Enhancement of Inter-plane

Coupling and Superconductivity in

Cu0.5Tl0.5Ba2(Ca3−yM y )Cu4O12−δ (M = 0,
Pr, Y, Er, Gd; y = 0.02) Samples

Nawazish A. Khan, M. Nadeem Ashraf &

Syed Hamza Safeer

Journal of Superconductivity and

Novel Magnetism
Incorporating Novel Magnetism

ISSN 1557-1939

J Supercond Nov Magn

DOI 10.1007/s10948-016-3565-4

1 23
Your article is protected by copyright and all
rights are held exclusively by Springer Science
+Business Media New York. This e-offprint is
for personal use only and shall not be self-
archived in electronic repositories. If you wish
to self-archive your article, please use the
accepted manuscript version for posting on
your own website. You may further deposit
the accepted manuscript version in any
repository, provided it is only made publicly
available 12 months after official publication
or later and provided acknowledgement is
given to the original source of publication
and a link is inserted to the published article
on Springer's website. The link must be
accompanied by the following text: "The final
publication is available at link.springer.com”.

1 23
 Author's personal copy
J Supercond Nov Magn
DOI 10.1007/s10948-016-3565-4
ORIGINAL PAPER
Enhancement of Inter-plane Coupling
and Superconductivity in Cu0.5Tl0.5Ba2(Ca3−yMy )Cu4O12−δ
(M = 0, Pr, Y, Er, Gd; y = 0.02) Samples
Nawazish A. Khan1 · M. Nadeem Ashraf1 · Syed Hamza Safeer1
Received: 17 February 2016 / Accepted: 21 May 2016
© Springer Science+Business Media New York 2016
Abstract Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M=0, Pr, Y,
Er, Gd; y=0.02) samples are synthesized at normal pressure
to see the effect of M+3 elements doping in enhancing the
inter-plane coupling of Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ
superconductors. These samples have shown the tetrago-
nal crystal structure in which the axis lengths increase with
doping of rare-earth impurities. In the resistivity measure-
ments, these samples have shown metallic variations of
resistivity from room temperature down to the onset of
superconductivity. The onset of superconductivity, the zero
resistivity critical temperature, and the magnitude of dia-
magnetism are suppressed with the doping of rare-earth
impurities at Ca sites. The excess conductivity analysis has
shown suppression in the onset temperature of 3D and 2D
Lawrence-Doniach (LD) conductivity regimes. The coher-
ence length along the c-axis (ξc(0) ), the inter-layer coupling
(J ), and the Fermi velocity (VF ) of the carriers are sup-
pressed with Y doping, whereas the values of these param-
eters increase with the doping of Er and Gd. However, the
values of Bc0 (T ), Bc1 (T ), and Jc (0) are suppressed with
the doping of Y, Er, and Gd. Moreover, the values of mag-
netic field penetration depth (λpd ) and the Ginzburg-Landau
(GL) parameter κ increase with the doping of rare-earth ele-
ments. Since the λpd is related inversely to the density of
mobile carriers in the conducting CuO2 planes, the increase
in values of these parameters indicates that the density of
mobile carriers is suppressed in the conducting planes with
 Nawazish A. Khan
nawazishalik2@yahoo.com
1 Materials Science Laboratory, Department of Physics,
Quaid-i-Azam University, Islamabad, 45320, Pakistan
the doping of rare-earth elements. These studies stress the
pivotal role of mobile charge carriers in the mechanism of
high-Tc superconductivity and have shown that M+3 rare-
earth elements develop some localization of the carriers
in their neighborhood, thereby suppressing the values of
essential superconductivity parameters.
Keywords Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M = 0,
