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J Supercond Nov Magn (2013) 26:15471552

DOI 10.1007/s10948-012-1931-4

O R I G I N A L PA P E R

Effect of Nano ZnO Doping on the Nature of Pinning of MgB2


Superconductors
M. Shahabuddin Intikhab A. Ansari
Nasser S. Alzayed Khalil A. Ziq A.F. Salem

Received: 5 November 2012 / Accepted: 30 November 2012 / Published online: 22 December 2012
Springer Science+Business Media New York 2012

Abstract The paper reports the JC (H, T ) of nano-ZnO


doped MgB2 samples calculated from MH loop measurements. Volume pinning forces at different temperatures have
been evaluated as a function of the field from the JC H
data. Two different scaling laws, one by Fietz and Webb
and another one by M. Eisterer, are used here to analyze
the pinning forces. All samples show the scaling behavior, which confirms the existence of grain boundary pinning. The XRD and RT data show the substitution of Zn at
Mg sites. The anisotropy in the sample is found to decrease
with the doping of the nano-ZnO. The improvement in the
JC (H, T ) of the sample with the nano-ZnO doping is due to
decrease in the anisotropy and increase in the volume pinning forces. The 2 % nano-ZnO doping is found to be the
optimal value in order to achieve the highest JC (H, T ) in
these samples.
Keywords MgB2 Nano-zinc oxide Critical current
Pinning force Scaling and anisotropy

materials in the magnetic field [1]. The occurrence of a high


JC , 105 106 A/cm2 , has been reported in the literature. The
JC in the pristine material, however, drops very rapidly as
the magnetic field increases. Serious efforts have been afoot
towards the enhancement of JC in the magnetic field [28].
Towards this end, the doping of nano-particles has shown
a great promise. The doping may have one or more effects
which combine to increase the bulk pinning strength. These
effects may be an enhancement in the H C2 and Hirr , producing lattice strain and forming wide distribution of point
pinning centers.
The magnitude and behavior of the JC in magnetic field
is described by the bulk pinning force density, FP = JC H .
Analyzing FP can be useful in the control of the JC in these
materials. The FP in superconductors is a function of temperature and magnetic field and is controlled by the microstructure of the materials. Fietz and Webb [9] observed
that the temperature and field dependence of FP follow a
scaling law of the form
FP = C(HC2 )m bp (1 b)q ,

1 Introduction
The importance of MgB2 lies in its simple crystal structure,
relatively high transition temperature (TC ) and low cost.
Nevertheless, its commercial utilization in high-field applications depends on the high critical current (JC ) of the bulk
M. Shahabuddin () I.A. Ansari N.S. Alzayed
Department of Physics and Astronomy, College of Science, King
Saud University, Riyadh 11451, Saudi Arabia
e-mail: mshahab@ksu.edu.sa
K.A. Ziq A.F. Salem
Department of Physics, College of Science, King Fahad
University of Petroleum and Minerals, Dehran, Saudi Arabia

where b = H /HC2 is the reduced field, HC2 is upper critical field and C is a constant depending on the sample
microstructure. The FP (b) shows a maximum at bpeak =
p/(p + q). The study of the normalized flux pinning force as
a function of the field gives the nature of the pinning mechanisms in a particular case [10]. For most of the superconductors JC becomes zero at fields lower than HC2 and, therefore,
the field H = H (JC 0) is used instead of HC2 to scale
the FP curves. In order to analyze the pinning properties of
MgB2 superconductors, H is the Hirr where the JC practically becomes zero.
Since the MgB2 possesses an intrinsic anisotropy
[11, 12], the super current never flows homogeneously in the
bulk sample when the magnetic field is applied as the differently oriented grains attain different properties. The clean

