Professional Documents
Culture Documents
KISHIN MOORJANI, FRANK J. ADRIAN, BORIS F. KIM, JOSEPH BOHANDY, TERRY E. PHILLIPS,
THOMAS J. KISTENMACHER, WILLIAM J. GREEN, ELISABETTA AGOSTINELLI,
BRADLEY G. BOONE, and RAY M. SOYA
HIGH-TEMPERATURE SUPERCONDUCTIVITY
The second stage of APL'S continuing program on high-temperature superconductors, including re-
cent advances, is reviewed. Present emphasis is on producing the high quality samples needed for current
experiments and envisioned devices, development of novel methods for judging sample quality, and de-
vice concepts using various novel structural features of the cuprate oxide superconductors, such as their
intrinsic Josephson junctions. Addititionally, some theoretical investigations and the interplay of super-
conductivity and magnetism in high-temperature superconductors are discussed.
INTRODUCTION
High-temperature superconductivity based on oxide thermally stable structures on technologically useful sub-
materials was developed less than three years ago. The strates at low processing temperatures. Furthermore,
initial "hype" that accompanied the discovery of super- normal metal contacts to superconducting oxides need
conductivity at temperatures above the boiling point of to be formed and it is imperative that the device struc-
liquid nitrogen must now be replaced with realistic assess- tures be able to withstand exposure to the ambient en-
ments of what can be achieved with the new materials, vironment without degradation of their performance.
and what their limitations may be. Progress toward that Certain applications require patterned film structures,
goal is being made continuously. The excitement is still and once again the deleterious effects of patterning tech-
present, although it has been largely transformed from niques must be minimized. For complete characteriza-
popular media to the scientific literature and conferences, tion of layers, it is essential not to rely only on standard
so as to allow researchers to calmly conduct the task of measurements (for example, the temperature-dependence
evaluating and understanding the fascinating behavior of the resistivity), but to develop novel methods to probe
of superconducting oxides. globally the characteristics of films and the structures
The highest confirmed value of the superconducting based on them. Buffer layers to enhance superconduct-
transition temperature, Tc ' remains at 125 K for the ing behavior and passivation layers to guard against
thallium-based oxides, though tantalizing reports of degradation are other important areas. Finally, the ubiq-
values of Tc almost twice as large emerge periodically. uitous anisotropic crystal structure and properties of all
The latter values, however, have never been widely the high-temperature superconducting ceramics discov-
reproduced and must therefore be considered uncon- ered to date demand fabrication of films with preferred
firmed. It should be emphasized that the confirmed orientation. Every superconducting ceramic system ex-
values of Tc represent highly satisfactory materials for hibits its own peculiarities; while the properties of com-
devices operating at 77 K. In this regard, elevated values pounds based on rare earths are sensitive to the ambient
of critical currents (greater than 5 x 10 6 A / cm 2 ) are environment, the bismuth-based materials are mechan-
now routinely observed in thin-film samples of various ically fragile and the thallium-based samples need care-
oxides, making possible the initial exploitation of super- ful handling because of their toxicity.
conductors in small-scale applications. Since semicon- Perhaps the most important aspect of superconduct-
ducting devices operate quite efficiently at 77 K, there ing oxides-their theoretical understanding-remains an
now exists an overlapping temperature region for semi- unachieved goal. The design of new materials with higher
conductor devices and superconducting thin films that values of Tc is, therefore, necessarily an empirical path.
