Journal of Alloys and Compounds 385 (2004) 3343

Synthesis and characterization of Er-substituted Bi-2223 H-Tc

glassceramic superconductors
Mehmet Ali Aksan , Mehmet Eyyphan Yakinci

Inn
niversitesi, Fen Edb. Fakltesi, Fizik Blm, 44069 Malatya, Turkey
Received 15 September 2003; received in revised form 20 April 2004; accepted 22 April 2004

Abstract
The Bi2 Sr2 Ca2 Cu3x Erx O10+ (x = 0.5 and 1.0) H-Tc system was prepared by glassceramic technique to investigate the microstructural
formation, thermal and transport properties. We have found that Er+3 ions have a solid solubility limit in the Bi-2223 system and this limit was
passed at x = 1.0. Below this limit glass samples were prepared and converted to the glassceramic form easily, but after the solid solubility
limit glass formation was diminished and crystallized samples were formed after melt quenching. The substitution had considerable effect
on the electrical properties comparing with the unsubstituted Bi-2223 material. The Tc values of the x = 0.5 and 1.0 sample were found to
be 71 0.1 K. The thermoelectric power data were analyzed in view of two band model with linear T-term and Xins two band model.
Thermoelectric power was obtained to be positive for the both samples, indicating that the hole type conductivity is dominant in the materials
prepared. The magnitude of thermal conductivity, , was also influenced by the Er concentration. When the Er concentration was increased
the magnitude of was suppressed. It strongly indicates that the impurities play a significant role in limiting the heat transport due to a strong
increase of the electronphonon-impurity scattering rate.
2004 Elsevier B.V. All rights reserved.
Keywords: Er-substituted Bi-2223; Glassceramic superconductors; BSCCO system; Thermal conductivity; Thermoelectric power

1. Introduction
It is interesting to alter the electronic structure of the
CuO2 planes by substitutions and thus the superconducting behavior of BSCCO system. Substitutions indicated
a dramatic effect on the Tc values of the systems. It has
been clearly seen that there are no significant differences
in the strengths of Tc suppression between magnetic and
non-magnetic substitutions in the BSCCO materials [1,2].
It should be emphasized that the Tc values of the systems
prepared decreased due to the impurities which cause the
scattering of the carriers in the CuO planes and/or due to
the variation of the carrier concentration by substitutions
[39]. The suppression of Tc due to the substitution of the
other elements for Cu has been attributed to the Abrikosov
and Gor kov pair breaking mechanism [10,11]. An increase
or decrease in the hole concentration in the CuO2 planes
and carrier localization induced by the structural disorders
are also useful to explain the decrease in Tc [12,13].

Corresponding author.
E-mail address: maksan@inonu.edu.tr (M.A. Aksan).

0925-8388/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2004.04.135

Thermoelectric power (TEP) investigation in solids is

one of the basic tools to understand the nature of charge
carriers which are responsible for the conduction process.
There have been many studies done on the TEP properties
of the high-Tc glassceramic BSCCO material. In most of
them, substitution effect on TEP properties, particularly for
the Bi-site, have been investigated [10,11,1419]. Most of
the works indicated either positive or negative TEP properties depending on the compositions and doping level or
preparation conditions. However, there exist few works on
substituting other elements, such as Fe and Ti, for Cu particularly in the glassceramic BSCCO system [10,15,16].
The most important observation is that the underdoped systems have positive and large TEP value which also shows
temperature-independent nature particularly at high temperatures, whereas the overdoped systems have negative and
small TEP values and varies almost linearly with temperatures. However, for the optimum carrier concentration case,
the value of TEP increases with temperature and reaches
the maximum at around Tc and then decreases. For the
TEP investigations on high-Tc materials, some important
models have been developed. But, no consensus has been

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M.A. Aksan, M.E. Yakinci / Journal of Alloys and Compounds 385 (2004) 3343

