a v i o l e t and X-ray photon beams produces substantial changes i n the surfaces [58]. Again, recent work has indicated that most of the changes are r e l a t e d to the presence of second phases and were not i n t r i n s i c to the superconductors. At the same time, studies by Rosenberg and coworkers [59] pointed out some of the d e t a i l s of photon stimulated desorption. Electron beams of high current or high energy also induce damage. Exposure of these materials to energetic ions, such as used i n Ar sputtering, leads to surface modification, s t r u c t u r a l changes, and the loss of superconductivity [53]. This damage points to the f r a g i l e character of these superconductors but also indicates that i t may be possible to s e l e c t i v e l y a l t e r portions of a t h i n film, for example writing nonsuperconducting lines on a superconducting template. An issue that has arisen repeatedly has been the p o s s i b l i t y of oxygen loss through the surface at room temperature. To our knowledge, there i s no clear evidence that oxygen i s l o s t under s t a t i c vacuum conditions. Instead, the exposure of f r e s h l y prepared surfaces to ultrahigh vacuum leads to the chemisorption of residual gases from the vacuum system. Recent work with single c r y s t a l s has provided evidence for the rearrangement of surface atoms a f t e r cleaving i n vacuum [60]. This has been attributed to transgranular fracture and the exposure of energetically unfavorable surfaces. Indeed, such e f f e c t s can be understood i n terms of the highly anisotropic unit c e l l , but the restructuring does not necessarily r e s u l t i n oxygen loss. Attempts to form contacts to surfaces or to investigate the e l e c t r i c a l properties of the high-temperature superconductors have often been complicated by nonreproducibility. This can be related to the chemical processes that occur at these surfaces. As d e t a i l e d studies of representative interfaces have shown, there i s a strong tendency for reactive metals to leach oxygen from the superconductor to form new metal oxide bonding configurations [53,61]. The r e s u l t of this i n t e r f a c i a l chemistry i s a heterogeneous t r a n s i t i o n region between the buried superconductor and the metal f i l m . In p a r t i c u l a r , a cross section through an interface based on the 1-2-3, 2-1-4 or 2-1-2-2 superconductors would show the superconductor; a region where oxygen has been removed, where the structure i s l i k e l y to be disrupted, and which i s not superconducting; a region where the metal adatoms have formed e l e c t r i c a l l y - r e s i s t i v e oxides; and the metal overlayer, possibly containing oxygen and dissociated superconductor atoms i n solution and at the surface. Such an interface i s shown schematically i n F i g . 1. These interfaces are metastable because thermal processing w i l l enhance oxygen transport to the metal layer and w i l l increase the amount of substrate disruption. Certainly, these interfaces would not form the ohmic contacts desired i n device applications. Likewise, the cladding of superconducting filaments with copper sheaths does not seem propitious since there w i l l be i n t e r f a c i a l interactions and the formation of a nonsuperconducting layer. The scale of this disrupted region i s at l e a s t 50 À for room temperature metal deposition and i s l i k e l y to be much larger i f the interface i s processed at a higher temperature.
8
CHEMISTRY OF HIGH-TEMPERATURE SUPERCONDUCTORS II
Overlayers/Contacts on Superconductors
Passivation
Reaction
metal extended interface superconductor
disrupted substrate
superconductor
Ti, Fe, Cu, La
Ag, Au Bi 0 ,Al 0 2
3
2
CaF
2
Fig. 1
3
AI, In, Pd, Bi Ge
Schematic showing passivation of high-T superconductor surface with Ag, Au, and composite materials ( l e f t ) compared to disruptive reaction f o r chemically active overlayers ( r i g h t ) .