can be exploited for hybrid devices. In this article, we discuss the considerable progress on
Device structures for hybrid microelectronics, how- high-temperature superconductors achieved at APL since
ever, pose their own constraints. I Among them are the our last Technical Digest article on the subject. 2 It cov-
cost-effectiveness of thin- and thick-film processing tech- ers the entire range from materials studies and thin-layer
niques that can be employed to form mechanically and formation to the design of novel techniques for their in-
156 John s Hopkin s APL Technical Digesc, Volume 11, Numbers J and 2 (1990)
High- Temperature Superconductivity
combination of them, is modulated. Previously, we have and also for studying the effect of inherent anisotropy
extensively exploited the method at microwave frequen- of these materials. An example of the latter is presented
cies in the magnetically modulated microwave absorp- in Figure 6, which shows the MAMMA spectrum and the
tion (MAMMA) technique, 2,7-9 which has the advantage simultaneously recorded unmodulated microwave resis-
that it can be employed to study electrically discontinu- tance of a Y-Ba-Cu-O crystal with a 30-0 DC magnet-
ous samples (such as powders, discontinuous films, etc.). ic field parallel to the e-axis.13 The microwave re-
The basic principle of the MAMMA method (an increas- sistance is increasing with decreasing temperature down
ing magnetic field decreases Tc) does not depend on the to 87 K, at which temperature the resistance drops and
presence of microwaves or microwave absorption in the a MAMMA peak is observed at 86 K. In addition, one sees
sample. Therefore, we expect that this technique can be that there is a second superconducting phase in the crys-
used in conjunction with any means of measuring loss tal, with a transition temperature around 81 K. Addi-
in superconducting samples, including DC resistance. We tional measurements show that there is more than one
have recently demonstrated this by a magnetically modu- additional phase present.
lated electrical resistance (MAMER) technique )~ ) 2 for de- Any magnetic anisotropy that may exist in the sam-
tecting superconductivity. The scope of magnetic ple can be investigated using this technique by obtain-
modulation methods to detect and study superconduc- ing MAMMA spectra as a function of the direction of the
tivity is thus enlarged to include a simpler MAMER con- DC magnetic field with respect to the different crystal-
figuration in samples that are electrically continuous. lographic axes of the crystal. MAMMA spectra were ob-
The method was first tested on a thin-film sample of tained with the magnetic field in each of three crystallo-
the conventional superconductor NbN. Figures 3A and graphic planes; Figure 7 shows representative spectra of
3B show the DC resistance and the MAMER response, the YBCO crystal with the magnetic field along the three
respectively, simultaneously recorded as a function of crystallographic axes.
temperature using 5-0 magnetic field modulation, The edges of the rectangularly shaped crystal platelet
H mod , and a 30-0 DC magnetic field, H Dc . The super- were arbitrarily labeled a and b since twinning precludes
conducting transition at about 15 K is extremely sharp the assignment of specific crystallographic axes to the
(about 0.2 K) and one sees that the MAMER response is, in-plane directions.
indeed, approximately proportional to the derivative of The MAMMA spectra with HUe and HUb (Figs. 7A and
the DC resistance with respect to temperature, as expect- 7B, respectively) are representative of all the spectra in
ed from a qualitative model of this method for the MAM- the a-c and b-c planes. There are clearly two different
MA case.
7 phases, separated by 5 K. Furthermore, some of the
The utility of the MAMER technique for a supercon- spectra in these two planes indicate the existence of a
ducting oxide is shown in Figure 4 for a EuBa2CU307_y very small amount of a third superconducting phase in
bulk sample, and the corresponding MAMMA response is the vicinity of 68 to 70 K. The direction of H has a rela-
shown in Figure 5. Both techniques provide a simple tively small effect on the position of the peaks, produc-
method for studying the effect of increasing field on Tc ing shifts in the values of Tc up to approximately 2 K.
I I I
A A
. - ....... ... , • ,_ •.. t.
- -
..,-------
-
- .--------
I I
I I I
B B
-
... -
- I
I I I
12 14 16 18 75 85 95 105
Temperature (K) Temperature (K)
Figure 3. A. The DC resistance and B the magnetically modu- Figure 4. A. The DC resistance and B the magnetically modu-
lated electrical resistance of a thin film of NbN as a function lated electrical resistance of EuBa2Cu307 _ y as a function of
of temperature. (Hoc = 30 G, Hmod = 5 G, and I = 100 j.l.A.) temperature. (Hoc = 1 kG, Hmod = 5 G, and I = 5 mAo
"...........,......-.-.
--- - - - - , . - /...
I
B
·",.~,,,,_·."•• 4 ,:....
-..............
--..............-,...................' -
~
,,---- . -.
~
75 85 95 105
Temperature (K) .......---...
