Applied Surface Science 258 (2012) 48524856

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Surface treatment of nickel substrate for the preparation of BSCCO lm through

solgel method
Huazhe Yang b, , Xiaoming Yu a , Yang Ji c , Yang Qi a,
a
Institute of Materials Physics and Chemistry, School of Sciences, Northeastern University, Shenyang 110819, PR China
b
Department of Biophysics, College of Basic Medical Science, China Medical University, Shenyang 110001, PR China
c
Stomatology Department of the General Hospital of Shenyang Military Area Command, Shenyang, 110840, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A modied degreasing-oxidization process was devised and settled to treat the surface of nickel (Ni)
Received 24 November 2011 substrates, and BSCCO lms were prepared on the treated NiO/Ni substrates by solgel method. X-ray
Received in revised form 9 January 2012 diffraction (XRD) and optical microscopy were adopted to clarify the function of different treatment on
Accepted 9 January 2012
phase formation and wettability of NiO/Ni substrates. Differential thermal analysis and thermal gravime-
Available online 31 January 2012
try analysis were adopted to conrm the desirable heat treatment process. XRD and scanning electron
microscopy were adopted to investigate the phase constituent and surface morphology of BSCCO lms.
Keywords:
Results demonstrate that both the surface wettability of the substrate to sol and the lattice matching
BSCCO
Nickel substrate
between the substrate and BSCCO can be improved through the modied treatment, which are favorable
Sol for the preparation of BSCCO lms.
Wettability 2012 Elsevier B.V. All rights reserved.

1. Introduction to be investigated systematically. To date, one of the well-known

Since the discovery of BiSrCaCuO (BSCCO) superconduc-
tors [1], much work has been done to apply this system in the eld
of large current transport. The rst generation (1G) silver-sheathed
BSCCO lms fabricated by the powder-in-tube (PIT) technique have
been proven to be desirable cables for application [2,3]. However,
the development of the lms is restricted due to the following
problems: (1) the relative long sintering time and the impurities in
BSCCO samples for solid state reaction; (2) the high cost of Ag sheath
in mass production. Therefore, new methods based on Ion-Beam-
Assisted Deposition (IBAD) and rolling assisted bi-axially textured
substrate (RABiTS) have been devised and settled to prepare novel
lms [4,5]. In these methods, solgel technique is attractive owing
to its low cost, easy handling, molecular level homogeneity and
high purity of the product [68].
In contrast to the conventional substrates for BSCCO lms (STO
and MgO, etc.) [9,10], nickel (Ni) is considered as a desirable sub-
strate owing to its low cost, good mechanical properties, high
texture and strong antioxidant ability [11], providing a feasible
approach to fabricate lms [1217]. Nevertheless, especially for
solgel method, the cleanliness of surface plays a crucial role in
the wettability of the substrates to sol coating [18], which is yet
conventional cleaning processes for substrates is the ultrasonic
washing with acetone and alcohol [19]. This degreasing process,
however, is not universal for all substrates. Therefore, it is impor-
tant to nd a simple and effective cleaning process besides the
conventional one to remove contaminants on the surface of Ni
substrates effectively. Furthermore, there is few investigations
concerning on the fabrication of BSCCO lms by solgel method
[20,21], which adopted substrates (such as STO) with high cost and
poor processability. As a potential alternative to STO, Ni substrate
also faces the challenge such as the magnetism and the undesir-
able lattice mismatch between Ni and BSCCO. Therefore, it seems
unavoidable to introduce heterogeneous buffer layers such as YSZ
on surface of Ni, which brings in the increase of difculty and cost
of preparation.
In this paper, a modied degreasing-oxidization process was
brought to clean and oxidize surface of Ni substrates, and BSCCO
lms were prepared directly on the as-treated NiO/Ni substrates.
The surface wettability of different substrates to sol was investi-
gated and the lattice matching model between NiO and BSCCO was
proposed. The investigation provides a novel point of view on feasi-
bility of the self-oxidized NiO homogenous buffer layer for BSCCO
lms.