1. SAHU ET AL.
Overview of High- Temperature Superconductivity
9
Ohmic contacts to these superconductors can be formed with Ag and Au overlayers [62]. These metals show minimal tendency to form oxides, and t h e i r deposition does not seriously disrupt the superconductor. For contacts, then, these metals appear to be the materials of choice. Two caveats should be noted, however. First, processing may lead to Au clustering, as has been observed f o r Au layers on many substrates. Second, i f the surface to be metallized has been exposed to the a i r , i t w i l l be coated with hydrocarbons, water vapor and the l i k e , and i t s superconducting properties w i l l most l i k e l y be compromised. Attempts using Ar-ion sputtering to remove these contaminants p r i o r to metallization have been successful, but almost c e r t a i n l y at the expense of the s t r u c t u r a l i n t e g r i t y of the surface. I t remains to be seen whether the amount of surface damage (and loss of superconductivity) compromises the e f f e c t i v e use of this approach to the f a b r i c a t i o n of ohmic contacts for devices. The protection of these superconductors i s also c r u c i a l i f they are to be integrated with other technologies. Much less i s known about such passivation issues, although attempts are presently under way to develop protective overlayers. Two types of materials that have been examined so f a r and appear promising are metal oxides and non-metallic insulators [63]. Metal oxides have been formed by the deposition of metal atoms i n an activated oxygen atmosphere to form a metal oxide precursor that does not leach oxygen from the substrate. The oxide layer then serves as a d i f f u s i o n b a r r i e r against oxygen loss or atomic intermixing. To date, e f f o r t s have been successful with the oxides of A l and B i , and i t i s l i k e l y that other oxides w i l l prove to be e f f e c t i v e as passivation layers and/or d i f f u s i o n b a r r i e r s . Those investigated so f a r are insulators, but future work may lead to conducting oxides that can serve as both contacts and passivators. The second type of material that shows promise f o r passivation and e l e c t r i c a l i s o l a t i o n i s CaF^ [63]. This large-bandgap ionic insulator has a high s t a t i c d i e l e c t r i c constant, can be r e a d i l y evaporated from thermal sources i n molecular form, and shows no tendency to modify the superconductor. As such, i t may be useful as a d i e l e c t r i c layer i n advanced devices. We also note that both organic and inorganic polymers may be useful as encapsulants. In fact, f u l l y protective coatings f o r high temperture superconductors may need to be developed to meet the s p e c i f i c demands of large- and small-scale applications. These protective coatings w i l l l i k e l y involve a multilayer structure that would consist of thin- or thick-films of metals, low d i e l e c t r i c ceramics, and possibly organic and inorganic polymeric films. These multifunctional coatings would be e f f e c t i v e as a d i f f u s i o n b a r r i e r , would withstand environmental stress and temperature cycling, and would maintain strong adhesion. S p e c i f i c opportunities e x i s t f o r the synthesis of precursor molecules, such as organometallics, for chemical vapor deposition (CVD), or sol/gel approaches for low temperature f a b r i c a t i o n of these multilayer protective coatings. Bulk Superconducting Ceramic Oxides Superconducting oxides have been known since 1964, but u n t i l recently the intermetallic compounds showed higher superconducting