Figure 5. A. The unmodulated microwave absorption and B
the magnetically modulated microwave absorption of 60 70 80 90 100
EuSa2Cu307 _ y' (Hoc 1 kG and Hmod 2 G.)= = Temperature (K)
60 70 80 90 100
Temperature (K)
WEAK-LINK SUPERCONDUCTIVITY
It is clear that the large differences between (1) the
Figure 6. The unmodulated microwave absorption (upper
curve) and the magnetically modulated microwave absorption
critical current and its dependence on temperature and
(lower curve) of the Y-Sa-Cu-O crystal. (Hoc = 30 G, parallel magnetic field in single crystals and ordered thin films
to the e-ruds). of the high- Tc superconductors, and (2) those of com-
posite polycrystalline samples result from different
critical-current-limiting mechanisms. Single crystals of
For the in-plane orientation of Figure 7B, the MAMMA the oxide superconductors are similar to conventional
spectrum is very similar to the HIIc spectrum, although type II superconductors in that in a strong magnetic field
the intensity of the Hlle spectrum is about 6 times they maintain a large enough superconducting region to
stronger. This is likely because the MAMMA response is carry sizable currents by trapping the flux in uniformly
proportional to dTc / dH, and IdTc / dHI Hllc > distributed regions within the superconductor. Unfor-
IdTc/dHIHl.C in these materials. However, when His tunately, in the ceramic superconductors these trapped-
in the a-b plane (Fig. 7C) a dramatic change occurs in flux regions are fixed or pinned only at temperatures con-
the MAMMA spectrum. The two peaks observed in the siderably below T c , and their motion above T c (the flux
other orientations have inverted in intensity and two new lattice melting temperature, Tm) produces interactions
158 John s Hopkins APL Technical Digest, Volume 11, Numbers 1 and 2 (1990)
High- Temperature Superconductivity
Hoc~500G ----~~r
rents that render the superconductor ineffective 15 (at
least for high current applications) above Tm. A mani-
festation of this effect is the marked tail that appears
below Tc in the resistance-versus-temperature curve of
Ai __ -1
single crystals of the ceramic superconductors in large
magnetic fields (on the order of 1 T). On the other hand,
the critical currents in bulk sintered samples consisting
rI >../... ............... . . .:.JJ
of a myriad of small crystalline grains are lower than
those in single crystals and have a greater magnetic field
~] r
dependence at low magnetic fields. These properties are
generally ascribed to the presence of structural disorder
(e.g., defects and dislocations) as well as compositional
1
i IL..--~~·:··~_~~
. ·~~L---·'
disorder (for example, impurities and grain boundaries) 30G
in the bulk samples, leading to the formation of weak
links that control the critical current and make it strongly
dependent on the magnetic field. Given the small, high-
ly anisotropic values of the coherence lengths in super-
· ··.····----l·
.l
conductin~ ceramics, even very small-scale disorder of Q)
~/r -1
likely to predominate, and single-crystal and oriented
thin-film samples, where weak links are far fewer and
flux motion effects come to the fore. These dissimilar
effects in the granular and single-crystal samples may ] _ 2 G______
1 . ··.·. . . .·.·.· / . J
even be of practical importance in optimizing the criti-
cal currents in the high- Tc superconductors because, al-
though the critical currents are generally lower in the
granular samples, the grain boundaries, dislocations,
etc., may provide flux-pinning sites and thereby reduce 70 80 90 100
the effects of flux motion. A compromise between per- Temperature (K)
fectly ordered single crystals or thin films and highly dis-
ordered polycrystalline samples may be needed to pro- Figure 8. Magnetic field dependence of the MAMER response
(dotted) and DC resistance (x 1, solid; x 10, dashed) of
duce high Tc superconductors capable of carrying use-
EuBa2Cu307 _ y using a current of 5 mA. (A, B, and C, 5-G
ful currents at temperatures close to Tc. In any event, modulation amplitude; 0, 1-G modulation amplitude.)
it is important to have methods capable of observing
weak-link effects. Here we describe how both the MAM-
MA and MAMER methods clearly differentiate the response perature side of the primary resistance transition. As the
owing to the intrinsic superconducting transition within static field is reduced to 30 G (Fig. 8B), the resistance
the individual crystallites of the granular sample from tail has been reduced considerably; clearly, the extent
that of the weak links between these granules. 12,17,18 of this resistive tail depends on the magnitude of the ap-
Figures 8A through 8D show the MAMER spectra and plied magnetic field. Correspondingly, the weak peak
simultaneously recorded resistance curves of a sample on the low temperature side of the intrinsic MAMER peak
of EuBa2 CU3 0 7_y (EBeO) in static magnetic fields of has evolved into a broad, reasonably well-defined peak.