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grain boundaries do not limit the current flow in magnesium


diboride [1] but act as efficient pinning centers [13] and
enable high currents in un-textured polycrystalline samples.
Secondary phases over the surface of the grains [14, 15] partially block the current flow, and reduce the effective area
over which the super-currents flow [16]. This problem is
further compounded by the presence of voids or insulating
phases that tend to enhance the current percolation, which is
a natural consequence of the magnetic anisotropy [17]. The
detailed analysis of the JC (H, T ) of nano ZnO doped MgB2
using scaling law described above has not been presented so
far.
The present paper analyzes the JC (H, T ) and the pinning
forces as a function of an external magnetic field at different temperatures in the nano-ZnO doped sample with stoichiometric combination Mg1x Znx B2 (where x = 0, 0.02,
0.04 and 0.06). Since Zn is divalent, it will preferably substitute the Mg site. This substitution will not affect the carrier density, rather it will affect the lattice parameter owing to the larger size of Zn and hence may introduce lattice strain. Another effect might be the formation of the
point pinning centers. The nano-Zn substitution may also
affects the grain growth, thus leading to an improvement in
the JC (H, T ).

2 Experimental
Four samples of Mg1x Znx B2 with the value of x ranging
from 0 to 0.06 were prepared using standard solid state reaction method under high vacuum as described elsewhere [18].
Here, the source of the Zn is the ZnO nano powder supplied by Sigma Aldriech. XRD measurements were carried
using the Cu K radiation for the phase identification. The
TC of the samples was determined from the ac susceptibility measurement using homemade susceptometer described
elsewhere [19]. The JC as a function of temperature and field
were calculated from MH loop using Beans critical state
model. The DC magnetizations of these samples were measured using a PAR-4500 Vibrating Sample Magnetometer
(VSM).

3 Results and Discussion


XRD pattern of all samples are shown in Fig. 1. It clearly
shows that there is only MgB2 phase with minor traces of
MgO and un-reacted Mg. The calculated lattice parameters
are shown in Table 1. From the table, it is very clear that
c parameter is increasing with an increase of the nano ZnO
doping concentration. On the other hand, the decrease in parameter a is very small.
This indicates that Zn has been substituted at the Mg site.
The atomic size of Zn is greater than that of Mg; hence its

J Supercond Nov Magn (2013) 26:15471552

Fig. 1 XRD of nano ZnO doped MgB2 samples. The percentage of


doping is mentioned against each spectrum. The percentage of doping
is according to formula Mg1x Znx B2

Table 1 The lattice parameters and residual resistivity (0 ) of MgB2


doped with different percentages of ZnO. The 0 were corrected for
void and impurity at grain boundary using Rowllen analysis
Doping %

a ()

c ()

0 ( cm)

3.0875

3.5200

3.5

3.0870

3.5265

3.9

3.0865

3.5245

3.9

3.0860

3.5290

4.0

doping has increased the size of the c without affecting the


lattice parameter a much.
This has been further verified by measuring the resistivity of all samples as a function of temperature which is
shown in Fig. 2. It is clear that the normal-state resistivities of pure, 2 % and 4 % doped samples are nearly the
same. There is a significant change in the normal-state resistivity of 6 % as compared to that of pure sample. This might
be due to void or impurity phase MgO at grain boundaries.
The values of residual resistivity 0 calculated according to
the Rowell technique [16] are tabulated in Table 1. The 0
does not change with the doping concentration. Since Zn
is divalent as Mg is, it does not affect the carrier density
in B-plane. At the same time, it is substituted at the Mg
site so its interaction with the conducting B-plane is very
weak. The substitution is further confirmed from the change
in the TC of the doped samples as shown in the inset of
Fig. 2.
The JC of all four samples here are shown in Fig. 3. It
clearly shows that there is an increase of an order of magnitude in the value of the JC of 2 % doped sample in the
temperature range from 4 K to 20 K. The 2 % sample has

J Supercond Nov Magn (2013) 26:15471552

Fig. 2 Resistivity as a function of temperature. The inset clearly shows


the change in TC and 40 K resistivity as a function of doping concentration (Color figure online)

Fig. 3 JC as a function of H at
different temperatures for
Mg1x Znx B2 (Color figure
online)