attained among the models developed. Some models have

been particularly used for high-Tc BSCCO materials, which
are: two band model with linear T-term [20]; NagosaLee
model [21]; phenomenological narrow band model [22];
Xins two band model [23]; three-state model [24]; and
HubbardHamiltonian model [25].
Thermal conductivity, (T), investigation also gives important information about the scattering mechanism of
charge carriers, electronphonon interaction and other physical properties such as carrier density and phonon mean free
path [2631]. In the last decade, there were many investigations have been made on (T) of high-Tc materials [2637]
and almost the same results were obtained. In general, for
(T) investigation of high-Tc materials three important approaches can be considered to the total (T) calculations: (i)
phonon contribution; (ii) electron contribution; and (iii) both
electron and phonon contributions. Many research groups
have investigated these valuable approaches for high-Tc
materials and results were reported [27,3235,3841].
However, there exits a difficulty on the (T) properties
of the high-Tc materials. In particular, compared with conventional metallic structures, the high-Tc superconductors
show unusual behavior just below their Tc . At that point,
thermal conductivity rises and reaches to the maximum and
then drops sharply. The explanation of the rapid rise and
the maximum point seen in a wide range just below Tc , is
summed up the two main points [26]. Firstly, decrease on
the scattering mechanism, because of the superconducting
state (T < Tc ), and secondly, an increase in the electron
mean free path due to decrease in the phonon scattering.
In many investigations, the value of the maximum was
also found to depend on the preparation method and/or the
chemical compositions [4247]. However, it is also important to see the effect of the quasi-particle contribution on
the rapid rise of (T) below the Tc as explained by many
groups [35,41]. There exist some other models that have
been widely accepted for materials in solid state. Particularly, for the graded materials, effective medium approximation (EMA) [36,48,49] and another model developed
particularly for the conventional low-Tc superconductors
by Bardeen et al. [50] that describes the phonon thermal
conductivity in the superconducting state. This model then
generalized by Tewordth and Wolkhausen in order to describe the phonon thermal conductivity of high-Tc superconductors in a wide range of temperatures [39]. However,
still many efforts have to be made both experimentally and
theoretically to understand the (T) mechanism of high-Tc
materials.
In the present study, we have prepared Bi2 Sr2 Ca2 (Cu3x
Erx )O10+ , where x = 0.5 and 1.0, high-Tc superconducting materials by glassceramic technique. There has been
no report found on the synthesis and characterization of
Bi2 Sr2 Ca2 (Cu3x Erx )O10+ glassceramic system in the literature and we have reported the crystallization, microstructure, electrical, TEP and (T) properties of these materials
for the first time.

2. Experimental
Glass samples with nominal compositions of Bi2 Sr2 Ca2
Cu3x Erx O10+ , where x = 0.5 and 1.0, were prepared by
the glassceramic technique. High grade (99.99%) oxide
powders of Bi2 O3 , SrCO3 , CaCO3 CuO and Er2 O3 were
mixed mechanically for 3 h. The mixture was melted in an
-alumina crucible at high temperature furnace between
1050 and 1250 C for 30 min to 3 h, which depends on the
composition. Molten mixture was poured onto a cold copper
plate and pressed quickly with another cold plate. Rapidly
quenched, dark, shiny and approximately 13 mm thick
amorphous materials were obtained. The glass samples prepared were then heated in P.I.D. controlled tube furnace in
oxygen atmosphere at 850900 C for 60240 h, depending on the substitution level. The optimum heat treatment
condition of each composition was derived from XRD,
SEMEDX, resistance and DTA results. The optimum
conditions were found to be 890 C/240 h for the x = 0.5
sample and 900 C/240 h for the x = 1.0 sample (Table 1).
After x = 1.0 substitution level, no glass formation was obtained even at very high temperature range, 12001250 C,
therefore, those samples were not investigated.
All samples prepared in this work were firstly examined
by X-ray diffraction analysis (XRD) to find out whether they
were fully amorphous or not. After heat treatment cycles,
samples were also investigated by XRD analysis to find out
the structural evaluation. All XRD analysis was performed
by using Rigaku RadB X-ray diffractometer with Cu K
radiation and a constant scan rate of 2 = 360 with a
0.2 /min scan rate.
Microstructural investigations were performed using Jeol
6400 scanning electron microscope (SEM) combined with
an energy dispersive X-ray analysis (EDX).
Differential thermal analysis (DTA) was used to determine the nature of the phase transformations within the materials prepared. During the DTA investigations 20 mg well
grained powder of each sample was examined between room
temperature to 1000 C using -alumina reference material
with automated Shimadzu network system 60 equipment.
The electrical property of the samples was carried out using a computer controlled four probe dc resistance measurement system with closed cycle He refrigerator (Leybold LT
10 system). Conductive silver paint was used for contacts.
Thermoelectric power (TEP) measurements were carried
out using the closed cycle refrigerator. The samples were
clamped between two thin copper plates. One of the copper
plates was placed on the cold head of the system and the
other on the top of the samples. Temperature gradient (established) from the cold to the hot part of the sample was kept
at
T 2 K through the measurements using 25  heater.
Voltages were recorded using Keithley 182 nano-voltmeter
and the temperatures were monitored with two calibrated
silicon diodes. The thermal conductivity, (T), measurements of the glassceramic samples were performed using
steady-state heat flow method using closed cycle refrigera-

