HOME | SEARCH | PACS & MSC | JOURNALS | ABOUT | CONTACT US

A water-based sol–gel technique for chemical solution deposition of (RE)Ba2Cu3O7−y (RE =

Nd and Y) superconducting thin films

This article has been downloaded from IOPscience. Please scroll down to see the full text article.

2006 Supercond. Sci. Technol. 19 1178

(http://iopscience.iop.org/0953-2048/19/11/015)

The Table of Contents and more related content is available

Download details:
IP Address: 130.226.56.2
The article was downloaded on 17/11/2009 at 09:15

Please note that terms and conditions apply.

INSTITUTE OF PHYSICS PUBLISHING SUPERCONDUCTOR SCIENCE AND TECHNOLOGY
Supercond. Sci. Technol. 19 (2006) 1178–1184 doi:10.1088/0953-2048/19/11/015

A water-based sol–gel technique for

chemical solution deposition of
(RE)Ba2Cu3O7−y (RE = Nd and Y)
superconducting thin films
B Schoofs1 , V Cloet1 , P Vermeir1,2 , J Schaubroeck2 , S Hoste1 and
I Van Driessche1
1
Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3,
9000 Ghent, Belgium
2
Department of Industrial Sciences, Hogeschool Gent, Association Ghent University,
Jozef Kluyskensstraat 2, 9000 Ghent, Belgium

E-mail: Bart.Schoofs@UGent.be

Received 19 August 2006, in final form 18 September 2006

Published 16 October 2006
Online at stacks.iop.org/SUST/19/1178
Abstract
The achievement of low-cost deposition techniques for high critical current
(RE)Ba2 Cu3 O7−y -coated conductors is one of the major objectives in
achieving a widespread use of superconductivity in power applications.
Chemical solution deposition techniques are appearing as a very promising
methodology to achieve highly textured oxide thin films at a low cost, so an
intense effort is being carried out to develop routes for all chemically coated
conductor tapes. In this work recent achievements will be presented towards
the goal of the development of an environmentally friendly, completely
water-based sol–gel technique for the deposition of thin superconducting
films on SrTiO3 single-crystal substrates using the dip coat technique. A
comparison is made between aqueous sol–gel synthesis of two
(RE)Ba2 Cu3 O7−y superconducting systems: YBa2 Cu3 O7−y and its
homologue NdBa2 Cu3 O7−y . Our conclusions are that YBa2 Cu3 O7−y still
remains the material of choice for coated conductor development using this
sol–gel technique, with a Tc,onset of 91 K and Jc of 0.3 MA cm−2 .
(Some figures in this article are in colour only in the electronic version)

1. Introduction member of this double perovskite family during in-flame

For the development of coated conductors with high Jc
performance, (RE)Ba2 Cu3 O7−y ((RE)BCO) superconductors
still remain the materials of choice due to their ability to
operate in high magnetic fields. In comparison to the well-
known YBa2 Cu3 O7−y (YBCO) system [1], NdBa2 Cu3 O7−y
(NBCO) is a particularly promising material because of
the superior conductive properties. It has the highest
superconducting transition temperature Tc and exhibits an
enhanced critical current density Jc in intermediate magnetic
fields [2]. In addition we have noted an increased rate
of crystal growth for the Nd-homologue relative to the Y-
spraying experiments [3]. As this material was only studied
in bulk material, we investigated and compared the thin film
synthesis and characteristics of both materials for future coated
conductor development.
Although different vacuum-based techniques yield high-
quality thin films for use as coated conductors, their relatively
high costs, low throughput and scalability pose impediments
to industrial implementation [4]. Considering this, alternative
low-cost and non-vacuum processes for the production of
(RE)BCO-coated conductors need to be developed in order
to facilitate their introduction into broad fields of application.