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the highest JC among all. On the other hand, the JC of 4 %


doped sample is higher than that of the 2 % doped sample at
30 K and 35 K above 1.5 T and 0.28 T, respectively. At 30 K
there is not much difference in JC of the two samples. However, at 35 K the difference between the two is quite pronounced. At lower field the 2 % doped sample has higher JC
while at higher field the 4 % sample has the higher one. So,
there is some kind of cross-over taking place in the 2 % and
4 % samples at a temperature of 30 K. This may be due to
two different types of mechanism involved in the enhancement of JC . If we examine the normal-state resistivity of the
2 % and 4 % nano ZnO doped sample in Fig. 2, the 4 %
sample has a little lower normal-state resistivity than that of
the 2 %. This means that the 4 % has a less void and impurity phase at grain boundaries as compared to that of the
2 %. This manifests that the actual current carrying crosssectional area is higher in the former than that of the latter.
Note that the cross-sectional area carrying the current is independent of the temperature. On the other hand, the pinning

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J Supercond Nov Magn (2013) 26:15471552

Fig. 4 Normalized pinning


force as function of (left
column) reduced field (H /Hirr )
and (right column) H /Hn . For
explanation see the text (Color
figure online)

strength is a function of the temperature. At lower temperatures (below 30 K), the pinning is higher in 2 % sample, in
comparison to that of 4 % sample and at higher temperature
(above 30 K) the pinning strength become weak and actual
connectivity of the grain is playing the role of carrying the
current. This explains the cross-over of the JC curves around
30 K for the two samples.
To understand the effect of nano ZnO doping on
JC (H, T ) we calculated the pinning force as a function
of magnetic field at different temperatures for different
samples and plotted the normalized volume pinning force

(f = F /Fmax ) as a function of reduced field i.e. H /Hirr .


These results are shown in the left column of Fig. 2. From
the Fig. 2, it is clear that dominant pinning exists in pure
(0 %), 2 % and 4 % nano ZnO doped samples as the data
for the different temperatures overlap and the scaling law of
f bp (1 b)q is observed. In case of a pure sample the
value of p = 0.52 and q = 2.3 which is very close to the
value of p and q for grain boundary pinning (p = 0.5 and
q = 2). In case of 2 % and 4 % doped samples the values
of p and q are 0.65 and 2.8, respectively. These values are
still close to the grain boundary pinning. In the case of the

J Supercond Nov Magn (2013) 26:15471552

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Table 2 The value of bpeak = H /Hirr and bnpeak = H /Hn for all samples at different temperature
T (K) 0 %

2%

4%

6%

bpeak = H /Hirr bnpeak = H /Hn bpeak = H /Hirr bnpeak = H /Hn bpeak = H /Hirr bnpeak = H /Hn bpeak = H /Hirr bnpeak = H /Hn
04

