ENERGY

Development of HoBCO Coated Conductor

Shuji HAHAKURA, Munetsugu UEYAMA, Masaya KONISHI and Kazuya OHMATSU

The authors have been developing HoBa 2 Cu 3 O 7-x (HoBCO) thin films using pulsed laser deposition (PLD)
method. HoBCO shows high critical current density when deposited on single crystal substrate such as
sapphire. Based on PLD technique, HoBCO coated conductor has been developed on flexible metal substrate.
For the development of HoBCO coated conductor, the authors had originally developed a basic technique of the
formation of buffer and superconducting layer. After the basic technique was developed, the authors have
started the development of long-length coated conductors. In the course of this development, the authors had
developed the techniques for forming crystal orientated buffer layer and superconducting multi-layer. As the
result of the development of long-length conductors, high critical current was achieved by the multi-layer
formation of superconducting layer using industrial large-scale excimer laser. Furthermore, with an aim to apply
the coated conductor to superconducting magnet, critical current was measured at low temperature and high
magnetic field. Excellent high critical current was observed, which satisfies the requirements for the coil of high
field magnet such as high resolution NMR magnet.

1. Introduction nique, Sumitomo Electric has been developing the

Since the discovery of high-Tc superconductors,
high-Tc superconducting wires have been developed
with an aim of applying them to the superconducting
cables, magnets, and fault current limiters. There are
two types of high-Tc superconducting wires, which are
Bi-silver sheathed tape wire and RE-123 (RE = rare earth
metal element and Y) coated conductor. At present, the
maximum length of a single Bi-2223 tape wire has
reached to the range of several hundreds of meters to 1
km, but the lengths of RE-123 coated conductors are
still in the range of short length to 100 meters.
However, RE-123 coated conductors have following
advantages; 1) critical current densities (Jc) are in the
106 A/cm2 range, which is about two magnitudes higher
than Bi-2223 tape wire, and 2) critical currents (Ic) are
very high at low temperature and high magnetic field.
The RE-123 coated conductors having higher properties
and longer length that can be used as the next genera-
tion high-Tc superconducting wires are anticipated to
be developed.
At present, the development of RE-123 coated con-
ductors is being conducted all over the world. The typi-
cal film forming methods are vapor deposition method
and liquid phase deposition method. In the case of
vapor deposition, pulsed laser deposition (PLD)
method is usually used. The PLD method has following
features; chemical composition of the formed film is
nearly the same as that of target materials, and deposi-
tion rate is high. On the other hand, in the case of liq-
uid phase deposition, development of large area RE-123
thin films by metal organic deposition method using
organic solution as the starting material is being under-
taken (1).
Using PLD method, Sumitomo Electric has devel-
oped HoBa2Cu3O7-x (HoBCO) thin films on sapphire
single crystals with a Jc of 5 MA/cm2. Based on this tech-
HoBCO coated conductors on metal tape substrates,
which are flexible and allow longer length. The typical
structure of coated conductor is metal substrate, buffer
layer, and superconducting layer starting from the bot-
tom. Buffer layer is required to 1) suppress the element
diffusion between superconducting layer and metal sub-
strate, 2) have excellent in-plane alignment (uniform
crystal orientation), and 3) have smooth surface.
Sumitomo Electric uniquely developed a basic tech-
nique of the formation of buffer and superconducting
layers. Based on this basic technique, the authors have
been proceeding with R&D joining Japan’ s national
project of “Collaborative Research and Development of
Fundamental Technology for Superconductivity
Applications”. In this report, the authors describe the
achievements of Sumitomo Electric’ s uniquely devel-
oped basic technique and the long-length coated con-
ductors developed in the national project.
2. Basic technique
Sumitomo Electric has focused on HoBCO as a RE-
123 material and developed coated conductors using
PLD method. Photo 1 shows the deposition of supercon-
ducting layer by PLD method. Laser beam is irradiated
to the sintered target and plume is produced. A thin
film is deposited on a substrate facing the target. In this
chapter, the authors describe the characteristics of
HoBCO and the technologies for forming buffer and
superconducting layers that are developed uniquely by
the authors.
2-1 Characteristics of HoBCO
HoBCO has the same crystal structure as YBCO,
which is most commonly under development around
the world. HoBCO and YBCO therefore have almost the