0953-2048/06/111178+07$30.00 © 2006 IOP Publishing Ltd Printed in the UK 1178

 The chemical solution deposition of (RE)Ba2 Cu3 O7−y superconducting thin films
One of the most promising chemical solution deposition routes
for the production of industrial long-length superconducting
tapes by a continuous system is the dip coating technique [5].
All the present chemical deposition techniques require the
presence of organic solvents to stabilize the highly reactive
metal organic precursors and thus possess a new restriction on
their widespread application.
Therefore and in conjunction with this dip coat
technique, we have developed an environmentally friendly
chemical solution deposition method based on aqueous
sol–gel chemistry. This inorganic metal-chelate sol–gel
route possesses considerable environmental advantages in
comparison to other presently investigated sol–gel routes
(alkoxides, TFA) [6, 7].
In general, the sol–gel process involves the evolution
of inorganic networks through the formation of a colloidal
suspension (sol) and gelation of the sol to form a 3D network
in a continuous liquid phase (gel) [8]. From a chemical point
of view, our sol–gel chemistry is based on the hydrolysis
and condensation of metal multidentate complexes. In this
work, the three metal salts are dissolved in water, with the
formation of unstable metal aqua complexes. To prevent fast
hydrolysis of these species leading to precipitation of metal
hydroxides, the rate of hydrolysis is controlled by adding
specific complexing agents, leading to the formation of metal-
chelates and stabilization of the precursor solution. By slow
evaporation of the solvent (water), multiple condensations of
these complexes will take place, leading to the formation of
a homogenous gel network. As this condensation mechanism
requires stable M–OH species to be present, it will only occur
after a judicious selection of several parameters: (i) the value
of pH which is related to the metal source, (ii) the choice
of complexing agent and (iii) the metal to complexing agent
ratio. For our systems, it should also be mentioned that the
function of a complexing agent is twofold: (i) stabilizing the
precursor solution through the formation of metal complexes
and (ii) allowing cross-linking during gelation through extra
functional groups in the ligands. As the quality of the final
product is highly dependent on the homogeneity and the
bonding behaviour of the metal complexes within the sol and
the gel, a systematic study of the chemical properties of the
gels derived from varying operational parameters has been
undertaken using potentiometric titrations. These data have
been described in detail elsewhere [9].
In this paper we describe the chemical synthesis and
superconducting properties of both YBCO and NBCO thin
films, with special attention to their microstructure and
morphology. Because of the requirement for high texture
in the superconducting layer, the microstructure across the
layer, starting from the interface with the substrate, has also
been investigated, resulting in preliminary clues about the
nucleation behaviour of the amorphous precursor film and the
growth of the final crystalline layer. The determining influence
of the thermal decomposition behaviour of the gel network
during its conversion to the (RE)BCO phase on the final film
morphology as well as on the superconductive properties was
already investigated and published earlier [10].
2. Experimental work
2.1. Preparation of the precursor solution
The YBCO and NBCO precursor solutions were prepared by
dissolving stable, cost-effective and easily available inorganic
salts in an aqueous solution of chelating or coordinating
ligands. As a result, solvation by water molecules is
discouraged, and neither hydrolysis nor precipitation is likely
to take place, and hence a very homogeneous solid material is
obtained after thermal treatment of the deposited gels.
In this study, a stoichiometric mixture of metal acetates in
a total concentration of 0.6 M is diluted in a water–acetic acid
mixture at 60 ◦ C. After refluxing this mixture during 12 h, pure
triethanol amine (TEA) is added dropwise as a complexing
agent in a metal:TEA proportion of 1:3. The pH of this mixture
at room temperature is equal to 6.75 and no further adjustment
is necessary.
Using this synthesis, clear blue precursor solutions with
a viscosity close to water are obtained. If stored in a closed
and dark container, these solutions are stable for several weeks
without the formation of precipitates.
2.2. Pretreatment of the SrTiO3 substrate
The (RE)BCO film has to be grown epitaxially on a substrate or
buffer. Polished (100) SrTiO3 (STO) single-crystal substrates
meet all the requirements for epitaxial growth of (RE)BCO
superconductors [11]. Because of the lack of chemical
interaction between both materials, STO is particularly
interesting for the exploration of thin superconducting film