M.A. Aksan, M.E. Yakinci / Journal of Alloys and Compounds 385 (2004) 3343

35

Table 1
Summary of the preparation conditions and physical properties of the samples, optimum: optimum treatment condition, p: hole concentration value per
Cu atom
Material (x)

Condition

Heating parameters
Temperature

( C)

Time (h)

Atmosphere

Tc (K)

Tzero (K)

T (K)

0.5
0.5
0.5
0.5
0.5
0.5

Non-optimum
Non-optimum
Optimum
Optimum
Optimum
Non-optimum

870
880
890
890
890
900

240
240
60
120
240
240

O2
O2
O2
O2
O2
O2

44
55
64
70
71

25
25
29
41
46

19
30
35
29
25

0.245
0.237
0.231
0.226
0.225

1.0
1.0
1.0
1.0
1.0
1.0
1.0

Non-optimum
Non-optimum
Optimum
Optimum
Optimum
Non-optimum
Non-optimum

880
890
900
900
900
910
920

240
240
60
120
240
240
240

O2
O2
O2
O2
O2
O2
O2

42
53
70
70
71

21
22
36
37
44

21
31
34
33
27

0.246
0.239
0.228
0.226
0.221

1.5

Non-glassceramic

tor system. The bottom of the sample was fixed to the cold
head of the cryostat system and the upper part of the sample was attached to a heater (25 ) which had an indium
sheated surface. The temperature difference was recorded
using two silicon diodes attached to the both end of the
samples.
3. Results and discussion
3.1. X-ray diffraction investigation
Under the preparation condition used, it was found
that the high-Tc phase formation largely depended on the

heating time, as well as on the heating temperature. In

contrast with other substitutions in Bi-2223 glassceramic
material, such as Ga and Pb (where 100160 h thermal
treatment time at 830850 C is necessary for high-Tc
phase formation [51,52]) long time (200400 h depending
on x) and high temperature (890900 C depending on x)
in Er-substituted material favors the growth of the superconducting phase (Table 1).
Fig. 1 shows the XRD patterns of the glass materials
and glassceramic samples heat treated under the optimum conditions. The structural data have been calculated
(only for samples heat treated under their optimum conditions) by using the least-square fit of the X-ray lines. The

Fig. 1. XRD pattern of the Er-substituted samples: (a) x = 0.5 glass sample, (b) x = 1.0 glass sample, (c) x = 0.5 sample heat treated at 890 C for
240 h, and (d) x = 1.0 sample heat treated at 900 C for 240 h.

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M.A. Aksan, M.E. Yakinci / Journal of Alloys and Compounds 385 (2004) 3343

micro-qualitative data obtained from the SEMEDX have

been taken into account.
The XRD pattern of x = 0.5 and 1.0 Er-subtituted glass
samples are shown in Fig. 1a and b, respectively. A large
halo was obtained at around 2
= 30 , which is a fundamental characteristics of the glass material, indicates the
short-range atomic order and the absence of periodicity in
the three-dimensional network.
Fig. 1c shows the XRD pattern of the x = 0.5 sample heat
treated at 890 C for 240 h (optimum condition). The sample consists mainly of the Bi1.95 Sr1.98 Ca0.9 Cu1.3 Er0.42 O8+
phase and this is close to the Bi-2212 superconducting
phase. However, a small amount of the Bi-2223 superconducting phase was also obtained without any Er concentration. The impurity (solid solution) phases were identified
as Cu2 Er2 O5 and Bi6 Ca7 O16 . The crystal symmetry was
found to be tetragonal and the unit cell parameters were
calculated to be a (= b) = 5.4304 and c = 31.8545 . In
fact, these parameters were found slightly different than the
Bi-2212 phase (a (= b) = 5.3941 and c = 30.6013 )
[53].
For the x = 1.0 sample after the heat treatment at 900 C
for 240 h as its optimum condition, a slight change occurred in the main XRD pattern, Fig. 1d. In conjunction
with the SEMEDX analysis, the main phase was found to
be Bi1.94 Sr1.97 Ca0.9 Cu0.9 Er0.89 O8+ . The peak intensity of
the Cu2 Er2 O5 phase increased at least twice compared to x
= 0.5 sample. The Bi6 Ca7 O16 impurity phase was also obtained. In this sample, the tetragonal symmetry of the main
phase remained unchanged and had unit-cell constants a
(= b) = 5.8230 and c = 31.5132 , indicating a decrease
in the c-axis and an increase in the a-axis.
In general, substitution of Er has an effect on the CuO
bond length and therefore the unit cell parameters. The increase of the a-axis and the decrease of the c-axis are believed to be due to incorporation of Er ions into the interstitial