14 · Development of HoBCO Coated Conductor

 1.2
(a) YBCO: Surface Protection
YBCO: No Protection
1.0 HoBCO: Surface Protection
HoBCO: No Protection

Jc/Jc (t=0) at 77k

0.8

0.6

0.4

0.2

0.0
0 100 200 300 400 500 600
Time (hr)
Photo 1. Formation of HTS thin film by PLD method
1.2
(b) YBCO: Surface Protection
same characteristics. In a precise sense, however, they YBCO: No Protection
have different characteristics because their RE elements 1.0 HoBCO: Surface Protection
HoBCO: No Protection
are different.

Jc/Jc (t=0) at 7k
0.8
One of the problems of oxide superconductor is
the deterioration of properties by moisture. This could
0.6
be a problem also in the case where oxide superconduc-
tor is applied to the products. So the authors examined
0.4
the moisture resistant properties of YBCO and HoBCO.
Samples of YBCO and HoBCO formed on a 3 inch- 0.2
es diameter LaAlO3 single crystal, respectively, were
used for testing moisture-related deterioration. The 0.0
samples were stored under the same high-temperature 0 400 800 1200 1600
high-humidity conditions (temperature: 60 degrees Time (hr)
Celsius, humidity: 70%), and the variation of Jc was
investigated. Four types of measurement conditions Fig. 1. Ic degradation tests for HoBCO and YBCO under high temperature,
high humidity conditions; (a) short measurement interval (1 day),
were adopted for both YBCO and HoBCO. Table 1
(b) long measurement interval (1 week)
shows these measurement conditions. One parameter is
for protective layer, and the other is measurement cycle.
Photoresist was used for protective layer. The reason Microstructures of YBCO and HoBCO film surfaces
why measurement cycle was varied was that when the were observed using atomic force microscope (AFM).
sample cooled with liquid nitrogen is brought out to the The observed area was 5 square µm. Figure 2 shows the
air during the measurement, dew condensation is AFM observation results. HoBCO shows smoother sur-
formed on the sample’ s surface and deterioration is face and has less deposited substances than YBCO. It
promoted. was also confirmed that HoBCO is chemically stable and
composition fluctuation is low, meaning that HoBCO is
more advantageous to the application to products.
Table 1. Measurement conditions of Ic degradation test The second characteristic of HoBCO is high deposi-
Condition Surface Protection Measurement Interval Measurement Period tion rate. Deposition rate is a very important factor for
A No Protection
1 Day 21 Days
B Photoresist
C No Protection (a) (b)
1 Week 55 Days
D Photoresist

Figure 1 shows the test results. The comparison

between the samples with and without photoresist pro-
tective layer confirmed that protective layer is very effec-
tive for preventing deterioration. The comparison
between YBCO and HoBCO confirmed that Jc deterio-
ration of HoBCO is smaller than that of YBCO, which
means that HoBCO shows better moisture resistance
than YBCO. The test also confirmed that Jc deteriora- Fig. 2. Surface morphology of (a) HoBCO and (b) YBCO measured by
tion is faster with shorter measurement cycle. AFM (scan area: 5µm×5µm)