2. Experimental method
Corresponding authors. Tel.: +86 24 83678479.
E-mail addresses: hzyang@mail.cmu.edu.cn (H. Yang), qiyang@imp.neu.edu.cn Ni substrates were cut into 0.7 cm 0.7 cm pieces, and the clean-
(Y. Qi). ing process was performed by applying the degreasing sequence in

0169-4332/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2012.01.055
 H. Yang et al. / Applied Surface Science 258 (2012) 48524856
Fig. 1. Flowchart of the preparation of Bi-2212 lms through solgel method.
Reagent I (acetone and alcohol) or Reagent II (toluene, acetone and
methanol), followed by an ultrasonic cleaning in de-ionized water,
respectively. Then, the heat treatment and oxidation process were
carried out by annealing at 1000 C for 1 h in vacuum followed by
heating at 1100 C for 3 h in atmosphere to prepare NiO/Ni sub-
strates. Finally, the self-oxidized NiO/Ni substrates were stored in
methanol to reduce the contamination.
The BSCCO precursor sol was obtained from a mixture of
nitrate solution, ethylene diamine tetraacetic acid (EDTA) and
triethanolamine (TEA), and the process to prepare the sol was
described in detail elsewhere [21,22]. Then, the sol was spin-coated
on the surface of self-oxidized Ni substrates, followed by drying
at 150 C for 10 min, and the spin-coating process was repeated
for10 times. Thereafter, the BSCCO lms can be obtained through
the subsequent heat treatment process. Flowchart of the experi-
mental process was shown in Fig. 1. X-ray diffraction (XRD) with
Cu-K radiation and optical microscopy were adopted to moni-
tor the changes taking place on the nickel surface as a result of
the modied degreasing-oxidization process; differential thermal
analysis and thermal gravimetry (DTA-TG) analysis was operated
from room temperature to 1000 C at the speed of 10 C/min to
obtain the desirable heat treatment process; XRD and scanning
electron microscopy (SEM) were adopted to investigate the phase
constituent and surface morphology of BSCCO lms prepared on
NiO/Ni substrates derived from the modied cleaning process.
3. Results and discussion
3.1. Treatment of nickel substrate
As a substrate, the cleanliness process plays a crucial role in
changing the wettability of surface, so it is essential to develop a
scalable surface cleaning process for Ni substrates before the intro-
duction of buffer layers and BSCCO lms. Therefore, Reagent I and
Reagent II were adopted as degreasing agent to clean surface of Ni
substrate, respectively. Then, two types of NiO/Ni substrates can be
obtained by heating in vacuum and oxidizing in atmosphere. XRD
patterns of the NiO/Ni substrates are in Fig. 2.
4853
Fig. 2. NiO/Ni substrates cleaned with (a) Reagent I (acetone and alcohol) and (b)
Reagent II (toluene, acetone and methanol).
In Fig. 2, curves (a) and (b) are XRD patterns of the NiO/Ni sub-
strates cleaned with Reagent I and Reagent II, respectively. From the
two curves, the relative intensity ratios of NiO (2 0 0) to Ni (2 0 0)
peak (INiO(2 0 0) /INi(2 0 0) ) are different. For NiO/Ni substrates cleaned
with Reagent I, INiO(2 0 0) /INi(2 0 0) < 1, as is shown in curve (a). Fur-
thermore, there are a few unknown phases in the substrate. While
for NiO/Ni substrates cleaned with Reagent II, INiO(2 0 0) /INi(2 0 0) > 1,
as shown in curve (b). Furthermore, the unknown phases disappear
or weaken. Therefore, NiO/Ni substrates cleaned with Reagent I is
decient in oxidation degree, which means that NiO layer is not
thick enough compared with substrate cleaned with Reagent II. As
a result, substrate cleaned with Reagent II is better in the fabrication
of NiO buffer layers.
Fig. 3(a)(c) shows digital images of sol spin-coated on NiO/Ni
substrates derived from different cleaning processes. Fig. 3(a) is
the image of the sol spin-coated on NiO/Ni substrate washed with
Reagent I. The dispersive droplet of sol can be seen after spin-
coating process owing to the large contact angle. While for NiO/Ni
substrate cleaned in the modied degreasing process (Reagent II),
the sol coating after spin-coating is uniform, as shown in Fig. 3(b).
Even after the drying process (150 C/10 min), only trivial shrink-
age can be seen as shown in Fig. 3(c), which demonstrates that the
uniformity of sol coating can be maintained. Optical microscope
are adopted to monitor the detailed difference in the wettabil-
ity of the two types of NiO/Ni substrates to sol before and after
spin-coating process, as shown in Fig. 4(a)(d). Fig. 4(a) and (c)
is surface images of NiO/Ni substrates treated by different pro-
cess, and Fig. 4(b) and (d) is the corresponding surface image of
Fig. 4(a) and (c) after spin-coating, respectively. Compared with the
NiO/Ni substrate cleaned with Reagent I, wettability of NiO/Ni sur-
face to sol is remarkably enhanced after cleaning with Reagent II,
which is in consistent with result of Fig. 3. Therefore, the modied
degreasing-oxidization treatment is superior to conventional sur-
face treatment in improving the surface wettability of substrate to
sol.
In fact, the investigations on the cleaning process for Ni sub-
strates have been carried out for many years. Some cleaning pro-
cesses such as ash pickling and chemical cleaning [18] have been
proved to be effective in reducing contamination attached on the
nickel surface, yet these cleaning processes are difcult to control.
Therefore, it is necessary to nd a simple and effective candidate
to clean the surface of Ni substrates. The impurities in Ni sub-
strates typically contain some dust and some organic substances
brought in the preparation procedure. These organic contaminants
may be different in polarity, and some of these contaminants
4854 H. Yang et al. / Applied Surface Science 258 (2012) 48524856