sites in the unit cell rather than occupation of the Cu sites.

Also, it is said that the atomic radius of Er3+ (r = 0.88 )
is bigger than Cu2+ (r = 0.72 ) atoms. If one can suppose the valance state of the Er ions is 3+ and remains unchanged in the matrix, it is inevitable that a distorted band
structure and thus a change on the unit cell dimension. However, to clarify this point at least Notron diffraction data or
high-resolution transmission electron microscope (HTEM)
work must be done.
3.2. Scanning electron microscopy (SEM) and energy
dispersive X-ray analysis (EDX)
The surface morphology and microanalysis of the samples
have been examined by SEM and EDX analysis. The surface
morphologies of the samples for x = 0.5 and 1.0 after heat
treated at their optimum condition are shown in Fig. 2a and
b, respectively. As seen in Fig. 2a, for the x = 0.5 sample,
randomly oriented flake-like grains were obtained, which is
the typical glassceramic BSCCO structure for long time
heat treated samples.
In the case of the x = 1.0 samples, slightly different surface morphology was obtained, Fig. 2b. Most of the flaky
grains have formed smaller than the x = 0.5 sample, but
some grains formed as 250300 m long whiskers. The
EDX analyses of whisker were showed single phase Bi-2212
composition without any contaminations.
The micro-qualitative analysis, the EDX result of polished
surface, of the x = 0.5 sample showed that the sample consists of four different phases, Bi1.95 Sr1.98 Ca0.9 Cu1.3 Er0.42
O8+ , Bi-2223, Cu2 Er2 O5 and Bi6 Ca7 O16 as denoted
zone 14 in Fig. 3a. In the case of the x = 1.0 samples, the EDX analysis showed that the main phase was
Bi1.94 Sr1.97 Ca0.9 Cu0.9 Er0.89 O8+ , the previously obtained
phases were grown together in the main matrix with similar
composition, Fig. 3b.

Fig. 2. The surface morphologies of the samples for: (a) x = 0.5 and (b) 1.0 after being heat treated at their optimum condition.

M.A. Aksan, M.E. Yakinci / Journal of Alloys and Compounds 385 (2004) 3343

37

Fig. 3. Polished surface morphology of the samples for: (a) x = 0.5 and (b) 1.0 after being heat treated at their optimum condition; (1) denotes
Bi1.95 Sr1.98 Ca0.9 Cu1.3 Er0.42 O8+ in the x = 0.5 sample/Bi1.94 Sr1.97 Ca0.9 Cu0.9 Er0.89 O8+ in the x = 1.0 sample, (2) Bi-2223, (3) Cu2 Er2 O5 , and (4)
Bi6 Ca7 O16 .

3.3. Differential thermal analysis (DTA) investigation

One of the important benefits of the thermal analysis
experiment is its usefulness in selecting appropriate (heat
treatment) temperatures for the heat treatment cycles of the
glassceramic materials as well as for the investigation of
the phase development.
The DTA curves of the x = 0.5 and 1.0 Er substituted
samples are shown in Fig. 4. A standard heating rate,
= 10 C/min, was used during the experiments. Before the
crystallization peak temperature an endothermic activity was
obtained at 490 C for both x = 0.5 and 1.0 samples. This
is the characteristic property of glass material as obtained
in the conventional glass samples, which is suggested that
both materials are in the glass form.
For the x = 0.5 Er-substituted sample, two exothermic
peaks were obtained at 509 and 547 C, Fig. 4a. The first
peak at 509 C corresponds to the nucleation assisted crystallization process, and the second peak at 547 C indicates the
formation of the impurity phases such as Cu2 Er2 O5 and/or
Bi6 Ca7 O16 . The exothermic activities at 781 and 890 C
correspond to the formation of the Bi-2201 and Bi-2212
phases.
Similar thermal activities have been obtained for the x
= 1.0 sample. However, the peak temperatures increased approximately 10 C, except the new peak obtained at 499 C
which is believed that large nucleation centers occur initially
and then convert rapidly to a crystalline form (Fig. 4b).
In general, basic properties of glass to glassceramic
phase transition have been obtained for both samples. Compared with the unsubstituted Bi-2223 material, no partial
melting activities (an endothermic dip which promotes single phase crystal growth in BSCCO) were obtained between
830 and 850 C. It is known widely that Er is an infusible
element particularly in the conventional glassceramic

