Applied Surface Science 258 (2011) 3843

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Applied Surface Science

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

The preparation of c-axis epitaxial Bi-2212 lms on STO(1 0 0) by solgel method

Xiaoming Yu a,c , Huazhe Yang b,c , Yang Qi a,d,
a
Institute of Materials Physics and Chemistry, School of Sciences, Northeastern University, Shenyang 110004, PR China
b
Department of Biophysics, College of Basic Medical Science, China Medical University, Shenyang, 110001, PR China
c
Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, PR China
d
Key Laboratory for Anisotropy and Texture of Materials, Ministry of Education, Northeastern University, Shenyang 110004, PR China

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

Article history: Bi2 Sr2 Ca1 Cu2 O8+ (Bi-2212) lms were grown on (1 0 0) oriented SrTiO3 (STO) substrate using solgel
Received 8 June 2011 spin-coating method. The effects of heat treatment conditions and coating times on the phase formation
Received in revised form 2 August 2011 and surface morphology were investigated using thermal analysis, optical microscope, X-ray diffraction,
Accepted 2 August 2011
and scanning electronic microscopy. Mixed phases were formed from 820 to 840 C, and Bi-2212 single
Available online 6 August 2011
phase was obtained at 830 C for 3 h. c-axis epitaxial lms with smooth surfaces were obtained by drying
at 600 C and coating for 5 times.
Keywords:
2011 Elsevier B.V. All rights reserved.
Bi2 Sr2 Ca1 Cu2 O8+ lms
STO(1 0 0)
Solgel
Morphology

1. Introduction
Up to date, Bi2 Sr2 Can1 Cun O2n2 (BSCCO) superconductors have
inspired intensive concerns owing to its high Tc , absence of
rare element and excellent physical properties [15]. A lot of
investigations on epitaxial growth of BSCCO lms have been
reported in order to obtain Josephson superconducting devices
[69].
BSCCO lms have been prepared by various physical meth-
ods [1013]. However, these methods are restricted by vacuum
apparatus, which consumedly enhances the cost and difculty
of preparation. Therefore, an economical and simple method is
in urgent need. Some chemical methods such as metalorganic
decomposition (MOD) [14,15] are adopted to fabricate BSCCO lm,
but the raw material is toxic and expensive and the reaction is
not convenient to adjust. However, solgel technique is one of
the most effective way to prepare lms because of low cost, easy
handling, molecular level homogeneity [16,17], and it is especially
suitable for the preparation of multicomponent cuprate super-
conductors oxide lms such as BSCCO and YBa2 Cu3 Ox (YBCO).
The YBCO lms on different kinds of substrate [1720] have been
investigated, while the works for aggregation-free and better grain
connectivity are in progress. However, the report on the fabrica-
tion of BSCCO lms by solgel method is relatively rare, and the
adoption of alkoxide has also increased the cost of this method
[21]. In the meanwhile, the evaporation of water and decomposing
of chelator induce the shrinking of precursor lms, which could
be the reason for degeneration of the component homogeneity
and integrity of surface in cuprate superconductors oxide lms.
Therefore, the quality of lms that affect the electrical transport
properties needs to be further improved. Our group [22] recently
found that compared with other technique [2325], the Pechini
gel process had a remarkable effect on the component homogene-
ity of precursor gel and thereby can enhance the properties of
BSCCO powders, providing a potential process to improve the phase
purity and crystallinity of BSCCO lm by solgel method. How-
ever, experimental parameters to fabricate epitaxial BSCCO lms
with high properties by this Pechini method have not been inves-
tigated.
In this paper, BSCCO lms were prepared on STO(1 0 0) substrate
by solgel method. The effect of drying process, coating times and
heating conditions on quality of lms were investigated in detail.
The surface morphology and phase purity of Bi-2212 lm was
improved, and cracks were eliminated by optimal parameter. This
was the preliminary study for the preparation of superconducting
devices.

Corresponding author at: Institute of Materials Physics and Chemistry, School
of Sciences, Northeastern University, Shenyang 110004, PR China.
Tel.: +86 024 83678479; fax: +86 024 83683674.
E-mail address: qiyang@imp.neu.edu.cn (Y. Qi).
2. Experimental
Single crystal STO(1 0 0) wafer was adopted as substrate.
Analytical reagent Bi(NO3 )3 5H2 O, Sr(NO3 )2 , Ca(NO3 )2 4H2 O and
Cu(NO3 )2 3H2 O were used as reactants in a molar ratio of

0169-4332/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.08.002
 X. Yu et al. / Applied Surface Science 258 (2011) 3843 39

Table 1 3. Results and discussion

Experimental conditions.