500, 30, 10, and 2 G, respectively, using a 5-mA excita- Lowering the static field to 10 G (Fig. 8C) results in a
tion current. The MAMER response in a 500-G field (Fig. narrowing and a shift to higher temperature of the sec-
8A) is characterized by a derivative peak, subsequently ondary MAMER peak, effecting increased amplitude rela-
referred to as the intrinsic peak, occurring at a temper- tive to the intrinsic peak and, concomitantly, a continued
ature (Tc) at the inflection point in the resistance curve. reduction of the resistive tail. In a 2-G static field and
An additional, though more subtle feature-a very broad with I-G modulation amplitude (Fig. 8D), the intrinsic
secondary weak peak in the MAMER response-is also peak is barely discernible as a weak shoulder on the sec-
observed on the low temperature side of the main tran- ondary peak, and the tailing is further reduced.
sition. In the x 10 expansion of the resistance curve (Fig. The correlation of the secondary MAMER peak with
8A), note that there is significant tailing on the low tem- the resistive tail, with its extreme sensitivity to small mag-
Johns Hopkins APL Technical Digest, Volume 11 , Numbers I and 2 (1990) 159
K. Moorjani et al.
-I
[+ [ (
1 exp - {3 1 -
Ie (T,H)
I )JJ (5)
(2)
For a single Josephson junction, aR wlaH, which deter-
mines the MAMER signal, is obtained by using Equations
where {3 is an empirical constant representing the abrupt- 4 and 5 in Equation 3 as
~
0:
UJ
~
<:
. ',:~
~
-grn ~ ______________________
10 G --J
"S
o
where the factor N normalizes the summation, and H av cu
()
is the average field. The sum has been carried out over '.
approximately 20,000 inequivalent junctions with Ho
randomly distributed in the range from 1 to 100 G. The
values of 10 , {3, H av ' and a were determined to provide 2G
a fit to the experimental data; the resulting values were
10 = 300 A, {3 = 0.5, H av = 5 G, and a = 30 G. 70 80 90 100
The MAMER response, M , for the sample was simu- Temperature (K)
lated by taking a linear combination of the correspond- Figure 10. Calculated field dependence of the MAMER re-
ing response for intrinsic and weak link material, sponse of EuBa2CU307_y using a current of 5 rnA.
('\,
I ...
gion, Figure 12 shows typical TOF spectra recorded at
several temperatures for the mean q value of 0.6 A -I.
The quasi-elastic intensity increases slightly when the
- I \ '.
temperature is lowered from 122 K to about 40 K and
",.
'--- thereafter decreases strongly with decreasing tempera-
30G ture. At 1.8 K no quasi-elastic intensity is detected.
I I The TOF spectra were fitted by a sum of a delta func-
50 60 70 80 90 100 tion (norm C 1) and a Lorentzian function (norm C 2
Temperature (K) and energy line width r) converted to time scale and con-
voluted with experimental resolution. As shown in Fig-
Figure 11. Calculated MAMER response of EuBa2CU307 _ y us- ure 12, this procedure yields rather good fits. The
ing 100-mA current.
parameters C 1, C 2 , and r are shown as functions of
temperature in Figure 13. The elastic intensity, C 1, is
constant between 122 K and 40 K, then starts to increase
pared_ On the basis of crystal chemistry and the ionic when the temperature is further reduced. Concomitant-
radii involved, Fe is expected to substitute for Cu. The ly, we observe a strong decrease of the quasi-elastic in-
substitution of Fe also has the advantage that one can tensity, C 2 • Although the error bars are very large
investigate the local environment of Fe, and therefore because of the rather poor statistical precision, a mini-
of Cu, by Mossbauer spectroscopy. mum of the quasi-elastic width, r, is suggested. This be-
The suppression of Tc with increasing Fe concentra- havior of the parameters is observed independently of
tion was demonstrated by the MAMMA technique 22 ,23 the q value considered.
