# The Hall effect in Zn-doped YBa2Cu3O7-δ revisited: Hall angle and the pseudogap

## Abstract

The temperature dependence of the Hall coefficient is measured with a high accuracy in a series of YBa<sub>2</sub>(Cu<sub>1-z</sub>Zn<sub>z</sub>)<sub>3</sub>O<sub>6.78</sub> crystals with 0$``$$`z`$$``$0.013. We found that the cotangent of the Hall angle, $`\mathrm{cot}\theta _H`$, starts to deviate upwardly from the $`T^2`$ dependence below $`T_0`$ ($``$130 K), regardless of the Zn concentration. We discuss that this deviation is caused by the pseudogap; the direction of the deviation and its insensitivity to the Zn doping suggest that the pseudogap affects $`\mathrm{cot}\theta _H`$ through a change in the effective mass, rather than through a change in the Hall scattering rate.

The strong temperature dependence of the Hall coefficient $`R_H`$ of the high-$`T_c`$ cuprates has been considered to be one of the most peculiar properties of their unusual normal state . The rather complex behavior  of $`R_H(T)`$ can be turned into a simpler one by looking at the cotangent of the Hall angle , $`\mathrm{cot}\theta _H\rho _{xx}`$/$`\rho _{xy}`$; it has been shown that $`\mathrm{cot}\theta _H`$ of cuprates behaves approximately as $`T^2`$, regardless of material  and carrier concentration . This remarkable simplicity in the behavior of $`\mathrm{cot}\theta _H`$ led to the idea  that $`\mathrm{cot}\theta _H`$ reflects a Hall scattering rate $`\tau _H^1`$, which is different from the scattering rate $`\tau _{tr}^1`$ governing the diagonal resistivity $`\rho _{xx}`$. There are two physical pictures to account for this apparent separation of the scattering rates: One picture considers that two distinct scattering times $`\tau _{tr}`$ and $`\tau _H`$, possibly associated with different particles, govern different kinds of scattering events . The other picture considers that the scattering time is strongly dependent on the position on the Fermi surface (FS) and that $`\rho _{xx}`$ and $`\mathrm{cot}\theta _H`$ are governed by the scattering events on different parts of the FS .

Separately from the above development, it has become a common understanding  that in underdoped cuprates a pseudogap in the density of low-energy excitations is developed at a temperature much higher than the superconducting transition temperature $`T_c`$. In underdoped YBCO, the in-plane resistivity $`\rho _{ab}`$ shows a clear downward deviation from the $`T`$-linear behavior below a temperature $`T^{}`$, which has been discussed to mark the onset of the pseudogap . This $`T^{}`$ is notably higher than the other characteristic temperature $`T_g`$ determined from the onset of a suppression in the Cu NMR relaxation rate , which has also been associated with the pseudogap. The presence of two different temperature scales, $`T^{}`$ and $`T_g`$, is intriguing. It was proposed recently that at the upper temperature scale $`T^{}`$ the CuO<sub>2</sub> plane starts to develop local antiferromagnetic correlations  or charged stripe correlations ; the lower temperature scale $`T_g`$ corresponds to the opening of a more robust pseudogap in the density of states , which can be observed by the angle-resolved photoemission  or by the tunneling spectroscopy .

It was previously discussed  that the pseudogap causes a deviation from the $`T^1`$ behavior in $`R_H(T)`$ at $`T^{}`$. The conspiring changes in $`\rho _{ab}(T)`$ and $`R_H(T)`$ at $`T^{}`$ leave the $`T^2`$ behavior of $`\mathrm{cot}\theta _H`$ unchanged at $`T^{}`$, which led to the belief that $`\mathrm{cot}\theta _H`$ is rather insensitive to the opening of the pseudogap. However, given the recent understanding that the pseudogap has two characteristic temperatures $`T^{}`$ and $`T_g`$, it is left to be investigated how $`\mathrm{cot}\theta _H(T)`$ behaves around $`T_g`$.

Since the pseudogap effect is expected to be related to the antiferromagnetic fluctuations , there have been efforts to investigate how the pseudogap feature is affected by Zn doping onto the CuO<sub>2</sub> planes, which produces spin vacancies. The reported Zn-doping effects on the pseudogap are not simple; for example, the pseudogap feature in $`\rho _{ab}(T)`$ in underdoped YBCO crystals is almost unchanged , while the suppression in the Cu NMR relaxation rate below $`T_g`$ is diminished with only 1% of Zn . To build a complete picture of the pseudogap effect, it is also useful to investigate how the Zn doping affects the pseudogap in the Hall channel.