synthesis prepared by this new sol–gel dip coating method.
After optimization of the synthesis process, this knowledge can
be extended to buffered metal tapes for long-length production
of applicable coated conductor systems [12].
The preliminary step before dip coating is a thorough
degreasing and cleaning process of the substrate’s surface. For
water-based sol–gel systems, this cleaning step is particularly
important because dip coating in an aqueous solution requires
a high wettability of the substrate. Poor wettability obviously
has a detrimental influence on the final properties of the layer,
such as morphology and adhesion, and ultimately Jc .
Cleaning is performed by applying a degreasing sequence
in acetone, methanol and trichloroethylene followed by an
ultrasonic cleaning in acetone. Finally the degreased substrates
are preheated in air at 450 ◦ C for 5 h. After cooling, the
substrates need to be stored in methanol in order to maintain
this wettability for several days and to reduce the deposition of
dust particles on the clean surface.
The evolution of wettability of the surface was determined
by contact angle measurements using the sessile drop
technique [13]. From figure 1, the change of contact angle
after every separate cleaning step can be determined. The
combination of the degreasing, ultrasonic cleaning and thermal
preheating steps leads to an almost complete wetting with the
contact angle decreasing from 75◦ for an untreated surface to
7◦ after applying the three-step cleaning procedure.
2.3. Dip coating and thermal process
In order to avoid dust contamination during thin film
deposition, all manipulation of cleaned and dip-coated films
1179
B Schoofs et al
Figure 1. Sessile drop contact angle measurement on STO substrates
(A: degreased STO; B: ultrasonic cleaned STO; C: preheated at
450 ◦ C; D: untreated STO; E: combination of three cleaning steps).
are performed in a dedicated clean room at a class 10 000 and
computer-controlled precision dip coater in a laminar flow box
at class 10. Dust particles are removed from all solutions by
filtering the solutions with 0.45 μm hydrophilic polypropylene
(GHP) membrane filters.
The (RE)BCO precursor films on STO substrates were dip
coated at a maximum withdrawal speed of 170 mm min−1 .
One single dip of the cleaned substrate at this speed leads to
a final layer thickness of approximately 500 nm, as was later
determined from AFM measurements. This thickness should
be sufficient for technological applications and thicker layers
can be obtained either by multiple dip coating sequences or by
increasing the viscosity of the precursor solution [14].
Immediately after dip coating, the liquid layer is converted
into a gel by heating the sample for several hours at 60 ◦ C
in a dust-free furnace. Subsequently, this amorphous gel is
transformed to the desired crystalline superconducting phase
by a heat treatment in a tube furnace dependent on the
type of superconductor. In order to obtain highly textured,
superconducting YBCO films, the samples were sintered
at 940 ◦ C for 5 h in pure oxygen. After this sintering
process the layers were annealed at 450 ◦ C for 5 h, also
under a 100% oxygen atmosphere. The preparation of
NBCO material is much more sensitive to the proper choice
of synthetic parameters. As is well known, the NBCO
system exhibits a strong tendency for Nd/Ba substitution
with the formation of Nd1+x Ba2−x Cu3 O7−y solid solution
phase, which has detrimental effects on the superconducting
properties of the final layer [15, 16]. Our earlier investigations
showed that the Nd/Ba substitution in spray-dried and sol–gel
prepared bulk material could be depressed by the use of high
sintering temperatures in combination with a reduced oxygen
atmosphere [17]. Therefore the dip-coated and dried layers
were heated at 10 ◦ C min−1 to 940 ◦ C for 7 h under a reduced
oxygen atmosphere containing 1% O2 /Ar. After this sintering
1180
process the layers were annealed at 450 ◦ C for 5 h under a
100% oxygen atmosphere.
2.4. Characterization of the deposited thin layers
The thermal decomposition behaviour of the precursor gel
network was investigated previously by applying TGA–DTA
analysis (Stanton-Redcroft STA 1500) on bulk samples with
the same composition in metal ions and complexants as
the thin films. IR spectra (4000–400 cm−1 ) were taken at
room temperature (KBr-pellets) using a Mattson Unicam FTIR
spectrometer. The microstructure of the deposited layers was
characterized by x-ray diffraction (XRD; Siemens D5000,
Cu Kα ) using θ –2θ geometry in combination with pole figures
for determination of the degree of biaxial texture of the layer.
Local defects in the layer and at the substrate–layer interface
were identified using high-resolution TEM measurements (Jeol
JEM 3010). Combining these results, it was also possible
to observe the initial nucleation during conversion of the
amorphous layer to the oriented crystalline phase. The overall
morphology of the thin films was characterized by optical