matrices and that it is very difficult to prepare glass material

if high Er concentrations used in the initial batch [54].
In this work, we attempted to prepare glass sample with
high Er concentration, but failed. This suggests that the solid
solubility of Er in the Bi-2223 system is limited.
3.4. Electrical properties
The electrical resistance (RT) properties of the samples
prepared are summarized in Table 1 and RT plots of selected
samples are given in Fig. 5.
As shown in Fig. 5a, x = 0.5 sample after the heat treatment at optimum condition, has metallic behavior from room
temperature to the Tc value. The critical temperature, Tc ,
was found to be 71 0.1 K and the zero resistance was obtained at Tzero , 46 0.1 K.
The x = 1.0 Er-substituted sample, heat treated at 900 C
for 60 h, showed a semiconducting behavior from room temperature to the Tc value, Fig. 5b. The superconducting behavior started at 70 0.1 K and the Tzero value was reached
at 36 0.1 K. However, when the heat treatment time of
x = 1.0 sample extended to 240 h at the same temperature
(optimum condition), the electrical behavior changes significantly and metallic property was obtained (Fig. 5c). The Tc
and Tzero values were found to be 71 0.1 and 44 0.1 K,
respectively.
In general, it is found that superconducting property of
the samples decreases if the Er concentration increased in
the Bi-2223 system. The results suggested that the phase coherence of the main Bi-2223 structure may in some way be
destroyed. It is also believed that the intergrowth of impurity solid-solution phases in the main matrices (as obtained
by the XRD and SEM investigations) and the formation of
weak coupling between the grains play an important role in
decreasing of the superconductivity.

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M.A. Aksan, M.E. Yakinci / Journal of Alloys and Compounds 385 (2004) 3343

Fig. 4. DTA curves of the samples taken at heating rate of = 10 /min: (a) x = 0.5 sample and (b) x = 1.0 sample. Insert shows the temperature region
between 450 and 600 C.

system, hole concentration in the CuO2 planes is believed

to change significantly.

3.5. Hole concentration

The number of holes per Cu atom has been calculated
using the formula given by Presland et al. [55]:
Tc
= 1 82.6(P 0.16)2
Tcmax

(1)

where Tcmax is taken 110 K for the Bi-2223 system and P

the number of the holes per Cu. Recently, this equation was
successfully applied to the doped/substituted Bi-based superconducting system [5660]. Previous calculations for the
unsubstituted Bi-2223 material had shown that the P-value
ranged from 0.116 to 0.16. In this work, the P-value of the
x = 0.5 and 1.0 samples (after the heat treatment under the
optimum) has been calculated to be 0.225 and 0.221, respectively, Table 1. The results obtained shows that the P-value
of our samples is higher than the unsubstituted Bi-2223 system and thus our samples are in the overdoped region. Since
the cation state of Er is 3+, extra charge transfers to the

3.6. Thermoelectric power (S)

The thermoelectric power, S, versus temperature plots of
x = 0.5 and 1.0 samples are shown in Fig. 6. For uniformity,
S measurements have been performed only for samples after
heat treatment under their optimum conditions.
For x = 0.5 Er-substituted sample, positive S value was
obtained and decreased linearly down to 80 K and then
dropped to zero at 68 K, Fig. 6a. This behavior is consistent
with the fact that S vanishes at temperature corresponding
to Tc .
When Er concentration increased to x = 1.0, a positive but
higher S value was obtained, Fig. 6b. The S value decreased
linearly down to 75 K as temperature decreased and dropped
to zero at 50 K. Er-substitution affected the Tc value and its
effect on S was qualitatively similar for both samples. This