0.14

0.31

0.131

0.33

0.131

0.3

0.1

0.21

10

0.13

0.29

0.18

0.36

0.18

0.35

0.11

0.21

15

0.15

0.30

0.17

0.36

0.17

0.32

20

0.16

0.34

0.18

0.39

0.18

0.34

0.19

30

0.16

0.32

0.19

0.41

0.19

0.4

0.21

0.37

35

0.18

0.35

0.18

0.38

0.21

0.34

6 % doping sample, the data at different temperatures do not


overlap well. The fitting of the data in the scaling law at 20 K
for 6 % gives the value of p and q equal to 0.52 and 2.1, respectively which are close to the grain boundary value. The
spread may be due to ambiguity in the determination of Hirr
in the sample of lower JC value.
To gain a better insight on the effect of the nano ZnO
doping on the pinning mechanism, we have studied the position of the Fmax in these samples which occur at a particular value of b which is termed bpeak here. In the case of the
grain boundary pinning, the Fmax occurs at bpeak = 0.2 and
for point pinning it occurs at bpeak = 0.33 for magnetically
isotropic materials. The variation in magnetic anisotropy
ab /H C ) and percolation threshold P are also respon (HC2
C
C2
sible for the shift of the peak from its standard value in the
dominant pinning mechanism of grain boundary or point
pinning. This deviation of the peak position in different pinning mechanisms has been studied theoretically by the Eisterer [20].
He showed that the anisotropy significantly changes the
field dependence of the volume pinning force in polycrystalline samples. In the case of MgB2 , the value of PC does
not vary much (0.25 to 0.30) but varies from 1 (dirty)
to 5 (clean). The peak position (bpeak ) is more sensitive to
the anisotropy as compared to the PC . For details see reference [20]. Thus, sometimes it becomes difficult to identify the pinning mechanism from the peak position without
prior knowledge of and PC in the present scaling law using reduced field, b = H /Hirr . Eisterer has proposed a new
scaling law in which f has been plotted as a function of
H /Hn where Hn is the field at which the pinning force becomes half of its maximum value Fmax . His argument for
it is that the peak position shifts very little i.e. 3 % only
for the extreme case of anisotropy in case of grain boundary pinning (bnpeak = 0.341 to 0.352) and 6 % in case of
the point pinning (bnpeak = 0.465 to 0.491). The difference
in the peak position in different pinning mechanism (0.34
to 0.46) is enough to distinguish it. In this scaling the data
for different temperatures overlap very well before the Hn
field. This scaling in the nano ZnO doped sample is shown

0.34

in right column of Fig. 4. Of course it gives better overlapping of the data measured for the different temperatures. The
value of bpeak (the peak position in H /Hirr plot) and bnpeak
(the peak position in H /Hn plot) for different samples at
different temperature are shown Table 2. The error in the
value of the peak position at 4 K is large due to the flux
instability in the MH loop at lower field and difficult to
get accurate JC (H ). Eisterer has shown that bpeak or bnpeak
shift towards lower value as anisotropy increases. From the
Table 2, it is clear that the grain boundary pinning is dominant pinning mechanism in all four samples at different temperature. If we compare the value of bpeak of pure samples
with that of the doped sample it shows the doping has increased its value. This indicates that nano ZnO doping has
decreased the anisotropy from pure to dirty. The pure sample
is highly anisotropic while the 2 % and 4 % doped sample is
less anisotropic. The value of bpeak is nearly constant from
10 K to 35 K in 2 % and 4 % samples. From this one infers that the 2 % and 4 % samples are more homogeneous
in comparison to the 6 % sample in which bpeak varies with
temperature. Thus increasing the doping level decreases the
homogeneity of the samples.
In the magnetic field, the JC decreases faster in the pure
sample as compare to ones doped up to 4 % owing to higher
anisotropy in the former as compared to the latter. However,
further increase in the doping level not only causes the formation of voids and impurity phases at the grain boundaries,
but also increases the in-homogeneity in the sample. These
effects reduce the effective current carrying cross-sectional
area, thus leading to a decrease in the JC of the sample seen
at the 6 % doping concentration. In the present study, 2 %
doping of nano ZnO is the optimum value to get the better
JC (H, T ) behavior.

4 Conclusion
Using MH loop measurement, the JC (H ) of the 0 %, 2 %,
4 % and 6 % nano ZnO doped MgB2 samples were calculated at different temperatures. We find that the 2 % doped
sample shows the highest value of the JC at all fields and

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temperatures. The volume pinning force was analyzed using the scaling law proposed by Fietz and Webb [9]. It was
found that all samples show grain boundary pinning. The
pinning forces in the samples were also analyzed using the
scaling law proposed by Eisterer [20]. Toward this end, bpeak
for all samples at different temperatures has been tabulated.
The increase in the magnitude of the bpeak with the nano
ZnO doping indicates that the doping decreases the magnetic anisotropy of the samples. These bpeak values confirm
the occurrence of the grain boundary pinning. It can therefore be concluded that the decrease in the anisotropy is partially responsible for the enhancement of the JC (H ) values.
Acknowledgements This work was supported by NPST program
by King Saud University, Riyadh, under the project number 08ADV397-2.

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