Pr, Y, Er, Gd, y = 0.02) superconductors · Decoupling
of CuO2 planes · Enhanced flux pinning · Longer
coherence length
1 Introduction
Since the discovery of high-temperature superconductivity
in oxides, the understanding of its mechanism has become
a challenging task for the scientific community. The crystal
chemistry of high-temperature superconductors (HTSCs) is
well understood. The unit cell in almost all oxide supercon-
ductors consists of a charge reservoir layer and conducting
nCuO2 planes. It is also now well understood that the super-
conductivity lies in the conducting CuO2 planes, whereas
the job of the charge reservoir layer is to supply the carri-
ers to them. The superconducting planes are separated by
Ca atom, which act as a thin insulating Josephson coupling
layer between the CuO2 planes. The wave function of Ca
atoms therefore determines the inter-plane coupling. As a
consequence of higher density of filling states in the con-
ducting planes, their Fermi level is lower than the charge
reservoir layer that drives the frequent flow of the charge
carriers towards CuO2 planes. The 2D conductivity there-
fore becomes predominant in high-Tc oxide compounds
that reduces their dimensionality. Their reduced dimen-
sionality can be enhanced by enhancing their inter-plane
 Author's personal copy
coupling. In our previous studies, we have enhanced the
inter-plane coupling in Cu0.5 Tl0.5 Ba2 Ca2 Cu3 O10−δ super-
conductors by doping “Be” and “Mg” at the Ca sites [1,
2]. Partial substitution of Be and Mg at Ca sites not only
suppresses the c-axis length but also reduces the unit cell
volume of the final compound. The Tc (R = 0) and mag-
nitude of diamagnetism are improved with the substitution
of elements such as Be and Mg. In the current study, we
have tried to investigate the role of rare-earth M+3 ele-
ments doping in enhancing the inter-plane coupling and
their influence on the mechanism of high-Tc supercon-
ductivity. The atomic radii of doped elements [M+3 = Er
(1.75 Å), Gd (1.80 Å), Y (1.81 Å), Pr (1.82 Å)] are smaller
than that of Ca (1.97 Å) atom, and we expect that their
partial substitution would develop better inter-plane cou-
pling, provided there is no role of charge state of doped
atoms.
Superconductivity in Tl-Ba-Ca-Cu-O was discovered for
the first time by Sheng and Hermann, and there are many
compounds prepared under this system of superconduc-
tors [3]. K. Takamuku et al. [4] prepared single crystals
of Bi2 Sr2 Ca1−x Yx Cu2 Oy by means of the traveling sol-
vent floating zone (TSFZ) method. The X-ray diffraction
of the so-synthesized samples has shown a suppression
of the lattice constant along the c-axis with the increase
doping of Y atoms in the final compound. K. Nanda
Kishore and S. Satyavathi [5] studied the superconduct-
ing properties of Y-doped Bi1.7 Pb0.3 Sr2 Ca2−x Yx Cu3 Oy
(0.0 ≤ x ≤ 0.1) samples and found that the major phase
of Bi-2223 found in undoped samples transforms to Bi-
2212 phase due to Y substitution. In the high-Tc Bi-2223
phase, the lattice parameters were not changed, whereas in
the low-Tc Bi-2212 phase, the c-axis parameter decreases
with increased Y doping. The thermoelectric power mea-
surements of these samples have shown that the hole
concentration in the conducting planes decreases in both
phases due to Y substitution. A. Ehmann et al. [6] syn-
thesized Bi0.5 Cu0.5 Sr2 YCuO7 − z above 970 °C from the
proper starting materials. Their samples have shown the
tetragonal structure following P4/mmm space group with
cell parameters a = 3.815 Å and c = 11.73 Å. The as-
prepared samples have shown no superconductivity down
to 5 K, but these samples turn superconducting with post-