Fig. 3. Photograph of sol spin-coated on different NiO/Ni substrates: (a) substrate cleaned with Reagent I; (b) substrate cleaned with Reagent II; (c) substrate cleaned with
Reagent II followed by drying process.

Table 1
Polarity list of different solvent at room temperature.

Solvent Toluene Acetone Methanol Alcohol De-ionized water

Temperature ( C) 20 25 25 25 20
Dielectric constant 2.4 20.7 32.6 24.3 80.4

such as parafn are not easy to be removed by acetone and alco-
hol because of their weak polarity. The remnant impurities may
react during the heat treatment to form other impurities which
are difcult to decompose even at high temperature. As a result,
the oxidation process is inuenced and NiO layer derived is unde-
sirable. In view of the mentioned-above, the modied process is
performed by applying a degreasing sequence in toluene, acetone
and methanol followed by an ultrasonic cleaning in de-ionized
water. The polarities of the different solvent are list in Table 1.
Toluene is weak in polarity, and it can get rid of organic con-
taminants with weak polarity, acetone and methanol can remove
organic contaminants with medium polarity and de-ionized water
can remove some inorganic contaminants with strong polarity. In
this way, the degreasing-oxidization process can be carried out
favorably, and the treated substrates are stored in methanol to
maintain the cleaning surface from dust. Consequently, dense NiO
layer with desirable surface wettability is obtained, which is favor-
able to the subsequent preparation of uniform BSCCO coating.
3.2. Preparation of BSCCO lm
DTA-TG analysis was adopted to investigate the desirable heat
treatment process for the preparation of BSCCO coating, as shown
in Fig. 5. Three temperature region of reaction can be seen as fol-
lowing: 1. Room temperature-220 C. A remarkable weight loss
takes place from 150 C to 220 C. Besides, a obvious endothermic

Fig. 4. Optical microscopic images of Ni substrates cleaned with Reagent I before (a) and after (b) the process of spin-coating, and Ni substrates cleaned with Reagent II
before (c) and after (d) the process of spin-coating.
 H. Yang et al. / Applied Surface Science 258 (2012) 48524856 4855

Fig. 5. DTA-TG analysis of sol.