In this paper, we report the results of our measurements of the Hall effect in YBa<sub>2</sub>(Cu<sub>1-z</sub>Zn<sub>z</sub>)<sub>3</sub>O<sub>y</sub> crystals with $`y`$=6.78, which corresponds to an underdoped concentration. At this composition $`y`$=6.78, which gives $`T_c`$$``$75 K in pure crystals, a peak in $`R_H(T)`$ can be clearly seen and also the pseudogap feature in $`\rho _{ab}(T)`$ is clearly discernible (due to the rather wide $`T`$-linear region above $`T^{}`$); from the literature, we can infer that $`T^{}`$ is about 200 K (Ref. ) and $`T_g`$ is about 130 K (Ref. ). Our measurements of three samples with different Zn concentrations (z=0, 0.006, and 0.013) found that a deviation from the $`T^2`$ behavior in $`\mathrm{cot}\theta _H`$ takes place in all the samples at the same temperature $`T_0`$ which is very close to $`T_g`$, indicating that the pseudogap indeed affects $`\mathrm{cot}\theta _H`$ near $`T_g`$ and that the effect is robust against Zn doping.

There have been several publications reporting the effect of Zn doping on $`R_H`$ in YBCO, but the results are not converged. The data by Chien, Wang, and Ong indicate that $`R_H`$ of optimally-doped crystals increases with increasing $`z`$ in the whole temperature range above $`T_c`$ and the $`T`$ dependence becomes less pronounced  \[it is possible that in their samples the effective carrier concentration is changing, because the slope of $`\rho _{ab}(T)`$ is increasing with $`z`$\]. Mizuhashi et al. reported that $`R_H`$ increases over the whole temperature range with $`z`$ (almost like a parallel shifting), while the slope of $`\rho _{ab}(T)`$ in the $`T`$-linear part is unchanged . On the other hand, Walker, Mackenzie, and Cooper reported that, in their Zn-doped crystalline thin films, $`R_H`$ at 300 K remains essentially unchanged, while at low temperatures $`R_H`$ is progressively suppressed with increasing $`z`$ . In the present work, we therefore paid particular attention to reduce the errors in the measurement of $`R_H`$; the Hall voltage is measured with magnetic-field sweeps at constant temperatures, and errors due to the geometrical factors are minimized by making small voltage contacts and by determining the sample thickness with a high accuracy. We note that making the voltage contacts on the side faces (not on the top face) of the crystals is essential in reducing the error and increasing the reproducibility.

The Zn-doped YBCO single crystals are grown by a flux method using pure Y<sub>2</sub>O<sub>3</sub> crucibles . All the crystals measured here are naturally twinned. The oxygen content is tuned to $`y`$=6.78 by annealing the crystals with pure YBCO powders in air at 575C for 37 h, and subsequent quenching to room temperature. The final oxygen content is confirmed by iodometric titration. The actual Zn concentration in the crystals are measured with the inductively-coupled plasma (ICP) spectrometry with an error in $`z`$ of less than $`\pm `$0.001.

The measurements are performed with a low-frequency (16 Hz) ac technique. Longitudinal and transverse voltages are measured simultaneously using two lock-in amplifiers during the field sweeps at constant temperatures. For the transverse signal, we achieved a high sensitivity by subtracting the offset voltage at zero field (the offset comes from a slight longitudinal misalignment between the two Hall voltage contacts). The temperature is stabilized using a high-resolution resistance bridge with a Cernox resistance thermometer. We confined the maximum magnetic field to 4 T, with which the error of the Cernox thermometer caused by its own magnetoresistance is negligibly small in the temperature range of the present study. The magnetic field is applied along the $`c`$-axis of the crystals. To enhance the temperature stability, the sample and the thermometer are placed in a vacuum can with a weak thermal link to the outside. The achieved stability in temperature during the field sweeps is better than a few mK. The data are taken from $`4`$ T to $`+4`$ T, and then the asymmetrical component is calculated to obtain the true Hall voltage. The final accuracy in the magnitude of $`R_H`$ and $`\rho _{ab}`$ reported here is estimated to be better than $`\pm `$5%, and the relative error in the data for each sample is less than $`\pm `$2%.

Figure 1 shows the temperature dependence of $`\rho _{ab}`$ for the three Zn concentrations. Above $``$200 K, $`\rho _{ab}`$ of all the three samples shows a good $`T`$-linear behavior and the slope of this $`T`$-linear part does not change with $`z`$. As shown in the inset to Fig. 1, a downward deviation from the $`T`$-linear dependence takes place at the same temperature for all the three samples, indicating that the upper pseudogap temperature $`T^{}`$ does not change with $`z`$. This result is in good agreement with the previous reports .

Figure 2 shows the temperature dependence of $`R_H`$ for the three samples. Our results are somewhat different from previous results on single crystals , but rather resemble that of the thin film result . Notably, $`R_H`$ around 250 K does not change with $`z`$, while the peak at 110 K is clearly suppressed with increasing Zn concentration. Still, the behavior of $`\mathrm{cot}\theta _H`$ is in good agreement with the previous studies; as is shown in Fig. 3, $`\mathrm{cot}\theta _H`$ changes approximately as $`T^2`$ in a rather wide range, and the Zn impurities add a $`T`$-independent offset which is roughly proportional to $`z`$.