Sample Coating times Sintering temperature ( C) Heating-up time (h) 3.1. Effect of TEA
1# 10 820 1
2# 10 825 1 The complexation is in optimized state with the pH 7 for EDTA,
3# 10 830 1 and TEA is used for adjusting pH. Effect of TEA on the formation of
4# 10 835 1 Bi-2212 has been investigated by our preliminary work [22]. How-
5# 10 840 1
ever, function of TEA on the preparation of BSCCO lms is not clear.
6# 10 830 2
7# 10 830 3 In the investigation, role of TEA is as follows:
8# 10 830 4
9# 10 830 5 1. Stabilization of sol. It is hydrogen bond that links the sol network,
10# 10 830 6
11# 7 830 5
but it is so easy to breakdown during drying even spin-coating
12# 5 830 5 process, which could degenerate the nal surface morphology
of lm. The three branch of ethyl hydrate in TEA structure as
shown in Fig. 1 could inset into the network, which maintain
and stabilize the structure even though the hydrogen bond is
broken.
2. Good inltration. Because of ideal intersolubility with water and
working as chelate, TEA improves the inltration of sol with STO
substrate that decides the degree of spreading out for sol. Uni-
Fig. 1. The ionization equilibrium of TEA. form coating of sol on substrate is the primary step for nal
smooth surface morphology of lm.
3. Stable pH. The ammonia is widely used to adjust pH for its cost
effective and good intersolubility with water. But the decrease
Bi:Sr:Ca:Cu = 2:2:1:2, and ethylenediamine tetraacetic (EDTA) as of pH due to evaporation of ammonia degenerate the complex-
chelating agent to obtain blue sol. The pH was maintained at 7 ation of EDTA. The ionization reaction of TEA as shown in Fig. 1
with the injection of triethanolamine (TEA). Then, the blue sol was is reversible, and the concentration of OH is kept as a constant.
heated in water bath at 65 C to get proper viscosity. The sol was TEA acts as buffering agent to maintain the pH with 7.
spin-coated on STO substrate and dried to form precursor lm. The
whole process was repeated to get a certain thickness. Finally, the 3.2. Drying process
BSCCO lm was obtained by sintering at different temperature for
3 h. Experimental conditions were list in Table 1. X-ray diffraction Fig. 2(a) shows the TG/DTA curves for the precursor gel heated
(XRD, Cu K), thermal analysis (DTATG), optical microscope, and from room temperature (RT) to 860 C. TG curve reveals that after
scanning electronic microscopy (SEM) were performed to inves- the initial loss of water, a single sharp mass loss occurred from
tigate the crystallinity, thermal stability and surface morphology, 200 to 250 C. The evaporation of bound moisture in gel net-
respectively. work and decomposing of NH4 NO3 contributed to this stage. The

