3.1. Electrical resistivity analyses.
Temperature dependence of electrical resistivity in the range of 140 K down to 85 K, for (Bi, Pb)-2223 / (ZnO NPs)x (x = 0.0, 0.1, 0.2, 0.3, 0.5 and 1 wt%) composites are plotted in Fig. 1(a). All the composites have shown metallic-like behavior in the normal state above onset critical temperature \({T}_{C}^{on}\), where an abrupt fall in resistivity begins, followed by a transition to zero resistance \(\rho =0\), (superconducting state) at offset temperature \({T}_{CO}\). As observed, the magnitude of the electrical resistivity in the normal state decreases with the increase of the ZnO NPs concentration up to 0.2 wt% and then increases for samples with higher ZnO NPs concentrations. The normal state electrical resistivity depends on porosity, inter-granular coupling, grain boundaries scattering, and impurities. As mentioned, the normal state resistivity is minimum for 0.2 wt% ZnO NPs added sample. It can be concluded that the porosity, heterogeneities, induced defects, and scattering produced by the grain boundaries and ZnO additive are the lowest in this sample.
The onset critical temperature \({T}_{C}^{on}\) for different composites was determined from the crossing point of the extrapolated linear fit of the highest slope near the midpoint of the electrical resistivity jump and the linearly extrapolated straight line in the normal state of the \(\rho \left(T\right)\) curve (Fig. 1(a)). The obtained values of the \({T}_{C}^{on}\), and \({T}_{Co}\) and the broadening transition width \({\varDelta T}_{c}={T}_{c}^{on}-{T}_{co}\) are summarized in Table 1. As can be observed, the \({T}_{C}^{on}\) is about 108.5 ± 0.5 K and is almost constant for different composites. It indicates that the host crystal structure and the stoichiometry of the Bi1.6Pb0.4Sr2Ca2Cu3O10+δ superconductor phase are not affected by adding the ZnO NPs. This result agrees with the XRD results in our previous work [11], which demonstrate no change in XRD peak positions by ZnO NPs addition. It has been found that the addition of a small amount of ZnO NPs leads to the enhancement of \({T}_{CO}\) from 96.0 K for ZnO free sample to 101.0 K for the sample with 0.2 Wt% ZnO NPs. For higher additive values, \({T}_{CO}\) is decreased and reach 88.5 K for the sample with x = 1.0 wt%. The obtained results also show that the transition width is decreased from 12.5 K to 6.0 K as the ZnO NPs concentration enhances from 0.0 wt% to 0.2 wt%, and then increased for further enhancement of the ZnO NPs concentration until reached to 20.5 K for the sample with 1.0 wt% additive.
As observed, the \(\rho \left(T\right)\) curves show two drops as the temperature is decreased below the onset of superconducting transition. To more exact studying of the transition region, we differentiated each electrical resistivity by temperature, \(d\rho \left(T\right)/dT\), and plotted them as a function of temperature in Fig. 1(b). The temperature derivative of \(\rho \left(T\right)\) indicates two peaks. This dual step transition is due to the granular structure and weak link nature of the samples. The first peak at \({T}_{C}^{mf}\) (intra-granular transition temperature) is associated with intra-granular fluctuation and presents the pairing transition temperature within grains, and the second one at \({T}_{CJ}\) (inter-granular transition temperature) corresponds to the inter-granular coupling. In the temperature range between \({T}_{C}^{mf}\)and \({T}_{CJ}\), the superconducting grains are decoupled, and the system as a whole is resistive. Below \({T}_{CJ}\), the grains are coupled, or in other terms, phase-locked with zero phase difference across the inter-granular junctions [55]. The intra-granular transition temperature \({T}_{C}^{mf}\) is determined to be sensitively unchanged by the addition of ZnO NPs and is ~ 104 K for all samples. However, the inter-granular transition temperature \({T}_{CJ}\) is affected by the amount of ZnO NPs addition. As shown in Table 1, the \({T}_{CJ}\) increases from 99.5 K for the ZnO free sample to its maximum value of about 102.5 K for the sample with 0.2 wt% additive and then drops for higher values of ZnO NPs and reaches 96.5 K for x = 1.0 wt%. These results show that the inter-granular coupling between grains improves by increasing the ZnO NPs concentration up to 0.2 wt%.