microscopy (Leitz) and SEM (Philips 501), while surface
roughness and thickness of the layer were determined using an
interferometric profilometer (Wyko). The critical temperature
of the superconductive layers was determined by resistivity
measurements using a custom-made four-point test device. The
critical current density measurements were performed using a
Theva cryoscan.
3. Results and discussion
3.1. Thermal decomposition precursor
3.1.1. NBCO precursor. In order to establish the best
heat-treatment profile of both films, the decomposition
behaviour of both precursors was studied experimentally
by thermogravimetry by applying the same atmosphere as
during thin film synthesis. The TGA–DTA spectrum of
the precursor gel is shown in figure 2(a). (heating rate
5 ◦ C min−1 , 1% O2 /Ar atmosphere). The broad endotherm
beneath 200 ◦ C corresponds to the evaporation and release of
gel network water. Above 200 ◦ C, three exothermic peaks are
observed, corresponding to the stepwise decomposition of the
gel network. Intermediary products are formed at 220 and
350 ◦ C, while after the last decomposition step at 400 ◦ C no
further weight loss is noticed. IR spectroscopy showed that the
remaining species are formally metal oxides of Nd, Cu and Ba.
3.1.2. YBCO precursor. The TGA–DTA spectrum is
shown in figure 2(b) (heating rate 5 ◦ C min−1 , 100% oxygen
atmosphere). Again, the broad endotherm beneath 200 ◦ C
corresponds to the evaporation and release of gel network
water. Above 200 ◦ C, three exothermic peaks are observed,
corresponding to the stepwise decomposition of the gel
network at 200 and 280 ◦ C with formation of intermediates,
while after the last decomposition step at 420 ◦ C, the remaining
species are determined by IR spectra as being metal oxides of
Y, Cu and Ba.
The decomposition behaviour of the multi-metal gel
network is completely different to the thermal decomposition
 The chemical solution deposition of (RE)Ba2 Cu3 O7−y superconducting thin films
(a)
(b)
(c)
Figure 2. (a) TGA–DTA measurement of an acetate–TEA-based
NBCO sol–gel solution under a 1% O2 /Ar atmosphere.
(b) TGA–DTA YBCO precursor in 100% oxygen atmosphere.
(c) TGA–DTA measurement of the separate metal acetates.
behaviour of the separate metal acetates given in figure 2(c).
Most remarkable is the marked lowering of the decomposition
from the metal complexes to the respective oxides. The last
decomposition step in the mixture occurs at 400 ◦ C, whereas
for the separate metal salts the formation of the oxides takes
place at 300 ◦ C for Cu acetate, 500 ◦ C for Ba acetate, 650 ◦ C
for Nd acetate and 800 ◦ C for the Y acetate. This high
reactivity of the amorphous precursor is probably caused by
the homogenous distribution of the metal ions inside the gel
network.
3.2. Morphology
Figure 3(a) shows the SEM micrograph of the NBCO layer
deposited from the acetate–TEA precursor, while figure 3(b)
shows the SEM micrograph of the YBCO film. Thick
homogeneous and crack-free layers are obtained for both
materials.
Figure 4(a) shows the average roughness AFM measure-
ments of the acetate–TEA-based NBCO layer with values of
average roughness equal to Ra,acetate- TEA NBCO layer = 318 nm.
The average roughness measurement for the YBCO film, de-
rived under the same circumstances, is lower in comparison to
(a)
(b)
Figure 3. (a) SEM image of NBCO film (640×). (b) SEM image of
YBCO film (640×).
NBCO, with an Ra,acetate-TEA YBCO layer = 177.91 nm. These
observations are in contrast to the results obtained by vacuum
deposition techniques, where NBCO films show a lower Ra
value in comparison to YBCO films [18].
3.3. Microstructure
Figure 5 shows the θ –2θ XRD spectrum of the sintered and
annealed NBCO (blue curve) and YBCO (red curve) layer dip
coated on a (l 00) polished STO substrate. From the intensity of
the different (00l ) peak reflections, a strong c-axis orientation
of the layer can be observed. No peaks to be attributed to other
orientations of the (RE)BCO phase or impurity phases were
observed.
Figures 6(a) and (b) show the (103) pole figures for
the NBCO and YBCO layer and exemplifies a high in-plane
texture of the (RE)BCO phase. This is confirmed by the very
low degree of misorientation angles (average value of 3.05◦ for
NBCO, 2.66◦ for YBCO) calculated from the FWHM values in
the phi-scan.
It is well known that the good lattice match with the
STO single-crystal substrate induces the textured growth of
the (RE)BCO phase. For vacuum techniques, this is thought
to occur in an atomic layer-by-layer growth. However, using a
sol–gel system, one starts from a bulky amorphous layer which
is already present in large amounts on top of the substrate
and which has to be converted to the final crystalline phase
afterwards. To induce texture in this layer this means that the
initial nucleation of the (RE)BCO phase has to take place at the
interface between the substrate and the amorphous layer.
1181
B Schoofs et al