Fig. 2. DTATG curves of the gel and optical microscopy photos of precursor lm with different drying temperature.
40 X. Yu et al. / Applied Surface Science 258 (2011) 3843
Fig. 3. XRD patterns of samples with different sintering temperature.
exothermal peak at about 230 C originated from the decompos-
ing of NH4 NO3 . From 250 to 450 C, the evaporation of TEA caused
gradual mass loss. Then, another sharp loss took place from 450
to 540 C, while exothermal peak also occurred at this stage. The
decomposition of nitrate and EDTA contributed exothermal peak.
Above 540 C, mass loss is almost zero, and the disperse peak
reveals that the reaction at this stage is not a single one but a
complicate course.
Base on the TG/DTA curves, the drying temperature of precur-
sor lm is investigated deeply. The precursor sol loses uidity to
form precursor lm through drying process, and the nal surface
morphology of lm intensively depends on drying process. Dry-
ing at 400 C as shown in Fig. 2(b), the gel aggregates to form
porous frame due to the evaporation of water, TEA, and decom-
posing of NH4 NO3 . In Fig. 2(c) at 550 C, the decomposition of
nitrate and EDTA take place at this stage. The uniform surface of
the frame become porous and eventually frame is nearly trans-
parent, the reason is that EDTA is decomposed and its products
evaporate with only metal element left. Heating rapidly to 600 C,
the frame is nearly the same as Fig. 2(c) and the evaporation
and decomposing of matter is accomplished instantly. The gel is
nearly xed at its original spot without further shrinking. Com-
paring with gradual drying process at low temperature, there
is no component segregation due to the different dissolvability
among reactants for drying at higher temperature. Meanwhile,
the morphology for precursor lm becomes more uniform drying
at 600 C.
3.3. The effect of sintering temperature on phase purity
It is known that sintering temperature is one of the most impor-
tant parameters for the preparation of Bi-2212 lm. In this part, the
inuence of sintering temperature on phase purity is investigated.
Fig. 3 is the XRD patterns of Bi-2212 lm with different sin-
tering temperature. According to standard JCPDS data, the purity
of Bi-2212 phase improved with the sintering temperature up to
830 C and degraded with further increase of temperature. The
mixed phase is obtained when the temperature is 820 C. Increasing
temperature to 830 C, (0 0 ) peaks are displayed in XRD pattern
for sample 2#. The single Bi-2212 phase was obtained and growth
orientation is c-axis epitaxial except for small amount of impurity.
The Bi-2212 phase was decomposed with the temperature further
Fig. 4. XRD patterns of sample 3#, 610# with different heating-up time: 16 h.
increasing, and the diffraction peak of Bi-2201 and CaCu2 O3 can be
found. So the optimal sintering temperature for Bi-2212 is 830 C.
3.4. The effect of heating-up time on surface morphology
According to the DTATG analysis, a relatively broad disperse
peak appeared from 600 C to 860 C. For BSCCO lms, each element
partial melts and diffuses each other during phase formed process.
The dome peak originated from the synthesis reaction, which is so
complicated and slow to broaden the exothermic peak. The pri-
mary stage of diffusion of various elements will ultimately affect
the phase purity and surface morphology of lm, so the heating
processes from 600 C to the target temperature (830 C) need to
be investigated deeply. Samples 3#, 6#, 7#, 8#, 9# and 10# are
prepared varying heating-up time from 1 to 6 h.
As shown in Fig. 4, Bi-2212 is the main phase with a little
Bi-2201 and some impurities such as CaCuO2 and CaCu2 O3 . The
Bi-2212 peaks become sharper with increasing heating-up time,
which means the crystallization of thin lm is improved obvi-
ously. (0 0 2), (0 0 6) and (0 0 1 2) peaks of Bi-2201 appeared and
strengthen increasing the heating-up time from 1 to 4 h. The sam-
ple 7# has the strongest (1 1 5) peak of Bi-2201 at 2 = 29.6 and
the maximum peak of CaCu2 O3 . The c-axis epitaxial peak of Bi-
2201 reached the maximal for sample 8#, while non-epitaxial
(1 1 5) peak and the CaCuO2 impurity peak began to diminish. For
sample 9#, there are only (0 0 ) epitaxial peaks of Bi-2212. The
Bi-2201 and non-epitaxial Bi-2212 peaks for sample 10# appear
again with increasing the heating-up time. Because of relatively
wide phase-formed temperature zone, the Bi-2201 phase began to
form when the temperature is within its phase-formed tempera-
ture zone. Then, the CuCaO2 structural units will have enough time
and energy to insert into the formed Bi-2201 to form Bi-2212 phases
with increasing of heating-up time, which make the crystallization
and phase purity of the sample improve greatly. Therefore, sam-
ple 9# with 5 h heating-up has the best epitaxial characteristics of
Bi-2212 phase and least impurity peaks.
Table 2 displays the FWHM of (0 0 2) peaks and the proportion of
non-epitaxial to epitaxial for Bi-2212 phase with different heating-
up time. As the increasing of heating-up time, the FWHM (0 0 2)
decreases from 0.561(sample 3#) to 0.321(sample 8#) and reach
to a minimum 0.300 for sample 9#, then increases again to 0.339
 X. Yu et al. / Applied Surface Science 258 (2011) 3843 41

Fig. 5. SEM micrographs of samples with different heating-up time, sample 3#, 610#: 16 h.

(sample 10#). As for the proportion of non-epitaxial to epitaxial, and Ij,n are the integrated intensity of diffraction line n of phase i
the weight fraction of phase, Xi [26,27], is calculated as follow: and j respectively, and m is the number of phases in the mixture.
As shown in Table 2, the proportion of epitaxial for Bi-2212 phase
increases from 81.5% (sample 3#) to maximum of 96.4% for sample
 
Ih k li 1 9#, and decreases again with the increasing of heating-up time.
Xi = (1) In a word, the sample 9# with 5 h heating-up time has the best
Ki,n m
crystallization performance as well as the maximum proportion of
(Ih k l j /Kj,n )
epitaxial for Bi-2212 phase.
j=1
Fig. 5(a) shows the surface morphology of sample 3# heating-up
where Xi is the unknown weight fraction of phase i in the sample, for 1 h, layer structure are divided into upper and lower levels that
Ki,n and Kj,n are the RIR for diffraction line n of phase i and j, Ii,n can be seen clearly. The lower layer is relatively smooth, and the

Table 2
Parameters of different heating-up temperature.