10
CHEMISTRY OF HIGH-TEMPERATURE SUPERCONDUCTORS H
temperatures. In 1975 research s c i e n t i s t s at Ε. I. DuPont de Nemours [64] discovered superconductivity i n the system BaPb^_ Bi 0^ with a Τ of 13 Κ. The structure f o r the superconducting compositions i n this system i s only s l i g h t l y d i s t o r t e d from the ideal cubic perovskite structure. I t i s generally accepted tljiat a disproportionation of t h e Bi(IV) occurs, namely, 2Bi(IV)(6s ) -> B i ( I I I ) ( 6 s ) + Bi(V)(6s ) at approximately 30 percent B i . Sleight found that the best superconductors were single phases prepared by quenching from a rather r e s t r i c t e d single-phase region, and hence these phases are actually metastable materials. At equilibrium conditions, two phases with d i f f e r e n t values of χ would e x i s t ; the phase with a lower value of χ would be metallic and with a higher value of χ would be a semiconductor. I t i s important to keep i n mind that the actual assignment of formal valence states i s a convenient way of electron accounting; the actual states include appreciable admixing of anion functions. The system BaPb^_ Bi 0^ should be studied further since i t contains compositions showing the highest Τ f o r any superconductor not containing a t r a n s i t i o n element. Recently, f o r example, Cava and Batlogg [14] have shown that Ba ,K A 7 S almost 30 K, which i s considerably higher than the 13 Κ reported f o r BaPb , B i 5°3I^CuO^ reported by Longo and Ràccan [65] to show an orthorhombic d i s t o r t i o n of the K^NiF, structure with a - 5.363 Â, b - 5.409 Â and c - 13.17 Â. I t was also reported [66,67] that I^CuO^ has a variable concentration of anion vacancies which may be represented as I^CuO. Superconductivity has been reported f o r some preparations of^^L^CuO^. However, there appears to be some question as to the stoichiometry of these products since only a small portion of the material seems to exhibit superconductivity [68]. The extent of the anion vacancies has been recently reexamined [69], and the magnitude of this deficiency i s less than can be unambiguously ascertained by d i r e c t thermogravimetrie analysis which has a l i m i t of accuracy In χ of 0.01 f o r the composition L^CuO^ . However, s i g n i f i c a n t s h i f t s i n the Néel temperatures confirm a small v a r i a t i o n i n anion vacancy concentrations. In the L a Α 0υ0, phases (A - Ca,Sr,Ba) the substitution of the a l k a l i n e ear til c a t i o n f o r the rare earth depresses the tetragonal-to-orthorhombic t r a n s i t i o n temperature. The t r a n s i t i o n disappears completely at χ > 0.2, which i s about the composition f o r which superconductivity i s no longer observed. Compositions of La A CuO, can also be prepared [70,71] where A i s Cd(II) or Pbfïï) However, these phases are not superconducting, and i t appears that the more basic divalent cations are necessary to allow