and the values obtained correlated well with the values In the YBa2(CuO.ss Feo.12 )30 7-Y sample, the changes
obtained from the resistivity measurements. 24 In these with temperature of the fitted parameter (C), C 2 , r)
samples, the room temperature Mossbauer spectra re- are typical of spin freezing as observed in archetypal spin
vealed two distince Fe sites that correspond to two local glasses such as dilute CuMn or AuFe alloys. 26 The de-
oxygen coordinations of the two Cu sites which are well crease of the quasi-elastic intensity concomitantly with
established from x-ray, electron, and neutron diffrac- the increase of the elastic intensity can be explained in
tion studies. Since Fe, for the most part, has clearly sub- a picture of spin clusters: when temperature decreases,
stituted into the Cu sites that playa central role in the the growing of clusters with the lowest relaxation times
superconductivity of these materials, it is rather surpris- yields a progressive transfer from the quasi-elastic in-
ing that for a concentration of Fe of 30/0 or greater, the tensity to the resolution-limited or "elastic" peak. In
Mossbauer spectra reveal magnetic ordering at 4.2 K. YBa2(CuO.ss Feo. 12)30 7-Y, this change occurs around 40
The spectra are complex, they show a distribution of K, thus slightly above the freezing temperature evaluat-
magnetic hyperfine fields with a broad range of about ed from Mossbauer experiments (around 35 K). It should
200 to 400 kOe, and they resemble those of spin glass be noted that the determination of the temperature for
ordering in the sense that no sharp transition to the or- the spin freezing depends on the experimental resolution
dered state is observed, but instead a large broadening (the time scale of the experiment is somehow shorter with
in the wings is seen, and the spectra cannot be fitted by the neutron probe [10 -10 S here] than with the Moss-
assuming a constant angle between the local magnetiza- bauer probe [10 -7 s]).
tion direction and the electric field gradient. 23 The Finally, we recall that in the YBa2(Cuo.ss Feo.12 )30 7-y
coexistence of the magnetic ordering with large local sample, the freezing process and the superconductivity
magnetization and superconductivity implies either a ro- occur in the same temperature range (30 to 40 K). The
bust superconducting mechanism, or a rather short cor- persistence of superconductivity in spite of a noncollinear
relation length for electron pair formation, or both. magnetic ordering implies little interaction between the
The nature of the magnetic ordering cannot be ascer- superconducting and magnetic "lattice," possibly be-
tained from the complex Mossbauer spectra and there- cause of the preferential occupation of the Cu(I) site by
-50 5 1 0 0.5
O.sr-
Elastic intensity
45 K
0.3 '-
Quasi-elastic intensity
14 K
o 50 100 150
Temperature (K)
Figure 13. Temperature dependence of the three parameters
extracted from the fits. rand C2 are the energy line width and
the norm of the Lorentzian function used for the quasi-elastic
intensity, respectively, and C1 is the norm of the delta func-
tion used for the "elastic " intensity. Cross symbols (+ ) cor-
respond to measurements taken with decreasing temperature
whereas open symbols (0) correspond to a further increase of
temperature. No irreversibility effects are observed during this
procedure.
THEORY
o 100 200 300 400 500 We have performed theoretical investigations in order
Channel number to better understand the electronic structure and prop-
Figure 12. TOF spectra at several temperatures in erties of the high- Te superconductors in the normal
YBa2(CuO.88Feo.1 2b07 _ y' The intensities have been normalized state, which knowledge is a prerequisite for any realistic
to the same number of incident neutrons. The intensity of the challenge to the problem of the superconducting mech-
YBa2Cu 307 _ y sample at 57 K is also shown for comparison . anism itself. Of obvious interest are the mobile, charge-
(Reprinted , with permission, from Ref. 25.)