SEI TECHNICAL REVIEW · NUMBER 59 · JANUARY 2005 · 15

mass production of coated conductors. A comparison
was made between the deposition rates of HoBCO and
YBCO. A PLD method was used, and the laser power
dependence of deposition rate was examined. Figure 3
shows the result. The deposition rate of HoBCO
reached to 5 µm/minute, which is approximately two to
three times faster than that of YBCO. It is assumed that
the reasons HoBCO has faster deposition rate are that
compared with YBCO, HoBCO produces low activation
energy when becoming plasma and has higher crystal
growth rate.
5
4
Depo. rate (µm / min)
3
2
1
0 Ø (degree)
0 50
Fig. 3. Deposition rate vs laser power for HoBCO and YBCO
2-2 Buffer layer growth on metal substrate
The authors conducted the development of a tech-
nique for growing an orientated buffer layer on a Ni
alloy substrate. The size of the substrate used was 0.1
mm in thickness and 10 mm in width. The delta phi
value of (111) plane obtained by X-ray pole figure mea-
surement was in the range of 9 to 12 degrees. Textured
Ni alloy substrates were mirror-polished by mechano-
chemical polishing to the level of surface roughness
(Ra) of 5 nm.
In order to obtain a high Jc superconducting layer,
it is necessary for the buffer layer to achieve excellent
crystal orientation as well as high surface flatness. Buffer
layer structure is therefore very important, and several
kinds of combination of multi-buffer layer materials
were examined by vapor deposition method. PLD
1st Buffer Layer;
Internsity (a.u.)
0 90 180 270
Ø (degree)
Fig. 4. X-ray phi scan of homo-epitaxial buffer layer (1st buffer layer: YSZ,
2nd buffer layer: YSZ)
16 · Development of HoBCO Coated Conductor
method and sputtering method were used for vapor
deposition. Figure 4 shows in-plane x-ray phi-scan data
of homo-epitaxial buffer layers. In this case, both first
and second layers were yttria-stabilized zirconia (YSZ).
Figure 5 shows in-plane x-ray phi-scan data of hetero-
epitaxial buffer layers. In this structure, the first and sec-
ond layers were ceria (CeO2) and YSZ, respectively. As is
seen in these figures, good (100) epitaxial growth with
the delta phi value in the range of 9 to 10 degrees was
obtained for the YSZ/CeO2 hetero-epitaxial buffer layer
structure. Based on these results, the authors had devel-
oped a structure of CeO2 lattice-matched layer / YSZ
inter-diffusion prevention layer / CeO2 seed layer / Ni
alloy substrate.
HoBCO
YBCO
1st Buffer Layer; 2nd Buffer Layer;
Internsity (a.u.)
Internsity (a.u.)
0 90 180 270 360 0 90 180 270 360
Ø (degree)
100 150
Laser power (W)
Fig. 5. X-ray phi scan of hetero-epitaxial buffer layer (1st buffer layer: CeO2,
2nd buffer layer: YSZ)
2-3 Development of coated conductor on metal
substrate
For the formation of superconducting layer by PLD
method, thick films were developed using a multi-layer
deposition technique with an aim of producing a high
Ic coated conductor. A research laser with a laser power
of 100 W was used. The buffered metal substrate used in
the development was that with a delta phi value of 13
degrees and Ra of 5 nm (8).
The deposition techniques of single-layer deposi-
tion and multi-layer deposition were compared. Single-
layer deposition is a technique where a predetermined
film thickness is achieved by one layer deposition cycle.
Multi-layer deposition is a technique where a predeter-
mined film thickness is achieved by multi deposition of
thin layers.
Figure 6 shows the thickness dependence of Jc.
Figure 7 shows the thickness dependence of Ic. Jc
decreases as thickness increases, and the decrease in Jc
is smaller in multi-layer deposition than in single-layer
2nd Buffer Layer; deposition. In the deposition of 1.5 µm thickness, Jc > 1
MA/cm2 was observed for multi-layer deposition while Jc
Internsity (a.u.)
was almost 0 for single-layer deposition. As for Ic, in the
case of multi-layer deposition, it increased until the
thickness was 1.5 µm, and in the case of single-layer
deposition, Ic started to decrease from the thickness of
360 0 90 180 270 360
0.7 µm, and became almost 0 at the thickness of 1.5 µm.
Ø (degree) The reasons why a film formed by multi-layer depo-
sition shows higher properties than that formed by sin-
gle-layer deposition is assumed as follows; 1) because
each layer is thin, oxygen is easily taken into the film
 2.5
3. Development of long-length superconducting wire
Multi Layer Deposition