M.A. Aksan, M.E. Yakinci / Journal of Alloys and Compounds 385 (2004) 3343

39

Fig. 5. The RT plots of the samples: (a) x = 0.5 sample heat treated at 890 C for 240 h (optimum condition), (b) x = 1.0 sample heat treated at 900 C
for 60 h, and (c) x = 1.0 sample heat treated at 900 C for 240 h (optimum condition).

indicates that substitution of Er changes the distribution of

charges between the BiO and CuO planes and it may result
in an increase in the hole concentration in the CuO plane.
As mentioned in the introduction, several theoretical models have been used to explain the S behavior of high-Tc superconductors. The S data of the samples prepared in this
work are analyzed in view of two-band model with linear
T-term and Xin s two band model and discussion of the
results is as follow.
3.6.1. Two-band model with linear T-term
As explained by several research groups, the temperature dependence of S of high-Tc superconducting systems is

similar to that of mixed valance and heavy Fermion system

[20,57,61].
Forro et al. [20,61] have tried to fit their single crystal
Bi-2212 data using the formula explained by Gottwick et al.
[62]:
S=

B2

A=2

AT
+ T2

E0 EF
e

(2)
B2 = 3

(E0 EF )2 + 2
,
2 kB2

(3)

where E0 is the center of the resonance and the width of the

resonance. The main idea in this theory is that superimposed

Fig. 6. Temperature dependence of thermoelectric power, S, of the x = 0.5 sample heat treated at 890 C for 240 h and for the x = 1.0 sample heat
treated at 900 C for 240 h.

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M.A. Aksan, M.E. Yakinci / Journal of Alloys and Compounds 385 (2004) 3343

combination of both the conduction and valance band carriers [23]. This model is then applied successfully to the
Bi-based systems due to the structural similarity between
Bi and Tl based high-Tc materials by many research groups
[5759,6365]. In the two-band model for Bi-2223 system, it must be considered that one band is formed by the
CuO planes, which contribute to the metallic conduction
of holes and the other by the BiO planes that contribute
to the semiconductor-like behavior of electrons. For such a
two-band model the total S can be described by [66]
(S + + + S )
(5)

where = + + is the sum of the conductivities

by electrons and holes, + the electrical conductivity of
holes, the electrical conductivity of electrons and S+
and S are their respective Seebeck coefficients. While
CuO planes show metallic behavior, BiO planes display
semiconductor-type behavior. In this case, + is proportional to 1/T and is proportional to exp(Ec /kT). Assuming
+  , the TEP can be given by [23]:




S = DT + (E + FT) exp
(6)
T
where D, E, F, and are the fitting parameters.
We have also analyzed the S results of our glassceramic
samples on the basis of Eq. (6). The best fitting parameters
are given in Table 3. The best fit curves of our x = 0.5 and
1.0 samples are shown in Fig. 8. It has been found that the
experimental data of x = 0.5 sample is well fitted to Eq. (6)
but the fitting is not good for the x = 1.0 sample.
As seen in Table 3, significant difference between the
fitting parameters of both samples was found. The parameter
D, which is related with the contribution of mobile holes
in the CuO planes, has been increased significantly for x
= 1.0 sample (higher Er concentration case). An increase
on the D value indicates an increase in the number of the
mobile holes in the CuO planes [23,6365].
The experimentally determined value of was used
to evaluate the energy gap in the band structure for the
BiO layers. By considering the relations = Ec /kB and
Ec = Eg /2, the energy gap is calculated to be 3.516378
106 eV and 108.8273 106 eV for the x = 0.5 and
S=

Fig. 7. The fitting of two band model with linear T-term to the S data of
the samples. Solid lines show fitting curves.

on a broad band, there is localized peak density of states near

the Fermi level. This resonance peak gives the characteristic
temperature dependence of S. Forro et al. then added a linear
term to Eq. (2) to obtain the best fit of S data [20].
S=

AT
+ T
B2 + T 2

(4)

where T represents normal band contribution. The Eq. (4)

has been fitted successfully to the S data of Bi-based high-Tc
superconductors by many research groups [5759].
The S results of our samples fitted to Eq. (4) in the temperature range of 90270 K are shown in Fig. 7. The fitting
parameters A, B, , (E0 EF ) and are given in Table 2.
The experimental points of x = 0.5 sample fit well with
Eq. (4). But this is not the case for x = 1.0 sample. A and
(E0 EF ) values increased by increasing x. This suggests
that Fermi level should go down relatively to the top of the
band with increasing hole density in the system, while the
(E0 EF ) value increases with x in the system. This is in
contradiction to the expected result. The result indicates that
the normal band contribution, T, decreases with increasing
the substitution of Er.
3.6.2. Xin s two band model
The investigation of two-band model by Xin et al. on
Tl-based high-Tc materials indicates that S comes from the