Table 1
The deduced parameters from temperature dependance of electrical resistivity measurements.
x (wt%) | \({T}_{C}^{on}\) (K) | \({T}_{CO}\) (K) | \({\varDelta T}_{C}\) (K) | \({T}_{C}^{mf}\) (K) | \({T}_{CJ}\) (K) | hole concentration, p |
0 | 108.5 | 96.0 | 12.5 | 104.0 | 99.5 | 0.121 |
0.1 | 109.0 | 100.0 | 9.0 | 104.0 | 102.0 | 0.127 |
0.2 | 108.0 | 101.5 | 6.5 | 104.0 | 102.5 | 0.129 |
0.3 | 108.5 | 96.0 | 12.5 | 104.0 | 98.5 | 0.121 |
0.5 | 108.5 | 94.0 | 14.5 | 104.0 | 97.5 | 0.118 |
1 | 109.0 | 88.5 | 20.5 | 104.0 | 96.5 | 0.111 |
Furthermore, it is well-known that the variation of the hole concentration in the CuO2 planes could affect the \({T}_{CO}\). The concentration of hole carrier per copper ion, \(p\), can be determined using the following expression [56, 57]:
$$p=0.16-{\left[(1-\frac{{T}_{CO}}{{T}_{C}^{max}})/82.6\right]}^{0.5}$$
1
,
where \({T}_{C}^{max}\) is the highest critical temperature of (Bi, Pb)-2223 superconducting phase and taken as 110 K. The calculated values for hole concentration are recorded in Table 1. With increasing the content of ZnO NPs from 0.0 to 0.2 wt%, the hole concentration, p, increases from 0.121 to 0.129. For higher amounts of ZnO NPs, it decreases and reaches 0.111 for x = 1.0 wt%. The improved inter-grain connectivity and grain morphology are the primary sources of increased hole carrier concentration after the inclusion of ZnO NPs in the (Bi, Pb)-2223 matrix.
3.2. Thermally activated flux flow analyses.
In the mixed state of high-temperature superconductors, disorders and defects induce barriers for the vortex motion, and three different situations can be expected; (1) unpinned vortex liquid (UVL) state: the energy barrier U0 is lower than the temperature and can be neglected, (2) Thermally activated flux flow (TAFF) regime: The energy barrier U0 is higher than the temperature and plays a vital role in vortex motion. (3) Vortex-glass (VG) state: the barrier grows unlimitedly at low critical current density and the linear resistivity drops to zero [58]. In the TAFF and UVL regimes, the temperature dependence of resistivity is defined according to the TAFF theory as [59, 60]:
$$\rho \left(T, B\right)=\left(2{\nu }_{0}LB/J\right)\text{exp}\left(-{J}_{C0}BVL/T\right) \text{s}\text{i}\text{n}\text{h}\left(JBVL/T\right)$$
2
,
where \({\nu }_{0}\) is an attempt frequency for a flux bundle hopping, L is the hopping distance, B is the magnetic induction, J is the applied current density, JC0 is the critical current density in the absence of flux creep, V is the bundle volume, and T is the temperature [61]. If the applied current is small enough so that \(JBVL/T\ll 1\), Eq. (2) can be simplified to
$$\rho \left(T, B\right)=\left(2{\rho }_{c}U/T\right) \text{e}\text{x}\text{p}\left(-U/T\right)={\rho }_{0f} \text{e}\text{x}\text{p}\left(-U/T\right)$$
3
,
where \(U={J}_{c0}BVL\) is the thermal activation energy and \({\rho }_{c}={\nu }_{0}LB/{J}_{c0}\). The detailed definitions of U and ρc indicate that \(2{\rho }_{c}U/T\) is dependent on temperature and magnetic field [31]. In cuprates and FeAs-based superconductors, \({\rho }_{0f}=2{\rho }_{c}U/T\) is assumed as a temperature-independent constant [14, 31, 58, 61]. The temperature dependence of the activation energy U is usually assumed as \(U\left(T, B\right)={U}_{0}\left(B\right)(1-T/{T}_{C})\), where U0 is the apparent activation energy. In this assumption, the natural logarithm of electrical resistivity is expressed as
$$\text{ln}\rho \left(T, B\right)=\text{ln}{\rho }_{0}-{U}_{0}\left(B\right)/T$$
4
,