Samples 3# 6# 7# 8# 9# 10#

Heating-up time 1h 2h 3h 4h 5h 6h
FWHM (0 0 2) 0.561 0.384 0.366 0.321 0.300 0.339
Epitaxial phase (Bi-2212) 81.5% 88.8% 89.8% 92.2% 96.4% 92.3%
42 X. Yu et al. / Applied Surface Science 258 (2011) 3843
Fig. 6. XRD patterns of samples with different coating times, sample 9#, 11#, 12#:
10, 7, 5 times.
upper layer is not continuous. The layer structure is formed owing
to faster a, b-axes growth rate than that of c-axis. In Fig. 5(b), the
non-continuous situation of the upper layer is improved. It began
to link together when heating-up time is 2 h, but there are a lot of
holes on the surface. In Fig. 5(c and d), further increasing heating-up
time, the holes on surface gradually decrease and the layers struc-
ture trend to join together. In Fig. 5(e), the surface is uniform and
smooth for 5 h heating-up time. In Fig. 5(f), the surface morphology
of the sample is not changed signicantly except for some overlap-
ping lath structures. The phenomena can be explained as following:
the elements began to diffuse when the temperature is 600 C and
react with each other proved by the emergence of at exothermic
Fig. 7. SEM micrographs of samples with different coating times: (a) 10, (b) 7, (c) 5 times.
peak in the DTATG curves after 600 C. With the increasing of
heating-up time, the pores caused by evaporation and decompos-
ing of precursor from the gel can be relled with the diffusion of
elements, which became more sufcient. In this way, smooth and
uniform surface of lm is obtained.
3.5. The impact of spin-coating times
Sample 9# possess nearly pure Bi-2212 phase, best surface mor-
phology and crystallization, so the same heating conditions for
sample 11# and 12# are chosen with 7 and 5 spin-coating times,
respectively. Fig. 6 is the XRD pattern of samples with different
spin-coating times. The character of c-axis epitaxial growth of Bi-
2212 phase is display for all the three samples except for a small
amount impurity. With the decreasing of spin-coating times, the
thickness of lm also decreases, but the relative intensity of etch
peak increase obviously.
In Fig. 7(a), sample 9# has the relatively smooth surface except
for some lath structure. In Fig. 7(b), lath region can also be seen for
samples 11#. The surface can be divided into three parts accord-
ing to the height from top to bottom. A large number of particles
appear on top layer, microscale ake in middle layer, and large-
scale ake on bottom layer. Sample 12#, spin-coating for 5 times,
has a large area of layer structure. It is obvious that the growth pat-
tern is 2-dimension. Besides some microscale particles, the surface
becomes uniform and smooth without any pores. Because of island
growth mode, these particles grow up around nucleation centers,
and ultimately form ake structure as shown in Fig. 7(c).
To study the difference of superconducting performance among
these samples, temperature dependence of resistance for sample
is shown in Fig. 8. For sample 9#, with the decreasing of temper-
ature, resistance experience a increasing, slightly decreasing and
increasing process. This result is contributed to the competition
between the character of superconductor and semiconductor. The
 X. Yu et al. / Applied Surface Science 258 (2011) 3843
Fig. 8. RT curves for samples with different coating times.
superconducting transformation begins at 95 K, and superconduct-
ing character is the main feature. In other condition, semiconductor
character is the key part. Sample 11# has the similar character
with sample 9#, the only difference is that the resistance straight
decreases to minimum of 273.3  after initial increasing. For sam-
ple 12#, T(c,onset) is 97.7 K, and the residual resistance is about 2 .
The origin of residual resistance may be attributed to grain bound-
ary and impurity. So sample 12# has the better superconducting
property.
Therefore, c-axis epitaxial Bi-2212 lm with uniform and
smooth surface morphology is obtained through 5 spin-coating
times.
4. Conclusions
Experimental parameters to prepare c-axis epitaxial BSCCO
lms with smooth surfaces were investigated. The desirable pre-
cursor lm was obtained through drying sol coating at 600 C and
coated for 5 times, and the epitaxial BSCCO lm was then obtained
sintering at 830 C for 3 h. The investigation provides an optimal
process to obtain Bi-2212 lms, which contribute to the preparation
of superconducting devices.
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