2.0 One Layer Deposition Based on these results of its unique development,
Sumitomo Electric has been developing HoBCO coated
Jc at 77K, 0T (MA / cm2)

conductor by joining the national project of

1.5 “Collaborative Research and Development of
Fundamental Technology for Superconductivity
Applications” since FY 2003. In this national project, the
1.0 authors have developed HoBCO coated conductor
using a high-power high-stability industrial excimer
laser. This excimer laser operates at a wavelength of 248
0.5 nm (KrF excimer laser), and its laser power is 200 W
(maximum laser energy: 1 J, maximum repetition rate:
200 Hz).
0.0
0.0 0.5 1.0 1.5 2.0 3-1 Continuous deposition of buffer layer
Thickness (µm)
In order to decrease the influence of grain bound-
ary and improve the in-plane alignment, the authors
examined a technique for continuous deposition of
Fig. 6. Jc vs thickness for HoBCO films prepared by multi-layer deposition
and single-layer deposition
buffer layer.
Table 2 shows the AFM measurement results for the
surfaces of buffer layers, which are before and after the
optimization. After a buffer layer was optimized, surface
flatness and in-plane alignment were both improved.
200
Surface flatness (Ra) and maximum peak to valley (PV)
improved to the level of Ra = 3-10 nm and PV = 20-50
nm, respectively. As for in-plane alignment, the delta
150 phi value was in the range of 10 to 15 degrees before
Ic at 77K, 0T (A / cm-w)

optimization, but decreased to about 8 degrees after

optimization.
Multi Layer Deposition
100
One Layer Deposition Table 2. Surface of buffer layer measured by AFM

Surface Roughness Ra (nm) Peak to Valley PV (nm)

50
Before Optimized 5.4 ~ 12.8 47.7 ~ 389.1
After Optimized 2.7 ~ 9.7 21.8 ~ 54.6

0
0.0 0.5 1.0 1.5 2.0

Thickness (µm) 3-2 Continuous deposition of superconducting

Fig. 7. Ic vs thickness for HoBCO films prepared by multi-layer deposition
and single-layer deposition
during the deposition process, and 2) diffusional reac-
tion of elements is suppressed because deposition time
(i.e. heating time) is short. The reason why Ic declines
with the increase in thickness is also assumed as that the
film is deteriorated by the diffusional reaction of ele-
ments due to long heating time.
Furthermore, based on these results of multi-layer
deposition, continuous deposition was conducted on a
buffered metal substrate. Jc of 2.2 MA/cm2, which is at
the highest level in the world, was obtained at a moving
speed of 15 m/H. Furthermore, the sample prepared at
a moving speed of 5 m/H exhibited Ic of 176 A per 1
cm in width.
layer
A HoBCO superconducting layer was deposited on
a buffered Ni alloy textured substrate with an aim of
achieving high Jc, and then evaluated. For a short sam-
ple, a maximum Jc of 2.1 MA/cm2 was obtained at the
thickness of 0.15 µm.
Photo 2 shows the scanning electron microscope
(SEM) images of HoBCO superconducting layers.
Before the buffer layer was optimized, cracks that seem
to be caused by grain boundaries were observed at the
surface of the superconducting layer on a Ni alloy tex-
tured substrate. On the other hand, after the buffer
layer was optimized, the surface of HoBCO on the
buffer layer with excellent in-plane alignment and flat-
ness was very smooth.
The authors adopted the multi-layer technique and
developed thick films with an aim of achieving high Ic.
The conditions of multi-layer deposition of HoBCO
superconducting layer were examined using a buffered
metal substrate with a delta phi value of 8 degrees and
Ra of 5 nm. Figure 8 shows the result. A maximum Ic of
357 A/cm-w, which is at the highest level in the world,

SEI TECHNICAL REVIEW · NUMBER 59 · JANUARY 2005 · 17

 Grain Boundaries 3-3 Development of long-length superconducting
wire by continuous deposition
(a)
In order to adopt superconducting wires to com-
mercial use, it is necessary to achieve long length by
continuous deposition. Based on the results of continu-
ous deposition of buffer layer, the 2 m long buffer layers
were fabricated. Figures 9 and 10 show distributions of
in-plane alignment and surface roughness of 2 m long
buffer layers, respectively. The samples of A and B both
showed a delta phi value of less than 10 degrees and Ra
of less than 5 nm.