annealing at 500 °C. The highest superconducting tran-
sition temperature in the samples with nominal compo-
sition (Bi0.5 Cu0.5 )Sr2 Y0.8 Cu2.2 06.95 is observed at 68 K.
G. Gritzner et al. [7] synthesized superconductors having
a composition (Tl0.5 Pb0.5 )(Sr1−x Bax )2 (Ca1−y Gdy )Cu2 Oz
(x=0, 0.05, 0.1, 0.15, 0.2, 0.25; y= 0, 0.05, 0.1, 0.2, 0.3, 0.4)
via wet chemical gel techniques. The samples were heated
first at 850 °C followed by sintering at 925 °C for optimiza-
tion of the superconducting properties of the bulk material.
The X-ray diffraction revealed that these samples were
J Supercond Nov Magn
phased pure when x and y were equal or smaller than 0.2.
S. Xu et al. [8] prepared Gd-doped YBa2 Cu3−x Gdx O7−δ
(x = 0-0.15) poly-crystalline samples by the solid-state
reaction method. Their samples showed an orthorhombic
structure in which the lattice parameters and the volume
(V ) of the unit cell increased linearly with an increase of
x < 0.05 whereas their Tc is suppressed with the substi-
tution of Gd+3 for Cu in CuO2 planes. X. Zhao et al. [9]
prepared Bi2 Sr2 Ca1−x Gdx Cu2 Oy (x = 0–1.0) single crys-
tals by a self-flux method. The c-axis length of the unit
cell was found to decrease gradually with Gd doping. The
Tc of the samples, however, increases slightly at first and
then drops rapidly upon Gd doping, which these authors
suggested to be rising due to hole-filling effects. C.A.M.
dos Santos et al. [10] studied the effect of Pr doping in
Bi2 Sr2 Ca1−x Prx Cu2 O8+δ samples. Their samples showed
an orthorhombic crystal structure in which the lattice param-
eters were the linear function of Pr contents, and this system
represented a complete dissolution of Pr atoms at Ca sites.
The TCR slightly increased with x from 0 < x < 0.2,
rapidly decreased for x > 0.4, and vanished for x ∼ 0.6.
whereas the TCM obtained from magnetization measurement
remained unchanged. Xuefeng Sun et al. [11] studied the
effect of Pr doping on the structure and superconductivity
of Bi2 Sr2 Ca1−x Prx Cu2 Oy . These samples were prepared by
the self-flux method. Their Bi2 Sr2 Ca1−x Prx Cu2 Oy samples
showed an orthorhombic crystal structure in which the a-
and b-axes showed an increase whereas the c-axis length
decreases with the increasing Pr content. The authors sug-
gested this to be rising due to the smaller size of Pr+4
ions in comparison with Ca+2 ions. The Tc of the sam-
ples increases with initial low doping; however, its value is
suppressed with increased Pr concentration and completely
suppressed for Pr content of about 0.60. Y. Gao et al. [12]
studied Bi2 Sr2 Ca1−x Mx Cu2 O8 (M = Pr, Gd, Y) samples.
The XRD studies showed that these samples were tetrago-
nal in a structure having a P4/mmm space group with “Pr”
doping with 0 ≤ x ≤1.0. In their studies, the doping of
Pr at the Ca site caused a very little change in the a-axis,
whereas the c-axis length increased slightly. However, the
Tc of their samples is suppressed with Pr doping up to x=0.5
and their samples become semiconducting beyond Pr dop-
ing of x > 0.5. (Bi1.6 Pb0.4 )(Sr1.8 Ba0.2 )(Ca1−.x Erx )2 Cu3 Oy
(x=0, 0.002, 0.005, 0.010, 0.015, 0.020) samples of I.Gr.
Deac et al. [13] have shown that critical current and mag-
netic properties were strongly dependent on pinning forces
acting on inter-granular and intra-granular vortices. Their
undoped samples have shown a predominant single phase
of “2223,” whereas the contribution of the “2212” phase
is observed in the samples with Er doping of x=0.005
to x=0.020 and the “2201” phase was observed in traces.
Bi2 Sr2 Ca1−x Erx Cu2 O8+δ (0.0≤ x ≤1.0) samples of A.
Sattar et al. [14] have shown an orthorhombic crystal
 Author's personal copy
J Supercond Nov Magn