where \(\text{ln}{\rho }_{0}=\text{ln}{\rho }_{0f}+ {U}_{0}\left(B\right)/{T}_{C}\). This equation is known as the Arrhenius relation [31, 61, 62]. According to the Arrhenius relation, the plot of lnρ vs. 1/T should show a linear behavior in the TAFF region. Consequently, the temperature dependence of the derivative \(D=-\partial (\text{ln}\rho )/\partial \left({T}^{-1}\right)\) shows a distinct plateau in the TAFF region. The plots of \(-\partial (\text{ln}\rho )/\partial \left({T}^{-1}\right)\) vs. T, for composites with x=0.0, 0.2, and 1.0 wt%, as typical samples, are depicted in Figs. 2(a-c) to indicate the temperature region that satisfies the Arrhenius relationship. As can be observed, however, the plateau is not seen but rather increases as temperature decreases. Such behavior has been observed in cuprates and iron-based superconductors [14, 17, 31, 61]. To solve this contradiction in the TAFF model, Zhang et al. [63, 64] established a new model, called the modified TAFF model, by suggesting non-linear activated energy of the form \(U\left(T, B\right)={U}_{0}\left(B\right){(1-T/{T}_{C})}^{q}\). By applying this non-linear activation energy, in the TAFF regime, to Eq. (3), it can be derived that
$$\text{ln}\rho =\text{ln}\left(2{\rho }_{c}{U}_{0}\right)+q\text{ln}\left(1-T/{T}_{C}\right)-\text{ln}T-{U}_{0}{(1-T/{T}_{C})}^{q}/T$$
5
,
and
$$-\partial \text{ln}\rho /\partial {T}^{-1}=[{U}_{0}{\left(1-T/{T}_{C}\right)}^{q}-T][1+qT/({T}_{C}-T)]$$
6
,
where q is a free parameter. According to the condensation model, q = 2 is expected in the case of high-temperature superconductors with large anisotropy, which shows 2D vortex behavior, whereas q = 1.5 was seen in high-temperature superconductors with small anisotropy showing 3D vortex behavior [14, 15, 58]. To determine the TAFF regime, zero temperature activation energy U0, and q parameter, the \(-\partial \text{ln}\rho /\partial {T}^{-1}\) vs. T, Ln ρ vs. T, and Ln ρ vs. 1/T plots were fitted using Eqs. (5 and 6). The Ln ρ vs. T curves for composites with x = 0.0, 0.2 and 1.0 wt% are shown in Figs. 2(d-f), as typical samples. The red solid line shows the best fit with Eqs. (5). Moreover, the Ln ρ vs. 1/T curves for different samples are represented in Fig. 3. The solid lines demonstrate the best fits with the modified TAFF model. As can be observed, these best fits agree well with the experimental values in the temperature range T* < T < Tk, which indicate the TAFF regions for different samples. The Tk is defined as the temperature on the higher side deviating from the TAFF fitting. It is the characteristic temperature that determines the transition temperature from the TAFF regime to the unpinned vortex liquid phase [58]. The T* is defined as the critical temperature below which the curve deviates from TAFF fitting. It represents the upper-temperature limit of the critical region for the vortex liquid to vortex glass state transition [65].
The obtained values for Tk, T* and temperature width of TAFF region, \({\varDelta T}_{TAFF}={T}_{k}-{T}^{*},\) are summarized in Table 2. As can be observed, the Tk and T* increase with the increase of the ZnO NPs concentration up to 0.2 wt% and then decrease for higher values of the addetive. The \({\varDelta T}_{TAFF}\) is decreased from 6 K for the ZnO-free sample to 4 K for the sample with x = 0.2 wt% and then increased for higher values of the ZnO NPs and reached 12 K for the sample with x = 1.0 wt%. These results indicate that the TAFF region is shifted to the higher temperatures and gets narrower by adding the ZnO NPs up to 0.2%. For higher values of additive, the TAFF region gets wider and transferred to lower temperatures. The deduced values for zero temperature activation energy U0, determined by the fitting of the experimental data, using Eqs. (5 and 6) in the TAFF region, are shown in Fig. 4. As seen, by increasing the ZnO NPs concentration, U0 increases from ~ 0.4×105 K for the ZnO free sample to ~ 1.4×105 K in the sample with 0.2 wt% ZnO NPs and then decreases for higher values of additive and reaches ~ 0.17×105 K for the sample with 1.0 wt% ZnO. This indicates that the addition of the 0.2 wt% ZnO NPs improves flux pinning capability of the (Bi, Pb)-2223 superconducting phase significantly.