carrying holes (these are inherently present in non-
stoichiometric YBa2CU3 0 7_y and are introduced into
insulating La2Cu04 by alkaline earth doping). The key
the iron spins and to the small coherence length of su- questions relate to the orbital symmetry of the holes and
perconducting pairs. This situation does not exclude a their degree of coupling to the anti ferromagnetic Cu 2+
possible influence of the superconductivity on the iron (3d) spin system. Our analysis has emphasized a crystal
spin dynamics in the paramagnetic state. Such an effect field model that regards the oxide superconductors as
could be evident in a sample in which Tf is well below primarily ionic crystals, wherein the mobile holes move
Te. In YBa2(CuO.94Feo.6)30 7-y (Tf ::::: 18 K and Te ::::: along potential gradients comprised of the ionic crystal
f ohns H opkins A PL Technical Digest, Volume 11, N umbers 1 and 2 (1 990) 163
K. Moorjani et al.
164 Johns H opkins APL Technical Digest, Volume 11 , Numbers I and 2 (1990)
High- Temperature Superconductivity
Johns H opkins APL Technical Digest, Volume II, Numbers I and 2 (1990) 165
K. Moorjani et 01.
29Adrian, F . J., "Structural Implications of Nuclear Electric Quadrupole JOSEPH BOHANDY, a native of
Splittings in High-Tc Superconductors," Phys. Rev. B. 38,2426 (1988). Ohio, received B.S., M.S., and
30Adrian, F . J ., "Nature of The Conduction Band States in YBa2Cu307 Ph.D. degrees from Ohio State Uni-
as Revealed by Its Yttrium Knight Shift," Phys. Rev. Lett. 61, 2148 (1988).
versity. He joined APL in 1965 as
31 Kistenmacher, T. J ., " Substitution-Induced Superstructures in Cu(1)-
a member of the Microwave Physics
Doped YBa2Cul _x M x)30 7 Ceramics (M = trivalent cation)," Phys.
Rev. B 39, 12279 (1989). Group of the Milton S. Eisenhower
Research Center and worked on var-
ious problems in solid-state and
THE AUTHORS
chemical physics. In 1984, he became
KISHIN MOORJANI is a physicist a member of the Materials Science
in the Materials Research Group of Group of the Research Center,
APL's Milton S. Eisenhower Re- where he was involved in laser mi-
search Center. He is engaged in crochemical processing as applied to
problems related to high-temper- microcircuit fabrication. His recent
ature superconductors, photon-beam I principal professional efforts have
processing of materials, disordered been in the study and application of
structures, and nanocomposites. high-temperature superconductivity.
Born in India, he studied at the Uni-
versity of Delhi before receiving a
Ph.D. in theoretical physics from
The Catholic University of Ameri-
ca in 1964. In 1967, Dr. Moorjani
joined APL, where he is program
manager of the microphysics proj-
/ ect. He has coauthored a mono-
TERRY E. PHILLIPS is a senior
graph, Magnetic Glasses, and has
staff chemist in the Materials Sci-
published extensively in the field of condensed matter science. He has
ence Group of APL'S Milton S.
held several visiting appointments at universities both in the United States
Eisenhower Research Center. Born
and abroad. Dr. Moorjani teaches at The Johns Hopkins University
in Sunbury, Pa., he received a B.A.
G.W.c. Whiting School of Engineering and serves as chairman of the
degree from Susquehanna Univer-
University's Applied Physics Program Committee.
sity, and M.S. and Ph.D. degrees
in chemistry from The Johns Hop-
kins University in 1976. After com-
FRANK J . ADRIAN is a member pleting postgraduate studies at North-
of the Principal Professional Staff western University in low-dimen-
and is a senior scientist in APL's sional organic conductors, he joined
Milton S. Eisenhower Research Cen- APL in 1979. Dr. Phillips has been
ter. He joined the Research Center involved in problems in photoelec-
in 1955 after receiving an A.B. de- trochemical energy conversion, in-
gree in chemistry from The Catholic organic optical and electrical phase
University of America (1951) and a transition compounds, supercon-
Ph .D . degree in physical chemistry ducting materials, and materials characterized with X rays, nuclear mag-
from Cornell University (1955). His netic resonance, mass spectroscopy, and optical spectroscopic techniques.
primary research interests are the-
oretical and experimental investiga-
tions of the structure of molecules
and solids and the relationships be-
166 fohn s Hopkin s APL Technical Digest, Volume 11 , Numbers I and 2 (1990)
High -Temperature Superconductivity
John s Hopkin s APL Technical Digest, Volume 11 , Numbers 1 and 2 (1990) 167