structure with a space group of PMMM. By increasing the
concentration (x) of “Er,” the a-axis remained unchanged,
the b-axis increased, whereas the c-axis decreased with
increased Er doping. The 2212 phase was the major phase
for 0 ≤ x ≤ 1.0, whereas the pure major phase of
2212 was observed for 0 ≤ x ≤ 0.6. The authors sug-
gested the decreased in the superconductivity to be aris-
ing from the increased disorder induced by doped atoms
in the system. In order to increase the inert-plane cou-
pling, we have doped rare-earth elements on the Ca sites
in Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M = 0, Pr, Y, Er,
Gd; y=0.02) samples and studied their superconducting
properties. To the best of our knowledge, such studies
on Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12 samples have not been
carried out before.
2 Experimental
Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M = 0, Y, Pr, Er, Gd;
y = 0.02) samples were prepared by employing the two-
step solid-state reaction method. The precursor material of
Cu0.5 Tl0.5 Ba2 (Ca3 − y My )Cu4 O12 − δ (M = 0, Pr, Y, Er,
Gd; y = 0.02) samples was prepared using Y2 O3 or Pr2 O3

Fig. 1 X-ray scans of the

Cu0.5 Tl0.5 Ba2 (Ca3 − y My )Cu4 O12 − δ
(M = 0, Er, Gd, Y, Pr; y = 0.02)
samples
 Author's personal copy
or Er2 O3 or Gd2 O3 and Ba(NO3 )2 , Ca(NO3 )2 . 4H2 O and
Cu(CN) as starting compounds. These materials were mixed
for 1 h and fired twice at 880 °C in a quartz boat for
24 h. The precursor material after firing was mixed with
Tl2 O3 to give Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (y=0.02;
M=0, Y, Pr, Gd, Er) as a final reactant composition. The
thallium-mixed material was pressed under a pressure of
3.8 tons cm−2 to make disc-shaped pellets. These pellets
were enclosed in a gold capsule and sintered at 880 °C for
18 min. The samples were characterized by resistivity, ac
susceptibility, and Fourier transform infrared spectroscopic
measurements. The FTIR absorption measurements were
carried out by employing a Nicolet 5700 spectrometer in the
400–700 cm−1 wave number range. The crystal structure of
the samples was measured by X-ray diffraction scan using
Bruker DX 8 Focus by employing CuKαα radiations of a
wavelength of 1.54056 Å. The cell parameters were deter-
mined by a check cell computer refinement program. The
oxygen content in the final compound is optimized by car-
rying out post-annealing of the samples for 6 h in a tube
furnace in air atmosphere at 500 °C.
3 Results and Discussion
The X-ray diffraction scans of Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4
O12−δ (M = 0, Pr, Er, Gd, Y; y = 0.02) samples are
shown in Fig. 1. Most of the diffraction lines are fit-
ted to the tetragonal crystal structure by following the
P4/mmm space group. The length of axes of these sam-
ples is shown in Table 1. The a-axis length varies from
4.311 to 4.327 Å and the c-axis length from 17.752 to
17.981 Å in Cu0.5 Tl0.5 Ba2 (Ca3 − y My )Cu4 O12 − δ (M = 0,
Er, Gd Y; y = 0.02) samples; however, in the Pr-doped sam-
ples, the a- and c-axis length is significantly reduced, i.e.,
4.029 and 17.063 Å, respectively. The unit cell volume in
Cu0.5 Tl0.5 Ba2 (Ca3 − y My )Cu4 O12 − δ (M = 0, Er, Gd, Y;
y = 0.02) samples varies between 332.61 and 334.17 Å3 ,
whereas the volume for the Pr-doped samples is 276.98 Å3 .
A significant decrease in the volume of the unit cell shows
Table 1 Resistivity, susceptibility, and lattice parameters of the Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M = 0, Y, Gd, Er, Pr; y = 0.02) samples
Sample Resistivity
Tc (R = 0) (K) Tc (onset) (K)
M=0 107.4 116.8
M = Er 104.4 110.27
M = Gd 94.44 105.25
M=Y 95.47 114.7
M = Pr
J Supercond Nov Magn
that charge carriers in the Pr-doped samples are under
tremendous external pressure of the constituent ions.