Table 2
The deduced parameters from TAFF analyses.
x (wt%) | T* (K) | TK (K) | ΔTTAFF (K) | Tg (K) | s | U0 |
0 | 97.0 | 103.0 | 6.0 | 93.8 | 2.4 | 40894 |
0.1 | 101.0 | 105.0 | 4.0 | 99.8 | 1.5 | 83416 |
0.2 | 103.0 | 105.5 | 2.5 | 101.0 | 2.3 | 146217 |
0.3 | 98.0 | 103.0 | 5.0 | 94.9 | 1.9 | 34247 |
0.5 | 96.5 | 102.0 | 5.5 | 92.9 | 2.4 | 28935 |
1.0 | 89.5 | 101.5 | 12.0 | 87.4 | 2.0 | 17082 |
As observed in Figs. 2(d-f), the Lnρ curves begin to deviate upward from the solid red line, interpreted as the TAFF regime, in the temperature region below T*. It indicates a second-order phase transition from the vortex liquid phase to the vortex glass phase [14]. From this point of view, the deviation below T* is due to the increased effective activation energy caused by gradual vortex glass development as the temperature decreases in the vortex liquid phase. This temperature region is called a critical region present in the vortex liquid phase [14]. In the critical region, the vortex glass theory [66] predicts the temperature dependence of the linear resistivity through the relation \(\rho \left(T\right)\propto {\left(T-{T}_{g}\right)}^{s}\), where \(s=\nu (z+2-d)\) is the critical exponent and d is the dimensionality of the sample (d = 3 in the present samples), ν is the static index for vortex-glass correlation length, and z is the dynamic index for correlation time. According to Liu et al. [67], the electrical resistivity is given as
$$\rho \left(T\right)={\rho }_{n}{\left[\text{exp}(-{U}_{eff}/{k}_{B}T)\right]}^{s}$$
7
,
and the thermal activity energy in the critical region, present in the vortex liquid phase, is given as [14]
$${U}_{eff}={k}_{B}T\frac{({T}_{C}-T)}{({T}_{C}-{T}_{g})}$$
8
.
Moreover, according to the vortex glass phase transition theory [18, 23, 60], at the glass temperature Tg, one has \(\rho \left({T}_{g}\right)=0\). At the critical temperature TC, one has \(\rho \left({T}_{C}\right)={\rho }_{n}\), thus \(({U}_{eff}/{k}_{B}T)=0\). Hence one has \(0\le {U}_{eff}/{k}_{B}T\le 1\) in the temperature region \({T}_{g}\le T\le {T}_{C}\). A first-order series expansion in Eq. (7) around TC gives \(\rho \left(T\right)={\rho }_{n}{\left[1-\left({U}_{eff}/{k}_{B}T\right)\right]}^{s}\). Using Eq. (8) the temperature-dependent resistance in the vortex glass critical region is obtained as
$$\rho ={\rho }_{n}{\left(\frac{T-{T}_{g}}{{T}_{c}-{T}_{g}}\right)}^{s}$$
9
,
which is consistent with the vortex-glass theory. The experimental data in the vortex glass critical region has been fitted with Eq. (9). The dash lines in Figs. (2 and 3) represent the corresponding best fits for different composites. As can be seen, the fits agree well with the experimental values below T*. From the fitting using Eq. (9), the vortex glass temperature Tg and critical exponent s were evaluated. According to the vortex-glass theory, s ≤ 2.7 corresponds to the 2D vortex glass state while the values of s in between 2.7 to 8.5 correspond to the 3D vortex glass state [14, 17, 58]. As represented in Table 2, the obtained s values for different composites are smaller than 2.7, which indicates the 2D vortex glass state for the prepared composites. Therefore, all the samples undergo a phase transition from 2D vortex glass with s < 2.7 to 2D vortex liquid with q = 2 at Tg, which means that the 2D correlation created below Tg is maintained up to high temperature [14]. In other words, the 2D vortices in vortex liquid, which are determined from the q-values discussed above, are frozen into the 2D vortex glass with decreasing temperature, in agreement with the vortex glass theory [58]. As recorded in Table 2, by increasing the ZnO NPs concentration, the vortex glass transition temperature Tg increases from 93.8 K for the ZnO free sample to 101.0 K for the sample with 0.2 wt% ZnO NPs and then drops for more additives until it reaches 87.4 K for the sample with 1.0 wt% ZnO NPs.
