Biaxially textured CeO

2
seed layers and thin lms
on Ni substrates by chemical solution deposition
using inorganic cerium nitrate as a precursor
S. Chen
a,b,
*
, S.S. Wang
a
, K. Shi
a
, Q. Liu
b
, Z. Han
a
a
Applied Superconductivity Research Center, Tsinghua University, Beijing 100084, PR China
b
Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, PR China
Received 8 October 2004; accepted 12 November 2004
Available online 25 December 2004
Abstract
A solution process was used for the epitaxial growth of CeO
2
seed layers and thin lms on Ni substrate material
using inorganic cerium nitrate as a precursor. The precursor solution was prepared by dissolving cerium nitrate in acetyl
acetone, 2-methoxyethanol and glycol. The CeO
2
thin lms, spin coated on Ni substrates, were annealed at 5001100 C
in a 4%H
2
Ar atmosphere. X-ray diraction showed a strong c-axis orientation of the CeO
2
thin lms on the Ni {001}
(100) substrate. Out-of-plane and in-plane texture analysis, as well as pole-gure analysis, revealed a cube-on-cube tex-
ture in the lms. For CeO
2
seed layers, scanning electron microscope investigations showed a discontinuous structure,
whereas CeO
2
thin lms possessed a continuous dense structure. A CeO
2
buer layer grown on a CeO
2
seed layer
showed an enhancement in the biaxial texture.
2004 Elsevier B.V. All rights reserved.
Keywords: CeO
2
; Chemical solution deposition; Nano-island; Thin lm; Epitaxial growth
1. Introduction
A great deal of eort has been devoted to pro-
cesses for fabrication of YBCO coated conductors,
due to their high critical current density and intrin-
sically high irreversibility eld [1]. YBCO lms are
generally deposited on metallic substrates, usually
on Ni or Ni-alloys, for potential large scale electri-
cal applications. The electrical performance is con-
siderably degraded by the presence of high-angle
grain boundaries [2], presenting a technical chal-
lenge in the production of long lengths of super-
conductor. The rolling assisted biaxially textured
0921-4534/$ - see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.physc.2004.11.024
*
Corresponding author. Address: Applied Superconductiv-
ity Research Center, Tsinghua University, Beijing 100084, PR
China. Tel.: +86 10 6278 9339; fax: +86 10 6278 5913.
E-mail address: cs01@mails.tsinghua.edu.cn (S. Chen).
Physica C 419 (2005) 712
www.elsevier.com/locate/physc
substrate (RABiTS) method [3,4] has been devel-
oped to produce polycrystalline Ni tapes having
a strong (001) [100] cube texture orientation,
which serves as a template for the subsequent epi-
taxial growth of layers containing only low-angle
grain boundaries. However, due to interdiusion
problems, YBCO lms deposited directly onto Ni
or Ni-based substrates exhibit poor superconduct-
ing properties. By introducing single or multilayer
structures of such phases as yttria-stabilized zirco-
nia (YSZ) [5], MgO [6], SrTiO
3
[7], CeO
2
[8,9], and
La
2
Zr
2
O
7
[10], this problem has been successfully
overcome. CeO
2
buer layers have attracted spe-
cial interest and have been used both as a seed
layer and as a cap layer in sandwich-structured
buer layers [8,9]. CeO
2
has a compatible thermal
coecient and crystalline lattice parameter match,
as well as chemical stability, with the YBCO super-
conducting layer at elevated temperatures. Besides
conventional vacuum deposition methods, the sol
gel technique has also been adopted for the growth
of biaxially aligned CeO
2
buer layers. Recent re-
search has shown that using cerium organic salts,
such as cerium (III) acetylacetonate [8], cerium
(IV) methoxyethoxide [9], or cerium 2,4-pentanedi-
onate [11], as a precursor, biaxially aligned CeO
2
thin lms can be successfully grown on Ni sub-
strates. Inorganic cerium salts have also been used
to grow CeO
2
thin lms on Ni substrates but there
are several problems with this approach, the main
ones being crack formation and the development
of a randomly oriented texture [12,13]. In this
work, we present a novel method to prepare uni-
form biaxially textured CeO
2
seed layers and thin
lms from commercial inorganic cerium nitrate.
The crystalline quality and surface morphology
of the CeO
2
thin lms are discussed.
