# Triple sign reversal of Hall effect in HgBa2CaCu2O6 thin films after heavy-ion irradiations

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## Abstract

The triple sign reversal in the mixed-state Hall effect has been observed for the first time in ion-irradiated HgBa<sub>2</sub>CaCu<sub>2</sub>O<sub>6</sub> thin films. The negative dip at the third sign reversal is more pronounced for higher fields, which is opposite to the case of the first sign reversal near T<sub>c</sub> in most high-T<sub>c</sub> superconductors. These observations can be explained by a recent prediction in which the third sign reversal is attributed to the energy derivative of the density of states and to a temperature-dependent function related to the superconducting energy gap. These contributions prominently appear in cases where the mean free path is significantly decreased, such as our case of ion-irradiated thin films.

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The Hall anomaly in the mixed state of type II superconductors is one of the most attractive subjects, both experimentally and theoretically, in the field of vortex dynamics. According to classical theories , the vortex motion due to the Lorentz force should generate a Hall voltage with the same sign as observed in the normal state because normal electrons in the vortex cores effectively produce this voltage. To the contrary, a puzzling sign reversal of the Hall effect has been observed in various conventional superconductors, such as impure Nb  and V crystals , and Nb thin films , and in some high-T<sub>c</sub> superconductors (HTS), such as YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7</sub> crystals  and La<sub>2-x</sub>Sr<sub>x</sub>Cu<sub>2</sub>O<sub>4</sub> . Furthermore, a double sign reversal has been observed in highly anisotropic HTS, such as Bi<sub>2</sub>Sr<sub>2</sub>CaCu<sub>2</sub>O<sub>8</sub> crystals , Tl<sub>2</sub>Ba<sub>2</sub>CaCu<sub>2</sub>O<sub>8</sub> films , and HgBa<sub>2</sub>CaCu<sub>2</sub>O<sub>6</sub> (Hg-1212) films . Various models related to two band effects , induced pinning , a superconducting fluctuation , and a flux backflow  have been proposed to interpret these Hall anomalies, but they have not been able to explain the experimental results. Therefore, the origin of the mixed-state Hall effect still remains an unsolved subject.

An interesting microscopic approach based on a time-dependent Ginzburg-Landau theory has been proposed in a number of papers . In this approach, the mixed-state Hall voltage in type II superconductors is determined by the quasiparticle and hydrodynamic contributions of the vortex cores. Since the sign of hydrodynamic term is determined by the energy derivative of the density of states , if that term is negative, a sign anomaly can appear. This theory is qualitatively consistent with experimental results , especially for high magnetic fields and for temperatures near T<sub>c</sub>.

Recently, Kopnin  has developed a modified theory which includes an additional force arising from charge neutrality effects. In this theory, interestingly, he anticipated the possibility of a third sign anomaly when the system remains moderately clean, this anomaly would even occur at low temperatures. This implies that the third sign reversal could be observed if the mean free path of a system were reduced from the clean limit of $`l>\xi `$ to the moderately clean limit of $`l\xi `$, where $`l`$ is the mean free path and $`\xi `$ is the superconducting coherence length. This may be the case for columnar defects due to high-density ion irradiations.

Hg-1212 thin films are suitable candidates for observing the third sign reversal because the general trend of the negative dip at low field near T<sub>c</sub> still remains at higher fields , a situation which is clearly different from the cases of the Bi and the Tl compounds . This suggests that at higher fields, the negative contribution due to the additional transverse force  in the Hg-1212 compound is more substantial than that in either the Bi or Tl compounds.

In this Letter, we present the first report on an observation of triple sign reversal in superconducting Hg-1212 thin films containing columnar defects produced by 5-GeV Xe ions. The level of the dose, 1.5 $`\times `$ 10<sup>11</sup> ions/cm<sup>2</sup>, was equivalent to the mean distance, less than 258 $`\AA `$, between the columnar defects, thus effectively reducing the mean free path of the samples, even at low temperatures. Consequently, we were able to observe, for the first time to the best of our knowledge, the triple sign reversal predicted by the microscopic theory of nonequilibrium superconductivity. This observation will provide new insight, we believe, into the flux dynamics in type II superconductors.