The resistivity versus temperature measurements of
Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O14−δ (M=0, Er, Gd, Y, Pr;
y=0.02) samples are displayed in Fig. 2a. Except for the
Pr-doped samples, all Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ
(M=0, Er, Gd, Y; y=0.02) samples have shown metallic
variations of resistivity from room temperature down to
the onset of superconductivity; the Pr-doped samples have
shown a semiconducting behavior down to 77 K as shown
in Fig. 2b. Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M=0, Er,
Gd, Y; y=0.02) samples have shown the onset of supercon-
ductivity around 116.8, 110.3, 105.3, and 114.7 K and the
zero-resistivity critical temperature at 107.4, 104.4, 94.4,
and 95.5 K, respectively. The ac magnetic susceptibility
measurements of Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M =
0, Er, Y, Gd; y=0.02) samples are shown in Fig. 3. These
samples have shown the onset of superconductivity around
105.6, 110.1, 101.6, and 98.2 K (Table 1). The magnitude
of diamagnetism is suppressed with the doping of Er, Y,
and Gd; the Pr-doped samples have not shown any sign of
superconductivity down to 77 K.
The FTIR absorption measurements of Cu0.5 Tl0.5 Ba2 (Ca
3−y My )Cu4 O12−δ (M = 0, Y, Pr, Er, Gd; y = 0.02) sam-
ples are given in Fig. 4. Three absorption bands around
411–416, 474–475, and 612–618 cm−1 can be seen in these
spectra. The former two modes are related to the vibra-
tions of apical oxygen atoms of type Tl-OA -Cu(2) and
Cu(1)-OA -Cu(2); the last mode is related to vibrations of
planar oxygen atoms. Y doped samples, whereas it is hard-
ened in the Pr-doped samples. The CuO2 planar oxygen, the
apical oxygen mode of type Cu(1)-OA -Cu(2), is not signif-
icantly affected with the doping of Y, Pr, Er, and Gd at the
Ca sites; however, the apical oxygen mode of the type Tl-
OA-Cu(2) is slightly softened with the doping of Gd but it is
hardened with the incorporation of Y, Er, and Pr; the maxi-
mum hardening is observed in the Y- and Pr-doped samples.
The planar oxygen mode remains at the same position in
the Er-doped sample; however, this mode is softened in Gd
and the mode in Cu0.5 Tl0.5 Ba2 (Ca2−y My )Cu3 O10−δ (M =
Susceptibility Lattice parameters
MD Tc (onset) (K) a (Å) c (Å) V (Å3 )
0.00 105.58 4.312 17.765 330.63
0.08 110.06 4.319 17.781 331.68
0.02 101.58 4.315 17.752 330.53
0.04 98.22 4.311 17.981 334.17
4.029 17.063 276.98
 Author's personal copy
J Supercond Nov Magn
Fig. 2 a Resistivity versus temperature measurements of the
Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M = 0, Er, Gd Y; y = 0.02)
samples. b Resistivity versus temperature measurements of the
Cu0.5 Tl0.5 Ba2 (Ca3 − y My )Cu4 O12 − δ (M = Pr; y = 0.02) samples
Fig. 3 The AC susceptibility versus temperature measurements of
the Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M = 0, Er, Gd, Y; y = 0.02)
samples
Fig. 4 The FTIR absorption spectra of the Cu0.5 Tl0.5 Ba2 (Ca3−y My )
Cu4 O12−δ (M = 0, Er, Gd, Y; y = 0.02) samples
0, Er, Gd, Y, Pr; y = 0.02) samples is observed at 617, 617,
615, 612, and 619 cm−1 . The hardening of planar oxygen
mode in the Pr-doped samples is consistent with suppres-
sion in the unit volume and cell parameters. In order to see
the influence of Y, Pr, Er, and Gd doping at the Ca sites on
the intrinsic superconductivity parameters, we have carried
out fluctuation-induced conductivity (FIC) analysis of con-
ductivity data of Cu0.5 Tl0.5 Ba2 (Ca2−y My )Cu3 O10−δ (M =
0, Er, Gd, Y, Pr; y = 0.02) samples.
3.1 Excess Conductivity Analyses (FIC)
of Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M = 0, Y, Pr, Er,
Gd; y = 0.02) Samples
The excess conductivity analyses is carried out by using the
equation σ(T ) = σRT ε−λD ελ in the temperature
 Author's personal copy
J Supercond Nov Magn