10µm
20
18 A
16 B
(b) 14

∆Ø (˚ )
12
10
8
6
4
2
0
0 0.5 1 1.5 2

Position (m)

Fig. 9. In-plane alignment of 2 m buffer layers (3rd layer: CeO2)

10µm

Photo 2. SEM images of HoBCO layer on Ni alloy substrate;

(a) before buffer layer was optimized (Jc = 0.2 MA/cm2), and 20
(b) after buffer layer was optimized (Jc > 1 MA/cm2). 18 A
Surface Roughness (nm)

16 B
14
12
400 10
8
350
6
300 4
2
250
Ic (A/cm-w)

0
0 0.5 1 1.5 2 2.5
200
Position (m)
150

100 Fig. 10. Surface roughness of 2 m buffer layers (3rd layer: CeO2)

50
Based on the result of the fabrication of short-
0 length superconducting layer, 2 m long superconduct-
0.0 1.0 2.0 3.0 4.0 ing wires were test fabricated by continuous deposition.
Thickness (µm) The previously mentioned 2 m long buffer layers were
used for the deposition of superconducting layers.
Multi-layer technique was used for the formation of
Fig. 8. Ic vs thickness of HoBCO on buffered metal substrate
superconducting layer. Figure 11 shows the Ic distribu-
tions of the two conductors that were test fabricated.
was achieved. The multi-layer deposition technique sup- The distributions of Ic = 66-31 A and Ic = 94-42 A were
pressed the decline of Jc caused by an increase of thick- obtained, which confirmed that an Ic of 100 A class
ness, and Jc of 1 MA/cm2 was retained even at the thick- could be obtained under optimal conditions in the
ness of 3 µm. High Ic was thus achieved. deposition of several meters of superconducting layers.

18 · Development of HoBCO Coated Conductor

 200 Table 3. Parameters of HoBCO coated conductors and the results of Ic measured
180 at 77 K, 0 T and 4.2 K, 30 T
A
160 B A Series B Series
140 Samples
A-1 A-2 B-1 B-2
Ic (A/cm-w)

120
Thickness (µm) 0.47 0.92 0.55 1.25
100
80 Ic
23 45 132 166
77K, (A/cm-w)
60
40 0T Jc
0.49 0.48 2.39 1.33
(MA/cm2)
20
0 Ic
124 220 749 2,420
0.0 0.5 1.0 1.5 2.0 4.2K, (A/cm-w)
Position (m) 30T Jc
2.6 2.4 13.6 19.4
(MA/cm2)
Fig. 11. Ic distribution of 2 m HoBCO coated conductors Ic (4.2K, 30T)/
5.4 4.9 5.7 14.6
Ic (77K, 0T)

It is assumed that nonuniformity of the Ic distributions

in 2 m length is caused by the nonuniformity of flatness
and in-plane alignment of substrate and buffer layer.
4. Characteristics under low temperature and
high magnetic field
tion caused by magnetic field. The ratio of Ic at 30 T to
Ic at 0 T, which is represented by Ic(4.2 K, 30 T)/Ic(4.2
K, 0 T), was typically 0.5.
The results of high Ic at 4.2 K and 30 T indicate
that HoBCO coated conductor is capable of satisfying
the requirement for the coil of high field magnet such
as high resolution NMR magnet.