The fabrication process  and the transport properties  of the Hg-based thin films used in this study were previously reported in detail. The mid-transition temperatures T<sub>c</sub> of the as-grown thin films on (001) SrTiO<sub>3</sub> substrate were 122 - 124 K. The critical current density at zero field was $`10^6`$ $`A/cm^2`$ at 100 K. The X-ray diffraction pattern indicate highly oriented thin films with the c axis normal to the substrate plane. The minor phase of HgBa<sub>2</sub>Ca<sub>2</sub>Cu<sub>3</sub>O<sub>8</sub> was less than 5 %. The ion irradiation was performed at the Superconducting Cyclotron Center at Michigan State University by using 5-GeV Xe ions. The irradiation was done at room temperature along a direction normal to the film surface. The irradiation dose was 1.5 x 10<sup>11</sup> ions/cm<sup>2</sup>, which corresponded to a matching field, B<sub>ϕ</sub>, of $``$ 3 T. These ions produced continuous amorphous tracks with diameters of 50 - 100 $`\AA `$ in the Hg-1212 thin films. The Hall resistivity $`\rho _{xy}`$ and the longitudinal resistivity $`\rho _{xx}`$ were measured simultaneously using a two-channel nanovoltmeter (HP34420A) and the standard five-probe dc method. A magnetic field was applied parallel to the c axis of the Hg-1212 films. $`\rho _{xy}`$ was extracted from the antisymmetric parts of the Hall voltages measured under opposite fields. The applied current densities were 250 - 500 A/cm<sup>2</sup>. Both $`\rho _{xy}`$ and $`\rho _{xx}`$ were Ohmic at the currents used in this study.

Typical temperature dependences of $`\rho _{xx}`$ before (B<sub>ϕ</sub> = 0 T) and after heavy-ion irradiation (B<sub>ϕ</sub> = 3 T) for fields up to 8 T are shown in Fig. 1. A large enhancement of the zero-resistance temperature, T<sub>c,zero</sub>, which is due to strong pinning by the columnar defects, is clearly visible. This is consistent with the results of previous works  on HTS with columnar defects. We observe that the enhancement of T<sub>c,zero</sub> above 3 T is rather small compare to that of below 3 T, indicating that depinned vortices with a density of $`n_\varphi =(HB_\varphi )/\mathrm{\Phi }_o`$ really contribute to the resistivity, where $`\mathrm{\Phi }_o`$ is the flux quantum. The enhancement of pinning by the columnar defects becomes effective below the temperature T\* which is marked in Fig. 1 by an arrow.

Figure 2 (a) shows $`\rho _{xy}`$ before and after irradiation for H = 2, 4, 6, and 8 T. For the data at H = 2 T, the first sign reversal, which appears in the vicinity of the transition temperature, does not shift after the irradiation, while the second sign reversal shifts to higher temperature. These double sign reversals are not very rare for HTS. For the irradiated sample, however, if we look at $`\rho _{xy}`$ on a magnified scale we can observe a third sign reversal at a relatively lower temperature, as shown in Fig. 2 (b). The negative dip becomes clear with increasing field, a finding which is contrary to the one  for the first sign reversal in HTS. For the unirradiated thin films, however, no third sign change is observed for fields up to 8 T. The inset in Fig. 2 shows the third-sign-reversal regions where $`\rho _{xy}`$ is positive (P), negative (N), and zero (Z), $`i.e.`$, below the resolution in our experiment. Thus, we claim that we clearly observed a third sign reversal for the irradiated thin films.

Now the question arises as to why such a multiple Hall sign reversal is possible for some superconductors. Is there any relevant explanation for this phenomenon? Fortunately, a recent study by Kopnin  claims that such a phenomenon is possible if the force arising from the effects of vortex motion on the pairing interaction, which was neglected in previous works , is added to the Lorentz force. The additional force is induced by the kinetic effect of charge imbalance relaxation and thus depends on the difference between the charge densities of the system in the superconducting and the normal states. According to this theory, the Hall conductivity $`\sigma _H`$ due to the motion of a single vortex is determined by three terms: localized excitations, delocalized excitations, and an additional force term. Therefore, $`\sigma _H`$ can be expressed by the sum of three terms:

$$\sigma _H=\sigma _H^{(L)}+\sigma _H^{(D)}+\sigma _H^{(A)}.$$
(1)   
Using $`\mathrm{}=c=k_B=1`$, the Hall conductivity due to localized excitations,$`\sigma _H^{(L)}`$, is given by

$$\sigma _H^{(L)}\frac{Ne}{B}\frac{(\omega _o\tau )^2}{1+(\omega _o\tau )^2},$$
(2)   
where N is the density of carriers, $`\tau `$ is the relaxation time, $`\omega _o\mathrm{\Delta }^2/E_F`$ is the distance between the energy levels in the vortex core, and E<sub>F</sub> is the Fermi energy. The portion of Hall conductivity contributed by the additional force,$`\sigma _H^{(A)}`$, is

$$\sigma _H^{(A)}\frac{e}{B\lambda }\left(\frac{\nu }{\zeta }\right)\mathrm{\Delta }^2\beta (T),$$
(3)   
where $`\lambda `$ is the BCS coupling strength, $`\nu /\zeta `$ is the energy derivative of the density of states, $`\mathrm{\Delta }`$ is the superconducting energy gap, and $`\beta (T)`$ is a temperature-dependent function and is positive, which depends on temperatures in the following way: either $`\beta `$ = 1 near T<sub>c</sub> or $`\beta (T)\mathrm{\Delta }/[Tln(\mathrm{\Delta }/T)]`$ at low temperatures . Since the delocalized excitation term, $`\sigma _H^{(D)}`$, is due to the density of quasiparticles outside the vortex core, the sign of $`\sigma _H^{(D)}`$ is the same as the sign of the normal-state Hall conductivity and $`\sigma _H^{(D)}`$ is very small at low temperatures compared to $`\sigma _H^{(L)}`$ . Due to this, we will simply neglect $`\sigma _H^{(D)}`$ at low temperatures. It is found  that the tangent of the Hall angle, $`tan\mathrm{\Theta }\omega _o\tau `$, is very small $`(0.01)`$ for the dirty region near T<sub>c</sub> and approaches $`1`$ for the superclean region at T $`T_c`$. This is consistent with the theoretical calculation . $`\sigma _H^{(A)}`$ deduced from charge imbalance relaxation is determined by the energy derivative of the density of states $`\nu /\zeta `$ at the Fermi surface and by $`\beta (T)`$. Since this latter term is negative, the sign of $`\sigma _H`$ can critically depend on this term. If $`\sigma _H^{(A)}`$ is negative and if it is the dominant contribution, then $`\sigma _H`$ can be negative.

In order to estimate the sign of $`\nu /\zeta `$, we had better comment on the symmetry of the superconducting order parameters. Very recently, Himeda $`\mathrm{𝑒𝑡}`$ $`\mathrm{𝑎𝑙}.`$  calculated the microscopic structure of the vortex cores in HTS by using the two-dimensional t-J model for a wide range of doping rates. They argued that the density of states split into two levels due to mixing of the s- and the d-wave components in the underdoped regions. The typical density of states for d-wave superconductors was observed in the overdoped regions. This indicates that the sign of $`\nu /\zeta `$ in $`\sigma _H^{(A)}`$ should not be based on the BCS s-wave theory . Within the context of the Kopnin’s theory, however, we can estimate the sign of $`\sigma _H^{(A)}`$ from the experimental results. From the data for H = 2 T in Fig. 2, for example, the sign of the additional force term is negative simply because $`\sigma _H`$ is positive and $`\sigma _H^{(A)}`$ is negative; thus, $`\nu /\zeta `$ is negative.

According to Eq. (1), $`\sigma _H`$ allows multiple sign reversals as a function of temperature and mean free path. The sign reversals arise from competition between a positive $`\sigma _H^{(L)}`$ and a negative $`\sigma _H^{(A)}`$. For the dirty case with $`l<\xi `$, $`\sigma _H^{(A)}`$ is dominant because $`(\omega _o\tau )^210^4`$ is very small as T $``$ T<sub>c</sub>. Thus, the sign of $`\sigma _H`$ can be negative. For the clean case with $`l>\xi `$, $`\sigma _H^{(L)}`$ is dominant because the magnitude of $`(\omega _o\tau )^2`$ is very large compared to its magnitude for the dirty case; thus $`\sigma _H`$ is positive in the low-temperature region. This is a plausible interpretation for the double sign reversal observed in Fig. 2. The double sign reversal was also observed in highly anisotropic HTS, such as Bi- and Tl-based compounds .