Table 2 Widths of critical, 3D, 2D, and 0D fluctuation regions observed from fitting of the experimental data of the Cu0.5 Tl0.5 Ba2
(Ca3−y My )Cu4 O12−δ (M = 0, Y, Gd, Er; y = 0.02) samples using the AL model

Sample λCR λ3D λ2D λSW TCR−3D = TG T3D−2D T2D−SW Tcmf T∗ α = ρn (0 K) W = Tc
(K) (K) (K) (K) (K) (-cm) (K)

M=0 0.30 0.55 0.97 2.06 116.2 120.1 146.8 114.8 164.7 0.007 6.28
M=Y – 0.54 0.99 2.01 107.4 109.4 131.5 105.4 154.6 0.024 12.93
M = Gd 0.33 0.50 1.05 1.99 108.4 112.5 133.6 106.2 159.7 0.048 11.79
M = Er 0.35 0.51 1.01 2.03 113.4 117.4 135.5 109.4 162.6 0.002 7.60

regime around Tc and beyond. It can be written in the parameters are enhanced in the Er- and Gd-doped samples
form (Table 3).
The TG is the crossover temperature between the 3D
ln σ(T ) = ln σRT − λD ln(ε) (1) LD regime and the Ginzburg-Landau (GL) regime. The
temperature TG and the Ginzburg number NG in the transi-
  tion region are determined from the intersection of critical
T −T mf
The ε = T mfc is the reduced temperature and the λD is regime and 3D conductivity regime. By employing the TG
c
the dimensional exponent with values equal to 0.3, 0.5, 1.0, and NG equations and using the Ginzburg-Landau theory
and 2.0 for critical, 3D, 2D, and 0D conductivity, respec- [18–20], important superconducting parameters are calcu-
tively [15–17]. The expression of Lawrence-Doniach (LD) lated by using the equations:
model used for the conductivity analyses of polycrystalline  
 T − T mf   2
samples is of the form  G c 
NG =   = 0.5 K B Tc /B 2
γ 2 3
ξ (3)
 Tcmf  c(0) c(0)
 
σLD = e2 /(16d) (1 + J ε−1 )−1/2 ε−1 (2)
0
 2 Bc = √ (4)
Here, the J = 2ξc(0) /d ξ s the inter-layer coupling with 2 2π λpd(0) ξab(0)
d as the thickness of superconducting layers (˜18 Å in the
present case) and the ξ ξc(0) is the coherence length along Bc
Bc1 = √ ln κ (5)
the c-axis. In the analyses, various crossover temperatures, κ 2
such as TG , T3D−2D , and T2D−0D , are determined from the
log plot of the excess conductivity versus the reduced tem- √
perature (see Tables 2 and 3). These crossover temperatures Bc2 = 2κBc (6)
are determined from the intersection of various dimensional
exponents, such that λCR refers to the slope below TG , λ3D
above TG , λ2D to the slope value above T3D−2D , and λ0D to 4κBc1
Jc = √ (7)
the slope of exponent value 2 (Fig. 5a–d). The parameters 3 3λpd(0) ln κ
such as coherence length along the c-axis (ξc(0) ), the inter-
layer coupling (J ), the phase relaxation time of the carriers The Tcmf is the mean field critical temperature, which is
(τ τϕ ),φ and the Fermi velocity of the carriers (VF ) are sup- determined from the point of inflection of the temperature of
pressed in the Y-doped samples, but the values of these the derivative of resistivity (dρ/dT), and the κ = λ/ξ is the

Table 3 The superconductivity parameters observed from the FIC analysis of the Cu0.5 Tl0.5 Ba2 (Ca3 − y My )Cu4 O12 − δ (M = 0, Y, Gd, Er;
y = 0.02) samples using the AL model

Sample ξc(0) J NG λp.d Bc(0) Bc1 Bc2 κ J c(0) 103 VF × 107 Ebreak τϕ × 10−14
(Å) (Ao ) (T) (T) (T) (A/cm2 ) (m/s) (eV)

M=0 1.93 0.046 0.071 794.64 1.83 0.101 128.7 49.7 1.25 1.80 0.07 5.81
M=Y 1.75 0.038 0.114 816.68 1.783 0.097 128.7 51.04 1.18 1.45 0.06 6.29
M = Gd 2.18 0.058 0.136 1189.4 1.224 0.050 128.7 74.34 0.55 1.78 0.07 5.63
M = Er 2.43 0.073 0.076 1152.4 1.263 0.053 128.7 72.03 0.60 2.20 0.05 7.80
 Author's personal copy
J Supercond Nov Magn
1/2
Fig. 5 a ln(σ ) versus ln(ε) of the Cu0.5 Tl0.5 Ba2 (Ca3−y My )
Cu4 O12−δ (M=0,y=0.02) superconductor sample. b ln(σ ) ver-
sus ln(ε) of the Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M=Y, y=0.02)
superconductor sample. c ln(σ ) versus ln(ε) of the Cu0.5
Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M = Gd, y=0.02) superconductor sam-
ple. d ln(σ ) versus ln(ε) of the Cu0.5 Tl0.5 Ba2 (Ca3−y My )
Cu4 O12−δ (M=Er, y=0.02) superconductor sample
GL parameter. The phase relaxation time (τϕ ) of the Cooper
pair is calculated by using the following equation [21]:
π
τφ = (8)
8kB T ε0
 