Cu(III) to coexist with 0 ". The existence of Cu(I) and Cu(III) i n La^ gSr 2 4 consistent with the ESR spectra, which shows the absence O f square planar Cu(II), and the Pauli-paramagnetic behavior over the temperature range from 77 to 300 K. Since the Pauliparamagnetic behavior of La^ «Sr 2^ ^4 * consistent with delocalized electrons, this would also'indicate a high p r o b a b i l i t y for the existence of Cu(I)-Cu(III) formed as a r e s u l t of disproportionation of Cu(II) [72]. Subramanian et a l . [73] have recently substituted both sodium and potassium into I^CuO^, giving r i s e to the compositions L a A CuO, (A - Na,K). However, only the sodium substituted samples exfiifëitea superconducting behavior. x
Q
x
B i 0
a v e
a
T
o
f
5
w
a
2
s
2
χ
X
2
X
C u 0
i s
u
2
s
1. SAHU ET Al*
11
Overview ofHigh-Temperature Superconductivity
The compound Ba^YCu^O, shows a superconducting t r a n s i t i o n of - 93 Κ and c r y s t a l l i z e s as a defect perovskite. The unit c e l l of Ba YCu 0 i s orthorhombic (Pmmm) with a - 3.8198(1) A, b - 3.8849(1) Â and c - 11.6762(3) A. The structure may be considered as an oxygen-deficient perovskite with t r i p l e d unit c e l l s due to Ba-Y ordering along the c-axis. For Ba2YCu^0^, the oxygens occupy 7/9 of the anion s i t e s . One t h i r d of the copper i s i n 4-fold coordination and 2/3 are f i v e - f o l d coordinated. A reversible s t r u c t u r a l transformation occurs with changing oxygen stoichiometry going from orthorhombic at χ - 7.0 to tetragonal at χ - 6.0 [74]. The value χ - 7.0 i s achieved by annealing i n oxygen at 400-500°C, and this composition shows the sharpest superconducting t r a n s i t i o n . I t was shown by Davison et a l . [72] that these materials are readily attacked by water and carbon dioxide i n a i r to produce carbonates. Recently Maeda et a l . [75] reported that a superconducting t r a n s i t i o n of 120 Κ was obtained i n the Bi/Sr/Ca/Cu/O system. The structure was determined f o r the composition Bi2Sr2CaCu20g by several laboratories [76-78]. In most of the studies reported to date on the Bi/Sr/Ga/Cu/O system measurements were made on single c r y s t a l s selected from multiphase products. The group at DuPont selected platy crystals having the composition B i 3 2°8+ ^ ° " showed a Τ ~ 95 K. Crystals o r ~ S i r Ca Cu 0 for χ - 0.5 gave orthorhombîc c e l l constants a - 57399"Χ, S - 5.4Ϊ4 A, c - 30.904 A [76]. These c e l l dimensions are consistent with the results of other investigators [77,78]. The structure consists of pairs of Cu0 sheets interleaved by Ca(Sr), alternating with double bismuthoxide layers. Sunshine et a l . [78] have indicated that the addition of Pb to this system raises the Τ above 100 K. There are now three groups of superconducting oxides which contain thç^mixed Cu(II)Cu(III) oxidation states, namly La _ A CuO^ where A - Ba,Sr,Ca; KRa^CuJQ-j where R i s almost any lantftaniSe ; and 2 3 - x x 2 8 f Y ' Sheng and Herman have recently reported f 79 J on a nightemperature superconducting phase i n the system Tl/Ba/Ca/Cu/O. Two phases were i d e n t i f i e d by Hazen et a l . [80], namely Tl2Ba2CaCu20g and Tl Ba2Ca Cu 0- . Sleight et a l . [76,81] have also reported on the structure of Tl2Ba2CaCu20g as well as Tl2Ba2Cu0g. In addition, the