(a) (b)

(b)
(a)

Figure 4. (a) AFM measurement of the acetate–TEA-based NBCO

layer ( Ra = 318.45 nm). (b) AFM measurement of the acetate–TEA
Figure 6. (a) Pole figure of acetate–TEA-based NBCO layer.
based YBCO layer ( Ra = 177.91 nm).
(b) Pole figure of acetate–TEA-based YBCO layer.

(a)

Figure 5. XRD of (RE)BCO thin film.

(b)
This assumption was corroborated by HR-TEM measure-
ments at the interface (see figure 7(a)) where the orientation of
the HTSC layer starts immediately at the interface. In fact, this
study demonstrates that the quality of the biaxial textures ob-
tained in films deposited by an aqueous sol–gel method are at
least comparable to those obtained in vacuum-based deposition
technologies.
The diffraction pattern given in figure 7(b) corresponding
to this interface proves the correct growth of both the cubic
single-crystal substrate and the orthorhombic NBCO layer on
top.
This nucleation mechanism at the interface is also
confirmed by the TEM picture given in figure 8 proving that
the growth of the NBCO layer follows the defects present at the Figure 7. (a) HR-TEM picture of NBCO/STO interface.
substrate surface during thousands of packed unit cell layers. (b) Diffraction pattern of interface.
It can therefore be safely concluded that the textured
growth of the superconductor coating probably starts with development of a crystallization front proceeding through the
nucleation of the material at the interface followed by the amorphous gel.