HoBCO coated conductors are expected to be

applied to high field magnet. To evaluate the character-
istics of HoBCO coated conductor, Ic was measured at
low temperature and high magnetic field.
The Ic measurement was conducted at the Tsukuba
Magnet Laboratory of National Institute for Materials
Science. Using a hybrid magnet with the maximum
magnetic field of 30 Tesla, Ic was measured during the
course of the magnetic field decrease, after the magnet-
ic field was increased to the maximum value. The mea-
surement temperature was 4.2 K, and magnetic field was
applied parallel to the sample surfaces.
The HoBCO samples with film thickness ranging
from 0.47 to 1.25 µm were used in the measurement.
The samples were 10 mm in width and 0.1 mm in thick-
ness. Because large currents flow when Ic is measured at
low temperature and high magnetic field, the samples
were etched in across the width direction. The effective
width of the sample after etching was 1 to 5 mm.
Table 3 shows the parameters of the samples and
the Ic measurement results at 77 K, 0 T and 4.2 K, 30 T.
The A series samples are those that show Jc of more
than 1 MA/cm2 at 77 K, 0 T. The B series samples show
Jc of less than 1 MA/cm2 at 77 K, 0 T. The A series
HoBCO samples with 0.92 µm film thickness achieved
Ic(4.2 K, 30 T) = 220 A/cm-w. Ic(4.2 K, 30 T)/Ic(77 K, 0
t), which represents a comparison between Ic values at
4.2 K and 77 K, were nearly 5 for all samples.
The B series HoBCO samples with1.25 µm film
thickness achieved Ic(4.2 K, 30 T) = 2,420 A/cm-w. In
the case of this series of samples, Jc reached to 19.4
MA/cm2 and Je reached to 2.42 * 109 A/cm2. In the
comparison between the results at 4.2 K and 77 K, the B
series samples showed larger Ic(4.2 K, 30 T)/Ic(77 K, 0
t) values than the A series, one sample reaching to 15.
All HoBCO samples showed only small Ic degrada-
5. Conclusions
Based on the formation technology of high perfor-
mance HoBCO thin film on a single crystal, the authors
had advanced the development of HoBCO coated con-
ductors on metal substrates, which offer flexibility and
long-length. Compared with YBCO thin film, HoBCO
thin film showed better properties such as higher mois-
ture resistance and faster deposition rate. In the devel-
opment of HoBCO, Sumitomo Electric had developed
unique basic techniques for forming orientated buffer
layers and for multi-layer deposition of superconducting
layers on metal substrates. Based on these basic tech-
niques, the authors have developed long-length coated
conductors. The thick films formed by using industrial
large-scale laser equipment achieved Ic = 357 A/cm-w.
Furthermore, a continuous deposition technique for
buffer layer and superconducting layer has been devel-
oped. Critical current was measured for HoBCO coated
conductor at low temperature and high magnetic field.
Ic(4.2 K, 30 T) of 2,400 A/cm-w was observed, which sat-
isfies the requirement for the coil of high field magnet
such as high resolution NMR magnet.
6. Acknowledgement
A part of this work was supported by the New
Energy and Industrial Technology Development
Organization (NEDO) as the Collaborative Research
and Development of Fundamental Technology for
Superconductivity Applications.
The authors would like to thank Dr. T. Takeuchi

SEI TECHNICAL REVIEW · NUMBER 59 · JANUARY 2005 · 19

and Dr. N. Banno at the Tsukuba Magnet Laboratory of
National Institute for Materials Science for Ic measure-
ment under low temperature and high magnetic field.
The authors also wish to thank Dr. V.
Selvamanickam of SuperPower Inc. for supplying us a
part of substrates used in this work.
References
(1) T. Manabe, M. Sohma, I. Yamaguchi, W. Kondo, K. Tsukada, S.
Mizuta and T. Kumagai, Physica C 392-396 (2003) 937.
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(2001) 1339.
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Contributors

S. HAHAKURA
• Assistant Manager, Energy & Environmental Materials R&D Department, Electronics & Materials R&D Laboratories

M. UEYAMA
• Assistant Manager, Energy & Environmental Materials R&D Department, Electronics & Materials R&D Laboratories

M. KONISHI
• Assistant General Manager, Energy & Environmental Materials R&D Department, Electronics & Materials R&D
Laboratories

K. OHMATSU
• Coated Conductor Project Leader, Energy & Environmental Materials R&D Department, Electronics & Materials
R&D Laboratories

20 · Development of HoBCO Coated Conductor