Now, the problem is to explain the triple sign reversal. The first thing we should notice is that the triple sign reversal is observed only in the ion-irradiated samples. In that case, $`\sigma _H^{(L)}`$ decreases seriously because $`\omega _o\tau `$ is reduced drastically by a change from the clean to the moderately clean or the dirty case. Then, a third sign reversal in the mixed state is quite natural, and this interpretation is in good agreement with the experimental observations. To explain this in detail, we should point out that at low temperatures, $`\sigma _H^{(L)}`$ and $`\sigma _H^{(A)}`$ have different temperature dependences through $`\omega _o\tau `$ and $`\beta (T)`$. Since $`\beta (T)`$ increases as $``$ 1/T with decreasing temperature and $`(\omega _o\tau )^2`$ is still small for the moderately clean region, $`\sigma _H^{(A)}`$ can exceed $`\sigma _H^{(L)}`$ again at low temperatures , especially for the moderately clean case. As a result, we should expect a third sign reversal of the mixed-state Hall effect if high-density impurities exist, which is in agreement with our observation in Fig. 2.

At this point, it is meaningful to compare the temperature dependence of the Hall angles before and after ion irradiation, as shown in Fig. 3. As the temperature decreases from the normal state to the superconducting state, $`tan\mathrm{\Theta }`$ of the pristine sample increases steeply and then shows a peak at a relatively low temperature. The maximum magnitude of $`tan\mathrm{\Theta }`$ at H = 8 T is much larger than that observed in YBCO crystals  which are believed to be very clean superconductors. Note that $`tan\mathrm{\Theta }`$ is reduced significantly by the ion irradiation, even above T where the pinning is not important. This result should be explained by an impurity effect rather than by the pinning effect. This strongly supports the above interpretation that $`\sigma _H^{(L)}`$ can decrease if a clean system become a moderately clean after the irradiation.

Note that we observe the third sign reversal for Hg-1212 thin films irradiated with an ion dose of 1.5 x 10<sup>11</sup> ions/cm<sup>2</sup>, which corresponds to an average distance of 258 $`\AA `$ between the columnar defects. If we consider columnar defects with the diameter 50 - 100 $`\AA `$ and universal defects, such as oxygen vacancies, in the pristine thin films, the mean free path is very low and is much smaller than the value reported for YBCO crystals in the low-temperature region . Therefore, we can observe a triple sign reversal after heavy-ion irradiations because the irradiated thin films are probably moderately clean, even at low temperatures.

As a final note, since the above interpretation is based on the assumption that there are localized states at the core level, it is worth mentioning the existence of localized core states in d- wave superconductors. Localized core states, which are consistent with the predictions of theoretical works , have been observed in HTS by using various experimental probes, such as a far-infrared spectroscopy  and scanning tunneling spectroscopy . Furthermore, in the moderately clean case, Kopnin and Volovik  have observed that $`\sigma _H^{(L)}`$ for d-wave superconductors is similar to the previous result  based on s-wave superconductors. On the other hand, in a recent calculation  for the quasiparticle state in a d-wave superconductor, Frantz and Tesanovic have claimed that the bound state in the vortex core was not observed.

In summary, the Hall effect in Hg-1212 films has been studied before and after irradiation by high-energy Xe ions. After irradiation with a dose of 1.5 x 10<sup>11</sup> ions/cm<sup>2</sup>, we find that columnar defects play an important role not only as strong pinning sites but also as high-density impurities which can effectively reduce the mean free path even at low temperatures. As a result, we observe a triple sign reversal, which can be qualitatively interpreted within the framework of a recent model based on the nonequilibrium microscopic theory.

This work is partially supported by the Ministry of Science and Technology of Korea through the Creative Research Initiative Program. The work at University of Kansas is supported by AFOSR, NSF, NSF EPSCoR, and DEPSCoR.