τφ−1
By using τϕ , the coupling constant λ, λ = 2πkB T is deter-
mined. The Fermi velocity of the carriers and the energy
required to break apart the Cooper pairs are determined by
using the following expressions:
5π kB Tc ξc (0)
VF = (9)
2K
h
E= (eV) (10)
τφ (1.6 × 10−19 )
The value of the proportionality coefficient K in
the above equations is 0.12 [22]. By using NG for
Cu0.5 Tl0.5 Ba2 (Ca3−y My )Cu4 O12−δ (M=0, Y, Pr, Er, Gd;
y=0.02) samples, the values of Bc(0), Bc1(0), Bc2(0) ,
Jc (0), and κ = λ/ξ are determined by employing the
aforementioned equations [3–10]. It can be seen that the
values of Bc0 (T ), Bc1 (T ), and Jc (0) are suppressed with
the doping of rare-earth elements Y, Er, and Gd (Table 3).
The London penetration depth (λp.d ) and the GL param-
eter (κ) are enhanced with the incorporation of rare-earth
elements. Since the London penetration depth, λpd =
2
mc /4π ns e2 , λ is inversely proportional to the square
root of density of carriers, the increase in its value shows
that the density of mobile carriers is suppressed with the
doping of rare-earth elements. The thermodynamic critical
field (Bc ) is related to the free energy difference between the
normal and superconducting electrons. The suppression in
the values of these parameters suggested some sort of local-
ization of the carriers in the neighborhood of M+3 sites that
leads to a suppression in density of the Cooper pairs, hence
to the suppression of Bc and the values of aforementioned
parameters. The increase in the values of London penetra-
tion depth (λpd ) and the GL parameter (κ) also suggested
that weak superconductivity allows longer field external
penetration in the bulk of the material.
4 Conclusion
Cu0.5 Tl0.5 Ba2 (Ca3−y My ) Cu4 O12−δ (M = 0, Pr, Y, Er, Gd;
y=0.02) samples are synthesized by the two-step solid-state
reaction method at 880 °C, and their superconducting prop-
erties are studied. Except in the Y-doped samples, the cell
parameters in all rare-earth-doped samples are suppressed; a
maximum suppression is observed in the Pr-doped samples.
The Tc (R = 0) and magnitude of diamagnetism are sup-
pressed with the doping of rare-earth ions. In FTIR absorp-
tion measurements, Tl-OA-Cu(2) apical oxygen mode is
 Author's personal copy
softened with the doping of Gd; however, this mode is hard- References
ened with the doping of Y, Er, and Pr. The planar oxygen
mode in Cu0.5 Tl0.5 Ba2 (Ca2−y My )Cu3 O10−δ (M = 0, Er, 1.
Gd, Y, Pr; y = 0.02) samples is observed at 617, 617, 2.
615, 612, and 619 cm−1 . The hardening of planar oxy- 3.
4.
gen mode in the Pr-doped samples is also consistent with
the suppression in the unit volume and cell parameters.
The hardening/softening of phonon modes related to vibra- 5.
tions of oxygen atoms confirmed the incorporation of M+3
6.
ions in the Cu0.5 Tl0.5 Ba2 (Ca2 − y My )Cu3 O10 − δ unit cell.
From the excess conductivity analyses, the onset tempera-
ture of 3D and 2D LD regimes is suppressed with rare-earth 7.
doping; the Pr-doped samples have not shown the onset
8.
of superconductivity down to 77 K. The coherence length
along the c-axis (ξc(0) ), the inter-layer coupling (J ), and the 9.
Fermi velocity (VF ) of superconducting carriers decrease in
10.
the Y-doped samples, whereas their values increase in the