superconductor TI^^SLJCaJ^ ^^ Q been prepared by the DuPont group [82] and shows tne highest Τ of any known bulk superconductor, namely ~ 125 K. A series of oxides with high Τ values has now been studied for the type (A 0 ) x Ca .Cu 0°, , where A(III) i s Bi or T l , A(II) i s Ba or Sr, and η i s tfie number of Cu-0 sheets stacked. To date, η - 3 i s the maximum number of stacked Cu-0 sheets examined consecutively. There appears to be a general trend whereby T increases as η increases. Unfortunately, these phases involve rather complex ordering, crystals of the phases are grown i n sealed gold tubes, and excess reactants are always present. The t o x i c i t y as well as v o l a t i l i t y of thallium, coupled with problems i n obtaining reasonable quantities of homogeneous single-phase material, presents a challenge to the synthetic chemist. It will also be interesting to see i f these materials are t r u l y more stable over time than the La^ A Cu0^ or RBa2Cu^0y phases. 2
3
7
S r
C
a
Cu
9
y
x
>
w
n
i
c
n
2
X
y
9
3
9
8
2
2
B i
2
2
3
S r
C a
C u
0
0
11
n
a
s
2
c
x
x
12
CHEMISTRY OF HIGH-TEMPERATURE SUPERCONDUCTORS II
Acknowl eflgmepts Support by the Office of Naval Research is gratefully acknowledged. Literature Cited 1. Rice, T. M. Z.Phys.Β 1987, 67, 141. 2. Anderson, P. W. Mater. Res. Bull. 1973, 8, 153; Fazekas, P.; Anderson, P. W. Phil. Mag. 1974, 30, 432; Anderson, P. W., Science, 1987, 235, 1196. 3. Baskaran, G.; Zou, Z.; Anderson, P. W. Solid State Commun. 1987, 63, 973; Anderson, P. W.; Baskaran, G.; Zou, Z.; Hsu, T. C.Phys.Rev. Lett. 1987, 58, 2790; Anderson, P. W.; Zou, Z. Phys. Rev. Lett. 1988, 60, 132; Wheatly, J. M.; Hsu, T. C.; Anderson, P. W.Phys.Rev. Β 1988, 37, 5897. 4. Hirsch, J. E.Phys.Rev. Β 1985, 31, 4403. 5. Kivelson, S. Α.; Rokhsar, D. S.; Sethna, J. P. Phys. Rev. B, 1987, 35, 857. 6. Ruckenstein, A. E., Hirschfeld, P. J.; Appel, J. Phys. Rev. B. 1987, 36, 857. 7. Kotliar, G.Phys.Rev. Β 1988, 37, 3664. 8. Rice, M. J.; Wang, Y. R.Phys.Rev. B. 1988, 37, 5893. 9. Coffey, L.; Cox, D. L.Phys.Rev. B. 1988, 37, 3389. 10. Schrieffer, J. R.; Wen, X.-G.; Zhang, S.-C.Phys.Rev. Lett. 1988, 60, 944. 11. Emergy, V.Phys.Rev. Lett. 1987, 58, 2794. 12. Varma, C. M.; Schmitt-Rink, S; Abrahams, E. Solid State Commun. 1987, 62, 681. 13. Ruvalds, J.Phys.Rev. Β 1987, 36, 8869. 14. Cava, R. J.; Batlogg, A. B. Nature 1988, 332, 814. 15. Rice, T. M. Nature 1988, 332, 780. 16. Kao, Y. H. colloquium talk at SUNY-Buffalo on May 24, 1988. 17. Hardy, J. R.; Flochen, J. W.Phys.Rev.Lett. 1988, 60, 2191. 18. Mattheiss, L. F.Phys.Rev. Lett. 1987, 58, 1028. 19. Yu, J.; Freeman, A. J.; Xu, J.-H.Phys.Rev. Lett. 1987, 58, 1035. 20. Mattheiss, L. F.; Hamann, D. R. Solid State Commun. 1987, 63, 395. 21. Hybersten, M. S.; Mattheiss, L. F. Phys. Rev. Lett. 1988, 60, 1661. 22. Krakauer, H.; Pickett, W. E.Phys.Rev. Lett. 1988, 60, 1665. 23. Guo, G. Y.; Temmerman, W.; Stocks, G. J. Phys. C 1988, 21, L103. 24. Leung, T. C.; Wang, X. W.; Harmon, Β. N.Phys.Rev. Β 1988, 37, 384. 25. Sterne, P. Α.; Wang, C. S.Phys.Rev Β 1988, 37, 7472. 26. Arnold, G. B. In Novel Superconductivity: Kresin, V. Z.; Wolf, S. Α., Eds.; Plenum: New York, 1987; p. 323. 27. Gulasci, Zs.; Gulasci, M.; Pop, I. Phys. Rev. Β 1988, 37, 2247. 28. Phillips, J. C.Phys.Rev. Lett. 1987, 59, 1856. 29. Weber, W.Phys.Rev. Lett. 1987, 58, 1371; 1987, 58, 2154(E). 30. Prade, J.; Kulkarni, A. D.; de Wette, F. W.; Kress, W.; Cardona, M.; Reiger, R.; Schröder, U. Solid State Commun. 1987, 64, 1267.