To verify the accuracy of the obtained values for U0 from the above indirect approach, the temperature dependence of activation energy was calculated directly from the measurement data using the Arrhenius equation (Eq. (3)) by \(U\left(T, H\right)=-TLn\left[\rho (T, H)/{\rho }_{0f}\right]\). The calculated temperature dependence of activation energy for different composites has been shown in Figs. 5(a-f). As observed, all the samples show a similar temperature dependence. As the temperature decreases from the high temperatures the magnitude of U(T, H) increases slowly, then increases steeply. The TAFF region for different composites is also highlighted in Figs. 5(a-f), which has a different temperature range depending on the amount of ZnO NPs additive. As mentioned above, the temperature dependence of the activation energy on the TAFF region is given by \(U\left(T, H\right)={U}_{0}\left(H\right){(1-T/{T}_{C})}^{q}\). The U(T, H) had been calculated, using obtained values for U0, TC, and q, and has been plotted by solid red lines for different composites in Figs. 5(a-f). As observed in the figures, the agreement between the experimental data and the\(U\left(T, H\right)={U}_{0}\left(H\right){(1-T/{T}_{C})}^{q}\) relation, in the TAFF region, is excellent in all composites.
3.3. AC susceptibility analyses.
The AC susceptibility measurement is extensively employed as a non-destructive and effective tool for understanding and characterization of the intra-grain and inter-grain components in the polycrystalline high-temperature superconductors [40, 45, 55, 68–70]. The plots of the real part of AC susceptibility, χ́, and its derivative, dχ́ /dT, versus temperature at a frequency of 300 Hz and the AC background magnetic field of 250 A/m, for different composite samples are displayed in Figs. 6(a) and (b), respectively. A characteristic feature of the AC susceptibility in HTSCs is the presence of double drops in χ́ (T) and correspondingly two peaks in dχ́ /dT. The first peak at TC is related to the transition to superconducting state within grains and correlated to the intra-granular properties, and the second peak at TCJ is related to coupling matrix and correlated to the inter-granular properties. As mentioned above, in the temperature range TCJ < T <TC, the superconducting grains are decoupled, and the system as a whole is resistive. Below TCJ, the grains are coupled, or in other terms, phase-locked with zero phase difference across the inter-granular junctions. Wide/narrow separation of intra- and inter-granular peaks signifies a worse/better connection among the grains. As demonstrated in Fig. 6(b), TC is sensitively unchanged with ZnO NPs addition. However, TCJ associated with the occurrence of the weak links network among grains is sensitive to the amount of ZnO additive. This result indicates that the addition of the ZnO NPs does not have a sensitive effect on the intra-granular properties of samples, while it affects the inter-granular properties. TCJ was determined from the derivative of χ́ versus temperature graph (Fig. 6(b)). As shown in Fig. 6(c), by increasing the ZnO NPs concentration, TCJ increases from 95.5 K for the ZnO-free sample to 102 K for the sample with x = 0.2 wt% and then shows a decreasing behavior for higher values of ZnO NPs until it reaches to 93 K for the sample with x = 1 wt%. These results can be a clear sign of enhanced inter-granular properties with ZnO NPs addition. The observed behavior has a good agreement with obtained values from resistivity measurements.
High-temperature superconductor materials can be modeled as an array of weakly Josephson coupling. Grains coupling takes place via the Josephson currents in the layers among grains [40]. The Josephson coupling energy can be expressed as [40]:
$${E}_{j}=\frac{h}{4\pi e}{I}_{0}$$
10
,
where h is the Planck constant, e is the elementary charge, and I0 is the maximum Josephson's current that passes across the grain boundaries and according to Ambegaokar Baratoff expressed as [40, 71]:
$${I}_{0}=1.57\times {10}^{-8}\times \frac{{T}_{C}}{({T}_{C}-{T}_{CJ})}\times 100$$
11
.
The Josephson coupling energy, Ej, for different composites, has been calculated using the above equations, and its value, at H = 250 A/m, as a function of the ZnO NPs concentration is plotted in Fig. 6(c). As seen, the Ej is increased from ~ 0.037 eV to ~ 0.130 eV by increasing the ZnO NPs concentration from 0.0 to 0.2 wt% and then is decreased for higher ZnO NPs concentrations until it reaches 0.029 eV for the sample with 1.0 wt% additive. This result points out the significant improvement of the inter-granular coupling with the addition of the 0.2 wt% ZnO NPs. The stronger inter-granular Josephson coupling energy leads to the stronger trapping force, and, therefore, the greater critical current density will be.