Er- and Gd-doped samples. The values of Bc0 (T ), Bc1 (T ), 11.
and Jc (0) are suppressed with rare-earth doping. The Lon-
don penetration depth (λpd ) and the Ginzburg-Landau (GL) 12.
parameter (κ) are enhanced with the doping of M+3 ions,
13.
showing that the density of mobile carriers is suppressed
with the doping of rare-earth ions. These findings have 14.
shown that rare-earth ions develop localization of the charge
carriers in their neighborhood, which suppresses the den- 15.
sity of mobile charge carriers in the conducting CuO2 16.
planes. Due to this decrease in the density of mobile charge
carriers in the conducting planes, the values of supercon- 17.
ductivity parameters are suppressed. The thermodynamic
18.
critical field (Bc ) is related to the free energy difference
between the normal and superconducting electrons. The
decrease in the values of Bc also supports the theses of 19.
localization of the carriers in the neighborhood of M+3
20.
atoms.
21.
Acknowledgments The Higher Education Commission (HEC) of
Pakistan is acknowledged for its financial support through the indige- 22.
nous scholarship (Grant No. 17-5-3(PS3-284) HEC/Sch/2006).
J Supercond Nov Magn
Khan, N.A., Khurram, A.A.: Appl. Phys. Lett. 86, 152502 (2005)
Khan, N.A., Husnain, G.: Phys. C 436, 51 (2006)
Park, C., Snyder, R.L.: J. Am. Ceramic Soc. 78, 3171 (1995)
Takamuku, K., Ikeda, K., Takata, T., Miyatake, T., Tomeno, I.,
Gotoh, S., Koshizuka, N., Tanaka, S.: Phys. C, 185-189 (1991).
451-452 North Holland
Nanda Kishore, K., Satyavathi, S., Hari Babu, V., Pena, O.: Mater.
Sci. Eng. B38, 267–271 (1996)
Ehmann, A., Kemmler-Sack, S., Losch, S., Schlichenmaier, M.,
Wischert, W., Zoller, P., Nissel, T., Huebener, R.P.: Phys. C 198,
1-6 (1992)
Gritzner, G., Sudra, H., Eder, M.: J. Phys. Conf. Ser. 43, 462-465
(2006)
Xu, S., Wu, X.S., Liu, G., Liu, J.S., Du, J., Jiang, S.S., Gao, J.:
Phys. C 417, 63–68 (2004)
Zhao, X., Sun, X.F., Wang, L., Zhou, Q.F., Wu, W.B., Li, X.-G.:
Phys. C 336, 131–136 (2000)
dos Santos, C.A.M., Moehlecke, S., Kopelevich, Y., Machado,
A.J.S.: Phys. C 390, 21–26 (2003)
Sun, X., Zhao, X., Wu, W., Fan, X., Li, X.-G., Ku, H.C.: Phys. C
307, 67–73 (1998)
Gao, Y., Pernambuco-Wise, P., Crow, J.E., O’Reilly, J., Spencer,
N., Chen, H., Salomon, R.E.: Phys. Rev. B 45(13) (1992)
Gr.Deac, I., Pop, A.V., Ilonca, G., Deltour, R.: Phys. C 341-348,
1451–1452 (2000)
Sattar, A., Srivastava, J.P., Sharma, S.V., Nath, T.K.: Phys. C 266,
335–344 (1996)
Sato, T., Nakane, H., Mori, N., Yoshizawa, S.: Phys. C 344-360,
244–247 (2003)
Ghosh, A.K., Bandyopadhyay, S.K., Barat, P., Sen, P., Basu, A.N.:
Phys. C 264, 255–260 (1996)
Kaur, M., Srinibasan, R., Mehta, G.K., Kanjilal, D., Pinto, R.,
Ogale, S.B., Mohan, S., Ganesan, V.: Phys. C 443, 61–68 (2006)
Lawrence, W.E., Doniach, S.: Proceedings of the twelfth inter-
national conference on low temperature physics, edited by Eizo
Kanda (Keigaku Tokyo) pp. 361 (1971)
Abu Aly, A.I., Ibrahim, I.H., Awad, R.A., El-Harizy, A.: J. of
Supercond. Nov. Magn. 23, 1325 (2010)
Rojas Sarmiento, M.P., Uribe Laverde, M.A., Vera Lopez, E.,
Landinez Tellez, D.A., Roa-Rojas, J.: Phys. B 398, 360 (2007)
Solovjov, A.L., Dmitriev, V.M., Habermeier, H.-U.: Phys. Rev. B
55, 8551 (1997)
Ben Azzouz, F., Zouaoui, M., Annabi, M., Ben Salem, M.: Sol.
Stat. Phys. (C) 3, 3048 (2006)