1. SAHU ET AL.
Overview ofHigh-Temperature Superconductivity 13
31. Cohen, R. E.; Pickett, W. E.; Boyer, L. L.; Krakauer, H. Phys. Rev. Lett. 1988, 60, 817. 32. Thomsen, C.; Cardona, M.; Kress, W.; Liu, R.; Genzel, L.; Bauer, M.; Schönhers, Ε.; Schröder, U. Solid State Commun. 1987, 65, 1139. 33. Bates, F. E.; Eldridge, J. E. Solid State Commun. 1987, 64, 1435. 34. Liu, R.; Thomsen, C.; Kress, W.; Cardona, M.; Gegenheimer, B.; de Wette, F. W.; Prade, J.; Kulkarni, A. D.; Schröder, U. Phys. Rev. Β 1988, 37, 7971. 35. Chaplot, S. L.Phys.Rev. Β 1988, 37, 7435. 36. Sahu, D.; George, T. F. Solid State Commun. 1988, 65, 1371. 37. Bakker, H.; Welch, D.; Lazareth, O. Solid State Commun. 1987, 64, 237. 38. Shi-jie, X. J.Phys.1988,C21,L69. 39. Kubo, Y.; Igarashi, H. Jpn. J. Appl. Phys. 1987, 26, L1988. 40. Inouie, M.; Takemori, T.; Sakudo, T. Jpn. J. Appl. Phys. 1987, 26, L2015. 41. Bell, J. M.Phys.Rev. Β 1988, 37, 541. 42. Varea, C.; Robledo, A. Mod.Phys.Lett. Β 1988, 1, in press. 43. Sanchez, J. M.; Mejia-Lia, F.; Moran-Lopez, J. L. Phys. Rev. Β 1988, 37, 3678. 44. Khachaturyan, A. G.; Semenovskaya, S. V.; Morris, Jr., J. W. Phys. Rev. B, 1988, 37, 2243. 45. Wille, L. T.; Berera, Α.; de Fontaine, D. Phys. Rev. Lett. 1988, 60, 1065. 46. Khachaturyan, A. G.; Morris, Jr., J. W.Phys.Rev. Lett. 1987, 59, 2776. 47. Pokrovskii, Β. I.; Khachaturyan, A. G. J. Solid State Chem. 1986, 61, 137, 154. 48. Mattis, D. C. Int. J. Mod. Phys. Lett., in press. 49. Deutscher, G. In Novel Superconductivity: Kresin, V. Z.; Wolf, S. Α., Eds.; Plenum: New York, 1987; p. 293. 50. Lobb, C. J.Phys.Rev. Β 1987, 36, 3930. 51. Kapitulnik, Α.; Beasley, M. R.; Castellani, C.; DiCastro, C. Phys. Rev. Β 1988, 37, 537. 52. Hohenberg, P. C. In Proceedings of Fluctuations in Superconductors : Goree, W. S.; Chilton, F., Eds.; Stanford Research Institute, Stanford, 1968. 53. Meyer, H. M.; Wagener, T. J.; Hill, D. M.;Gao, Y.; Weaver, J. H.; Capone, D. W.; Goretta, K. C.Phys.Rev. Β 1988, 38, xxx. 54. Verhoven, J. D.; Bevolo, A. J.; McCullum, R. W.; Gibson, E. D.; Noack, M.A.Appl.Phys.Lett. 1987, 52, 745. 55. Yan, M. F.; Barnes, R. L.; O'Bryan, Jr., Η. M.; Gallagher, P. K.; Sherwood, P. K.; Jim,S.Appl.Phys.Lett. 1987, 51, 532. 56. Qui, S. L.; Ruckman, M. W.; Brookes, Ν. B.; Johnson, P. D.; Chen, J.; Lin, C. L.; Strongin, M.; Sinkovic, B.; Crow, J. E.; Jee, Chou-Soo Phys. Rev. Β 1988, 37, 3747. 57. Kurtz, R. L.; Stockbauer, R. Α.; Madey.T. E.; Mueller, D.; Shih, Α.; Toth, L.Phys.Rev. Β 1988, 37, 7936. 58. Chang, Y.; Onellion, M.; Niles.D. W.; Margaritondo, G. Phys. Rev. Β 1987, 36, 3986. 59. Rosenberg, R. Α.; Wen, C.-R.Phys.Rev. Β 1988, 37, 5841. 60. Weaver, J. H.; Meyer, Η. M.; Wagener, T. J.; Hill, D. M.; Peterson, D.; Fisk, Z.; Arko, A. J. Phys Rev. Β (in press).
14
CHEMISTRY OF HIGH-TEMPERATURE SUPERCONDUCTORS Π