Table 2
The fit parameters, A, B, and the estimated values of (E0 EF ) and of the system
X-value
0.5
1.0

A (V)
41.8234
820.513

B (K)
448.605
263.916

(V/K2 )
103

5.16885
1.07018 103

E0 EF (K)

(K)

0.243
4.76

813.68
478.67

Table 3
The fit parameters, D, E, and F and the estimated values of Eg
X-value

D (V/K2 )

0.5
1.0

29.4783
586.635

E (V/K2 )
29.4449
582.739

(K)
0.0203848
0.630883

F (V/K2 )
29.473
586.634

Eg (eV)
3.516378 106
108.8273 106

M.A. Aksan, M.E. Yakinci / Journal of Alloys and Compounds 385 (2004) 3343

41

Fig. 8. The fitting of Xins two band model to the S data of samples. Solid lines show fitting curves.

1.0 samples, respectively, which is consistent with those

obtained from scanning-tunneling spectroscopy studies on
Bi-based system [67,68]. However, a difference between
the Eg values of the samples were noticed. Therefore, the
change of , where depends of the energy gap between
BiO band and conduction band, indicates the change of
this band gap significantly. Possible cause of this change in
the band gap is the increase in impurity concentration in
the sample. In addition to that, the excess oxygen atoms incorporating into the BiO layers with the substitution may
also have an effect on the change of energy band gap.
3.7. Thermal conductivity (T)
The variation of the thermal conductivity with temperature, (T), for samples heat treated under their optimum

condition are shown in Fig. 9. In the metallic state (T > Tc )

for both samples, was decreased linearly as temperature
decreases to 90 K. Before a sharp rise with a maximum
just below Tc , a small minimum was obtained. The origin
of this minimum just above Tc has not clear. Similar behavior has been previously obtained by many research groups
[29,35,6971] and can be attributed to superconducting fluctuation contribution [35,46].
The origin of the maximum has also not been clarified
fully. As mentioned in the first section, it can be either an
electronic contribution or caused by the reduction of the
phonon scattering mechanism or both. However, in the recent studies, both on theoretical and experimental on the
high-Tc materials, showed that the increase of just below
Tc gives an evidence for enhancement of the quasiparticle
contribution to the heat conductivity and so an increase

Fig. 9. Temperature dependence of thermal conductivity, , of the x = 0.5 sample heat treated at 890 C for 240 h (optimum condition) and for the x
= 1.0 sample heat treated at 900 C for 240 h (optimum condition).

42

M.A. Aksan, M.E. Yakinci / Journal of Alloys and Compounds 385 (2004) 3343

of the quasi-particle mean free path [32,34,37,41,7278],

where the main source of the quasi-particle scattering in
the high-Tc materials is electronic in origin.
In this work, the magnitude of was influenced by the
Er concentration in the material. When the Er concentration was increased the magnitude of was suppressed. It
strongly indicates that the impurities play a significant role
in limiting the heat transport due to a strong increase of the
electronphonon-impurity scattering rate.

4. Conclusion
Structural formation, electrical resistance, thermoelectric power and thermal conductivity properties on the
Bi2 Sr2 Ca2 Cu3x Erx O10+ (x = 0.5 and 1.0) glassceramic
superconducting system have been studied. XRD investigations showed that Er has a large effect on the unit cell
parameters of the system. Both XRD and SEM-EDAX
observations indicate a solubility limit for Er ions in the
BSCCO system.
High Er concentration promotes impurity phase formation in the BSCCO system. We have also found that when
Er concentration increased in the Bi-2223 material, crystallization and also melting temperature increases significantly.
Electrical resistance measurements showed a decrease on
Tc and Tzero values of the samples when the Er concentration was increased and its effect on the S is similar for all
samples, it suggests that the substitution of Er changes the
distribution of charges between BiO and CuO planes and
more importantly it may be resulted in an increase in the
hole concentration in the CuO plane.
The obtained data on the thermal conductivity measurements have shown a strong relation between the Er concentrations. The maximum peak in Fig. 9 is shifted to the
lower temperature with increasing Er concentration in the
system. By considering the results from (T) measurements,
our data seems to support the electronic contribution to the
total thermal conductivity below Tc .

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