1182
 The chemical solution deposition of (RE)Ba2 Cu3 O7−y superconducting thin films
Figure 8. TEM picture of defects at the NBCO/STO interface.
3.4. Superconductivity
First, NBCO and YBCO bulk material was synthesized
for Tc analysis using the same sol–gel method described
in section 2.1. The resistivity measurement in liquid
nitrogen given in figure 9(a) clearly demonstrates a sharp
superconducting transition of the (RE)BCO material at 90 K.
Applying the same heat treatment as used for bulk
synthesis, we obtained an NBCO thin film with a too low Tc
value of 50 K. This is probably due to the presence of Nd for
Ba substitution in the crystal structure leading to the formation
of Nd123 solid solution phase with detrimental effects on the
superconducting behaviour of the phase. Using Plackett–
Burman statistical design, we optimized crucial synthetic
parameters during heat treatment of the thin films in order to
suppress this tendency for metal ion substitution. Studying
the results of this series of experiments and the accompanying
SPSS analysis we found a correlation between the value of Tc
and sintering time and a relation between the intensity of the
(005) reflection in XRD and the length of the c-axis of the
NBCO material. Using these optimized synthetic parameters
we were able to improve the Tc,onset value to 89 K, even though
the transition stays broad with a Tc,0 below 77 K. Therefore we
can conclude that, using this statistical analysis, we were able
to depress the Nd for Ba substitution in the thin film causing
the lowering in Tc , but the broadening of the transition has a
different origin.
In figure 9(b), the resistivity measurement of the YBCO
film is shown. A broad transition can also be seen here, but
the main difference with the NBCO films is the zero-resistance
temperature above 77 K.
Therefore, we were able to measure the critical current
density using liquid nitrogen with a Theva cryoscan. The
thin film showed a Jc value of 0.3 MA cm−2 . It can
therefore be concluded that the sol–gel synthesis of YBCO
is preferable in comparison to its NBCO counterpart because
of the lack of rare-earth metal ion substitution during the
thermal treatment. It can be expected that narrowing the
superconducting transition will further improve the value of Jc
which will be the subject of a future investigation focused on
the oxygen and carbon content of superconducting phase.
(a)
(b)
Figure 9. (a) Resistivity measurement of NBCO and YBCO bulk
material. (b) Resistivity measurement of YBCO thin film with Jc
value.
4. Conclusion
This paper presents interesting detailed investigations on
(RE)BCO (RE = Y and Nd) thin superconducting films on
SrTiO3 single-crystal substrates, synthesized by a completely
water-based sol–gel dip coating technique. This chemical
solution deposition technique using aqueous sol–gel precursors
offers a very simple, environmental friendly and up-scalable
approach for coated conductor development.
The comparison of the synthesis of both YBCO and
NBCO thin films using these precursors showed that highly
textured films of both materials can be derived by choosing an
appropriate chemical complexation method for the precursors
and an optimized thermal treatment of the amorphous dip-
coated layer.
Concerning the superconducting properties, the NBCO
thin films exhibit a low and broad superconducting transition
temperature even after a statistical optimization of the synthetic
parameters. This decrease of Tc is most likely caused by the
occurrence of Nd/Ba substitution in the NBCO film which
proves to be much more difficult to control in comparison to
bulk NBCO material. For its YBCO thin-film homologue,
better superconducting properties are achieved, with a Tc,onset
of 91 K and Jc values of 0.3 MA cm−2 .
Acknowledgments
This work was supported by a grant from the Institute for
the Promotion of Innovation by Science and Technology in
Flanders (Belgium; IWT Vlaanderen). The authors would like
to thank the Department of Materials Science and Metallurgy at
the University of Cambridge for performing AFM-profilometer
measurements and Oxford Materials and JEOL for performing
HR-TEM measurements. TEM measurements were performed
1183
B Schoofs et al
at Ugent, Department of Metallurgy and Materials Science.
The authors gratefully acknowledge access to the cryoscan
equipment provided by Theva. We would also like to thank
R Mouton for the technical support and the Department
of Solid State Physics at the University of Ghent for
performing x-ray diffraction measurements and scanning
electron microscopy.
References
[1] Palau A, Puig T, Obradors X, Usoskin A, Freyhardt H,
Fernández L, Holzapfel B, Feenstra R, Sánchez A and
Pardo E 2004 Physica C 408–410 866–8
[2] Tret’yakov Yu D and Goodilin E A 2001 Russ. J. Inorg. Chem.
46 S203–34
[3] Van Driessche I, Georgiopoulos E, Denul J, Tsetsekou A,
Andreouli C, De Roeck I, De Winter G, De Gryse R,
Bruneel E and Hoste S 2002 Physica C 372–376 1221–4
[4] Beaumont V, Mercey B and Raveau B 2000 Physica C
340 112–8
[5] Falter M, Häßler W, Schlobach B and Holzapfel B 2002
Physica C 372–376 46–9
1184
[6] Obradors X, Puig T, Pomar A, Mestres N, Sandiumenge F,
Piñol S, Castaño O, Cavallaro A, Palau A and
González J C 2004 Physica C 408–410 913–4
[7] Celik E, Akin Y, Sigmund W and Hascicek Y S 2004 Mater.
Sci. Eng. B 106 182–90
[8] Kakihana M 1996 J. Sol–Gel Sci. Technol. 6 7–55
[9] Schoofs B, Van de Vyver D, Hoste S, Herman G and
Van Driessche I 2006 J. Mater. Chem. submitted
[10] Schoofs B, Mouganie T, Glowacki B A, Cloet V, Hoste S and
Van Driessche I 2006 J. Sol–Gel Sci. Technol. at press
[11] Wang H, Foltyn S R, Arendt P N, Jia Q X, Li Y and
Zhang X 2005 Physica C 433 43–9
[12] Nast R, Obst B and Goldacker W 2002 Physica C
372–376 733–7 (part 2)
[13] http://www.dataphysics.de/english/messmeth sessil.htm
[14] Guglielmi M Encyclopedia of Materials: Science and
Technology
[15] Mozhaev P B, Komissinskii F V, Ivanov Z G and
Ovsyannikov G A 2000 Phys. Solid State 42 1590–5
[16] Yoshizumi M, Nakamura Y, Izumi T, Shiohara Y,
Ikuhara Y and Sakuma T 2001 Physica C 357–360 354–8
[17] Van Driessche I, Schoofs B, Bruneel E and Hoste S 2004 J. Eur.
Ceram. Soc. 24 1823–6
[18] Fabbri F, Padeletti G, Petrisor T, Celentano G and
Boffa V 2000 Supercond. Sci. Technol. 13 1492–8