61. Gao, Y.; Wagener, T. J.; Hill, D. M.; Meyer, Η. M.; Weaver, J. H.; Arko, A. J.; Flandermeyer, B.; Capone, D. W. In Chemistry of High-Temperature Superconductors: American Chemical Society Symposium Series 351, Nelson, D. L.; Whittingham, M. Stanley; George, Thomas F., Eds.; Washington, D.C., 1987, p. 212; Gao, Y.; Meyer, Η. M.; Wagener, T. J.; Hill, D. M.; Anderson, S. G.; Weaver, J. H.; Flandermeyer, B.; Capone, D. W. In Thin Film Processing and Characterization of High-Temperature Superconductors; American Institute of Physics Conference Proceedings No. 165, Harper, J. M. E.; Colton, R. J.; Feldman, Leonard C.; Eds.: New York, NY, 1987; p. 358. 62. Wagener, T. J.; Vitomirov, I. M.; Aldao, C. M.; Joyce, J. J.; Capasso, C.; Weaver, J. H.; Capone, D. W. Phys. Rev. Β 1988, 38, xxx; Meyer, Η. M.; Wagener, T. J.; Hill, D. M.; Gao, Y.; Anderson, S. G.; Krhan, S. D.; Weaver, J. H.; Flandermeyer, B.; Capone, D.W.Appl.Phys.Lett. 1987, 51, 1118. 63. See the chapter in this book by Meyer et al. 64. Sleight, A. W.; Gillson, J. L.; Bierstedt, P. E. Solid State Commun. 1975, 17, 299. 65. Longo, J. M.; Raccah, P. M. J. Solid State Chem. 1973 6, 526. 66. Johnston, D. C.; Stokes, J. P.; Goshorn, D. P.; Lewandowski, J. T.Phys.Rev. Β 1987, 36, 4007. 67. Mitsuda, S.; Shirane, G.; Sinha, S. K.; Johnston, D. C.; Alvarez, M. S.; Vaknin, D.; Moncton, D. E. Phys. Rev. B. 1987 36, 822. 68. Grant, P. M.; Parkin, S. S. P.; Lee, V. Y.; Engler, Ε. M.; Ramirez, M. L.; Vazquez, J. E.; Lim, G.; Jacowitz, R. D.; Greene, R. L.Phys.Rev. Lett. 1987, 18, 2482. 69. DiCarlo, J.; Niu, C. M.; Dwight, K.; Wold, A. (see this volume). 70. Shaplygin, I. S.; Kakhan, B. G.; Lazareo, Russ. V. B. J. Inorg. Chem. 1979, 24, 820. 71. Gopalaknshnan, J.; Subramanian, Μ. Α.; Sleight, A. W. to be published. 72. Davison, S.; Smith, K.; Zhang, Y.-C.; Liu, J-H.; Kershaw, R.; Dwight, K.; Reiger, P. H.; Wold, A. ACS Symposium Series No. 351, 1987, 65. 73. Subramanian, Μ. Α.; Gopalaknshnan, J.; Torardi, C. C. Askew, T. R.; Flippen, R. B.; Sleight, A. W. Science, submitted. 74. Gallagher, P. K.; O'Bryan, Η. M.; Sunshine, S. Α.; Murphy, D. W. Mat. Res. Bull. 1987, 22, 995. 75. Maeda, H.; Tanaka, Y.; Fukutomi, M.; and Asano, T. Jpn. J. Appl. Phys. 1988, 27, L209. 76. Subramanian, Μ. Α.; Torardi, C. C.; Calabrese, J. C.; Gopalaknshnan, J.; Morrissey, K. J.; Askew, J. R.; Flippen, R. B.; Chowdry, U.; Sleight, A. W. Science, 1988, 239, 1015. 77. Tarascon, J. M.; LaPage, Y.; Barboux, P.; Bagley, B. G.; Greene, L. H.; McKinnon, W. R.; Hull, G. W.; Giroud, M.; Hwang, D. M.Phys.Rev. Β communicated. 78. Sunshine, S. Α.; Siegrist, T.; Schneemeyer, L. F.; Murphy, D. W.; Cava, R. J.; Batloggg, B.; van Dover, R.B.; Fleming, R. M.; Olanim, S. H.; Nakahara, S.; Farrow, R.; Krajewski, J. J.; Zahurak, S. M.; Wasczak, J. V.; Marshall, J. H.; Marsh, P.; Rupp, Jr., L. W.; Peck, W. F. Phys Rev. Lett. communicated.
1. SAHU ET AL.
Overview ofHigh-Temperature Superconductivity 15
79. Sheng, Ζ. Z.; Hermann, A. M. Nature 1988, 332, 55; 1988, 332, 138. 80. Hazen, R. M.; Finger, L. W.; Angel, R. J.; Prewitt, C. T.; Ross, N. L.; Hadidiacos, C. G.; Heaney, P. J.; Veblen, D. R.; Sheng, Ζ. Z.; El Ali, Α.; Hermann, A. M. Phys. Rev. Lett. submitted. 81. Torardi, C. C.; Subramanian, Μ. Α.; Calabrese, J. C.; Gopalaknshnan, J.; McCarron, E. M.; Morrissey, K. J.; Askew, T.R.; Flippen, R. B.; Chowdry, U.; Sleight, A. W.Phys.Rev. Β submitted. 82. Torardi, C. C.; Subramanian, M. A. Calbabrese; Gopalaknshnan, J.; Morrissey, K. J.; Askew, T. R.; Flippen, R. P.; Chowdry, U.; Sleight, A. W. Science submitted. RECEIVED July 6,
1988