2. Experimental
The precursor solution was prepared in a dry-
glove box. The reagentscerium nitrate (Ce(NO
3
)
3

6H
2
O), acetyl acetone (CH
3
COCH
2
COCH
3
),
glycol (HOCH
2
CH
2
OH) and 2-methoxyethanol
(CH
3
OCH
2
CH
2
OH)were used as-received from
Beijing chemical reagents company (Beijing,
China). Cerium nitrate was used as starting mate-
rial. The cerium nitrate was pre-dried via vacuum
desiccation before being dissolved in acetyl ace-
tone at a molar ratio of 1:2. The solution was then
reuxed for 2 h before adjusting the concentration
to 0.25 M in a mixture of 2-methoxyethanol and
glycol. In order to study the eect of a seed layer
on the epitaxial growth of CeO
2
thin lms, some
precursor solution was diluted to 0.05 M for use
in the fabrication of a CeO
2
seed layer. The solu-
tions were syringed through a 0.2 lm lter and
stocked for one week before use. High purity
cold-rolled Ni (99.999%) tapes with a rolling
reduction of 98% were used as the substrate mate-
rial. The tapes were cleaned in an ultrasonic clea-
ner using chloroform, acetone and ethanol, prior
to heat treatment in a tube furnace at 1000 C
for 60 min with a 4%H
2
Ar gas ux. The annealed
Ni tapes were cut in pieces of size 10 10 mm
2
be-
fore use for lm/seed layer deposition. Detailed
characterization of the Ni substrates has been re-
ported elsewhere [14]. CeO
2
thin lms were depos-
ited on the Ni substrates by spin coating at a speed
of 3000 rpm for 30 s. Dierent subsequent anneal-
ing temperatures, between 500 and 1100 C, with
dierent heating rates and cooling rates were
investigated.
The decomposition behavior of the precursor
gel was characterized by thermogravimetric analy-
sis (TGA) and dierential thermal analysis (DTA).
For orientation characterization, a Rigaku X-ray
diractometer (CuKa radiation) was used to carry
out h/2h scans and out-of-plane x scans. A
four-circle diractometer (D/max-IIIA) was used
to collect pole gures and for the in-plane u
scan investigations. Microstructures of the CeO
2
thin lms were analyzed by using a LEO1530 ther-
mal eld emission gun scanning electron micro-
scope (FEG-SEM) equipped with an Inlens
detector. No conductive coating was applied to
the samples.
3. Results and discussion
3.1. Decomposition of the precursor gel
Fig. 1 shows TGA and DTA curves for the
0.25 M precursor gel. From the TGA curve the
8 S. Chen et al. / Physica C 419 (2005) 712
weight loss of the precursor gel was estimated as
about 50% at 1000 C. The DTA curve shows
the evaporation of residual water at about
100 C and the evaporation of 2-methoxyethanol
and acetyl acetone at 130 C. The pyrolysis of
residual organics is basically characterized by the
two-step exothermic process which occurs between
320 and 380 C. Analysis of the X-ray diraction
(XRD) measurements suggested that the exother-
mic peak at 640 C was associated with the forma-
tion of crystalline CeO
2
.
3.2. Microstructures of the seed layer and thin lm
0.05 and 0.25 M precursor solutions were used
for deposition of CeO
2
seed layers and CeO
2
thin
lms, respectively. The lms were subsequently
annealed at 1000 C for 60 min in 4%H
2
Ar.
Fig. 2(a) shows the CeO
2
seed layer on a Ni sub-
strate. Due to the low concentration of the pre-
cursor solution, the seed layer is discontinuous
and consists of uniformly aligned small CeO
2
is-
lands 1530 nm high and 100200 nm long. Most
of the islands are square or rectangular in shape.
It has been suggested by Miller and Lange [15]
and Clem et al. [16] that a discontinuous seed
layer is benecial in supplying nucleation sites
for subsequent epitaxial growth of thin lms.
Fig. 2(b) shows a CeO
2
thin lm grown on a Ni
substrate using 0.25 M precursor solution. The
lm is continuous, dense and has fully covers
the Ni substrate. The grain size is about
200 nm. Some micro-cracks can be observed on
the CeO
2
surface, most of which showed vertical
or parallel prolongations to each other. Trans-
crystalline cracks are also observed, suggesting
that the cracks were formed after the formation
of the CeO
2
lm. The mismatch of the ther-
mal expansion coecients between CeO
2
(7.45
10
6
K
1
) and Ni (12.7 10
6
K
1
) will cause a
compressive stress in the CeO
2
layer, which
should be helpful in suppressing the formation
of cracks. Cracks in CeO
2
thin lms on Ni
substrates are a well documented problem. Much
research has been done to investigate the forma-
tion and avoidance of crack formation [17,18].
Lim et al. [18], for example, reported that the
introduction of a thin layer of Y
2
O
3
between
the Ni and CeO
2
layer can help eliminate crack
formation.
Fig. 1. TGA/DTA curves for the 0.25 M CeO
2
precursor gel. A
heating rate of 5 C/min in ambient air was used.
Fig. 2. SEM micrographs of (a) a CeO
2
seed layer produced
from 0.05 M precursor solution; (b) a CeO
2
thin lm produced
from 0.25 M precursor solution. Both were deposited on a Ni
substrate and annealed at 1000 C for 60 min in a 4%H
2
Ar
atmosphere.
S. Chen et al. / Physica C 419 (2005) 712 9
3.3. Phase formation in the CeO
2
thin lm and seed
layer
To determine the temperature-dependence of
the formation of the CeO
2
phase, Ni substrates
with spin coated CeO
2
thin lms were placed in a
quartz tube and then purged with 4%H
2
Ar gas
ux for 10 min before being introduced into a pre-
heated furnace at 5001100 C for 60 min. The
resulting CeO
2
thin lms were then quenched to
room temperature inside the quartz tube. Fig. 3
shows XRD h2h scan proles of the resulting
CeO
2
thin lms on Ni substrates for various
annealing temperatures. The 2h peak at 33.08 be-
longs to the cubic CeO
2
phase and is indexed as the
(200) reection. The small peak at 2h = 44.54 and
strong peak at 2h = 51.89 correspond to the Ni
(111) and (200) reections, respectively. Films an-
nealed at 500600 C appear to be amorphous.