reaction takes place when the temperature is higher than 218 C. Fig. 7. XRD patterns of BSCCO lm prepared on the NiO/Ni substrate with different
Therefore, evaporation of water and decomposition of ammonium sintering temperature. The sintering temperatures of samples 1#5# is 830, 840,
850, 855 and 860 C, respectively.
nitrate take place in this temperature region; 2. 220500 C. There
is a strong endothermic peak accompanied with obvious weight
loss in the range of 440500 C, which is attributed to the decom- with other impurities instead of Bi2212 single phase are obtained in
position of organic substance; 3. 500900 C. There is no obvious sample 3#. Therefore, the current works demonstrate that NiO/Ni
weight loss in this temperature region. In addition, a diffused peak substrate treated with the modied degreasing-oxidization pro-
occurs from 800 C to 880 C, which hints that a series of phase reac- cess is suitable for the preferential growth of BSCCO grains. And
tion instead of the single one take place in this region, and Bi2201, it is necessary to further optimize the experimental parameters to
Bi2212 even Bi2223 phase can be formed. improve the purity of Bi-2212 phase.
In view of the result of DTA-TG analysis and our former investi- The respective lattice mismatch of NiO to Bi-2212 and Bi-2201
gation [2123], the heat treatment process is set as shown in Fig. 6. phases are about 30% and 22%, which are too large for preferential
The drying temperature is set at 150 C to preserve the uniformity or even epitaxial growth of BSCCO grains. According to this, former
of precursor lm; the preheated temperature is respectively set as efforts have been focused on the preparation of heterogeneous
260 C and 500 C to decompose ammonium nitrate and organic; buffer layers such as CeO2 , YSZ, to decrease the mismatch between
the sinter temperature is set around 850 C (830860 C), and sin- substrate and BSCCO lms. This effective way, however, enhance
tering time is 1 h. the difculty and cost of BSCCO lms preparation. It is very inter-
XRD patterns of samples derived are shown in Fig. 7. The sin- esting that the preferential orientation of BSCCO lms on NiO/Ni
tering temperature for samples 1#5# is 830, 840, 850, 855 and
860 C, respectively. It is clear that BSCCO phases experience the
process from single Bi2201 phase to the mixed phase of Bi2212 and
Bi2201 from 830 C to 850 C; afterwards, with the temperature
increase to 855 C, Bi2201 phase with little intergrowth phase of
Bi2212 and Bi2201 phase is formed; at last, Bi2201 phase disappear
when the temperature raised to 860 C. In addition (0 0 1) prefer-
ential orientation can be obtained in samples 2# and 3#. Therefore,
the desirable sintering temperature is 840 C for Bi2201 phase and
850 C for the mixed phase. In view of the potential application of
BSCCO lm, it is a pity that the mixed phases of Bi2212 and Bi2201

Fig. 8. Schematic lattice matching diagram between BSCCO and NiO, in which the
Fig. 6. Heat treatment process for the preparation of BSCCO lms. [1 1 0]NiO direction is oriented parallel to [1 0 0]BSCCO.
4856 H. Yang et al. / Applied Surface Science 258 (2012) 48524856
Fig. 9. SEM image of BSCCO lm prepared on the NiO/Ni substrate cleaned with
Reagent II.
lms can be realized in our experiment. In fact, some oxides such
as MgO were used as substrates for the epitaxial growth of BSCCO
phase [24], while the crystal structure and lattice constant of NiO
(a = 0.418 nm) are similar as MgO (a = 0.421 nm). Therefore, similar
as epitaxial growth of BSCCO phase on MgO substrate, it is possi-
ble to realize the preferential or even epitaxial growth of BSCCO
lms directly on NiO/Ni substrates through the orientation rota-
tion of BSCCO crystal in a-b plane, as shown in Fig. 8, in which the
[1 1 0]NiO direction is oriented parallel to [1 0 0]BSCCO . In this case,
the lattice mismatches between NiO to Bi-2212 and Bi-2201 grains
are about 9% and 10%, which is the same as the mismatch between
MgO and BSCCO phase. As a result, it is feasible to grow BSCCO lm
with preferential orientation. The reason of this interesting orien-
tation rotation growth mode of BSCCO may be attributed to the
spontaneous nucleation orientation of BSCCO under certain ther-
modynamic condition to decrease the lattice mismatch energy, and
the related investigation is in progress.
The surface morphology of the BSCCO lm is observed by SEM.
As shown in Fig. 9, a smooth surface of the lm can be obtained in
a large scale and no macroscopic cracking is found. In addition, the
thickness of BSCCO coating is about 1 m according to SEM image of
cross-section of sample. Therefore, the distortion of BSCCO lattice
is low enough to the preparation of BSCCO lms with good sur-
face morphology, which is in consistent with the schematic lattice
matching model preliminarily. The further evidence of the model
cannot be given for the current experimental results, and we are
going to address this question by TEM and HRTEM analyses. Con-
sequently, it can be obtained preliminarily that NiO/Ni substrate
without heterogeneous buffer layer is feasible to prepare BSCCO
lms with preferential orientation.
4. Conclusions
NiO/Ni substrate treated with the modied degreasing-
oxidization process is superior to the one treated with conventional
process in enhancing the surface wettability to sol, and uniform
BSCCO lms prepared successfully on the substrates. The investi-
gation provides a novel viewpoint on the lattice matching mode of
interface between homogenous buffer layer and BSCCO lms.
Acknowledgements
This work was supported by the National Science Founda-
tion of China (Grant No. 51172040). The authors would like to
acknowledge Professor Yafeng Lu from Northwest Institute for
Nonferrous Metal Research for the offer of Ni substrates, and Dr.
Xiaodong Zhang and Hao Zhu from General Hospital of Shenyang
Military Area Command for their encourage and suggestions during
the experiment.
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