After a 700 C anneal, the cubic structure starts
to form. This result is consistent with the DTA
analysis. At higher annealing temperatures the dif-
fraction peaks become stronger and sharper, indi-
cating better crystallinity in lms annealed at
higher temperatures. After a 900 C anneal, high-
quality CeO
2
is achieved. This result is similar to
that of Bhuiyan for organic cerium (III) acetylacet-
onate result [8], demonstrating that CeO
2
has
almost the same crystallization temperature
regardless of whether it is produced from organic
or inorganic starting material. Only the (200)
reection of the CeO
2
cubic phase is observed
across the temperature range investigated, denot-
ing a wide process window for formation of the
buer layer. For CeO
2
seed layers spin coated
from 0.05 M precursor solution, relatively weaker,
pure (200) reections could only be observed in
samples annealed above 700800 C.
3.4. Textures of the thin lms
Texture measurements, shown in Fig. 4, were
carried out on a CeO
2
lm processed at 1000 C
for 60 min. The full-width-at-half-maximum
(FWHM) values of the CeO
2
(200) and Ni (200)
x scans (Dx) were 4.9 and 5.7, respectively.
The FWHM values of the u scans (Du) were 7.1
for the CeO
2
(111) plane and 7.6 for the Ni
(111) plane. The pole gure (Fig. 5) of the CeO
2
solgel buer layer showed cube-on-cube epitaxy
on the textured Ni (100) substrate. From the pole
gure, as well as from the u and x scans, we can
conclude that the CeO
2
lm exhibits a biaxial
alignment on the Ni {001} h100i substrate. The
in-plane and out-of plane texture measurement
of the seed layer show improvement of the in-plane
texture. This may arise as a result of the thinner
thickness of the CeO
2
layer, thereby allowing a
better epitaxial texture transfer from the Ni
surface.
3.5. Enhancement of the texture on lms using seed
layer
To investigate the eect on buer layer quality
of using a CeO
2
seed layer, we also fabricated a
thin lm from a 0.25 M precursor solution onto
an annealed CeO
2
seed layer. Fig. 6 shows the
in-plane and out-of-plane textures of the CeO
2
buer layer grown on a 0.05 M seed layer. The
Dx values of the CeO
2
layer produced without
(in Fig. 4) and with a 0.05 M seed layer are 4.9
and 5.2, respectively, while the Du values are
7.6 and 6.2, respectively. The in-plane texture
of the CeO
2
lm is therefore decreased by 1.4 by
use of a 0.05 M seed layer. The enhancement of
the in-plane texture should be explained consider-
ing the interfacial energy. The interfacial energy
Fig. 3. XRD pattern for CeO
2
buer layers on Ni substrates
annealed at: (a) 500 C, (b) 600 C, (c) 700 C, (d) 800 C, (e)
900 C, (f) 1000 C, (g) 1100 C for 60 min in a 4%H
2
Ar
atmosphere.
10 S. Chen et al. / Physica C 419 (2005) 712
between the CeO
2
lm and the CeO
2
seed layer
should be smaller than that between CeO
2
lm
and Ni substrate, thus the CeO
2
lm could grow
epitaxially more easily on a CeO
2
seeded Ni sub-
strate than directly on the Ni substrate.
4. Summary
Inorganic cerium nitrate was successfully
adopted for the rst time as the starting material
for the epitaxial growth via chemical solution
deposition of CeO
2
thin lms on textured Ni
(100) substrates. The resulting CeO
2
buer layers
had cube texture epitaxy with the substrate.
XRD investigation of the temperature dependence
of crystallization showed that crystallization of
the CeO
2
lm begins at 600700 C in 4%H
2
Ar,
and has a wide process window. The additional
Fig. 5. Result of X-ray diraction pole gure of CeO
2
on Ni:
(111) of CeO
2
, showing a single cube-on-cube epitaxy.
Fig. 4. Results of X-ray diraction analysis of CeO
2
on Ni {001} h100i substrates: (a) x scan for CeO
2
(200); (b) x scan for Ni (200);
(c) u scan for CeO
2
(111); (d) u scan for Ni (111).
S. Chen et al. / Physica C 419 (2005) 712 11
introduction of a nano-dimensional CeO
2
seed
layer is helpful for the subsequent growth of
CeO
2
thin lms.
Acknowledgements
This work was supported by the National Nat-
ural Science Foundation of China under contract
No. 50371039 and by the National High Technol-
ogy Research and Development Program (863
program) under contract Nos. 2002AA306211
and 2002AA306281.
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Fig. 6. x and u scans for a CeO
2
thin lm deposited on Ni-
substrate with a 0.05 M CeO
2
seed layer.
12 S. Chen et al. / Physica C 419 (2005) 712