We note that the Zn-doping effect on $`R_H(T)`$ observed here is naturally expected in the context of the two scattering time scenario. One can infer that the primary effect of Zn-doping is to add some constant impurity-scattering rates to both $`\tau _{tr}^1`$ and $`\tau _H^1`$, because both $`\rho _{ab}(T)`$ and $`\mathrm{cot}\theta _H(T)`$ show essentially parallel shifts upon Zn-doping. Since one can approximately express $`\tau _{tr}^1`$$``$$`T`$ and $`\tau _H^1`$$``$$`T^2`$ in pure samples, the scattering rates in Zn-doped samples can be approximated as $`\tau _{tr}^1T+A`$ and $`\tau _H^1T^2+B`$. From the relation $`R_HH`$ = $`\rho _{ab}/\mathrm{cot}\theta _H`$ $`\tau _H/\tau _{tr}`$, $`R_H`$ is approximately written as $`R_H(T+A)/(T^2+B)`$ in Zn-doped samples. If we compare this expression with that for the pure samples, $`R_H^{pure}T/T^2T^1`$, we can infer that at high temperatures $`R_H`$ in Zn-doped sample should approach $`R_H^{pure}`$, while at low temperatures $`R_H`$ in Zn-doped sample is expected to become smaller than $`R_H^{pure}`$ (which can be easily seen when one considers $`T`$$``$0). The above heuristic argument implies that the weakening of the $`T`$ dependence of $`R_H(T)`$, combined with a $`z`$-independent room-temperature $`R_H`$, is a rather natural consequence of the Zn-doping in the two scattering time scenario, although this effect has not been well documented before.

Now let us analyze the data in more detail in regard of the $`T`$ dependence of $`\mathrm{cot}\theta _H`$. A close examination of Fig. 3 tells us that the data for $`z`$=0 and 0.006 are slightly curved in this plot; we found that the best power laws to describe the data in a wide temperature range are $`T^{1.85}`$, $`T^{1.9}`$, and $`T^{2.0}`$, for $`z`$=0, 0.006, and 0.013, respectively. In Fig. 4, we show plots of $`(\mathrm{cot}\theta _HC)/T^\alpha `$ vs $`T`$, which cancels out the power-law temperature dependence and therefore we can easily see the temperature range for the $`T^\alpha `$ dependence to hold well. Here, $`C`$ is the offset value (which increases with $`z`$) and $`\alpha `$ is the best power for each Zn concentration. It is clear from Fig. 4 that the power-law temperature dependence of $`\mathrm{cot}\theta _H`$ holds very well down to a temperature $`T_0`$ ($``$130 K) and then starts to deviate in all the three samples. Incidentally, the deviation occurs at a temperature very close to $`T_g`$, which is $``$130 K for $`y`$$``$6.78 (Ref. ). This is a strong indication that the change in $`\mathrm{cot}\theta _H(T)`$ is caused by the opening of the pseudogap . Our result shows that, unlike the Cu NMR relaxation rate, the Zn-doping does not diminish or shift the onset of the pseudogap marked by the change in $`\mathrm{cot}\theta _H`$ at $`T_0`$, at least up to the Zn concentration of 1.3%. Note, however, that the deviation from the power law becomes a bit weaker (or slower) with increasing $`z`$, which is similar to what is seen in the behavior of $`\rho _{ab}(T)`$ (inset to Fig. 1).

Given the fact that $`\mathrm{cot}\theta _H`$ is apparently affected by the pseudogap below $`T_0`$, it is useful to clarify how the pseudogap effect is reflected in the $`T`$ dependence of $`R_H`$, which is a result of the two different $`T`$ dependences  of the more fundamental parameters $`\tau _{tr}^1`$ and $`\tau _H^1`$. For this purpose, it is instructive to see how $`R_H(T)`$ would behave if $`\mathrm{cot}\theta _H`$ continues to change as $`T^\alpha `$ down to $`T_c`$. The inset to Fig. 2 shows the plots of the $`T`$ dependence of such hypothetical $`R_H^{hyp}`$ for the three samples, where $`R_H^{hyp}`$ is calculated by dividing $`\rho _{ab}`$ by $`(C+DT^\alpha )\times H`$, where $`D`$ is the $`T`$-independent value at temperatures above $`T_0`$ in Fig. 3. It is clear from the behavior of $`R_H^{hyp}`$ that $`R_H(T)`$ would not show a peak if $`\mathrm{cot}\theta _H`$ continues to change as $`T^\alpha `$ down to $`T_c`$. Therefore, we can conclude that the peak in $`R_H(T)`$ in underdoped YBCO is caused by the opening of the pseudogap.

It should be noted that the direction of the change in $`\mathrm{cot}\theta _H`$ at $`T_0`$ implies that $`\tau _H^1`$ is enhanced when the pseudogap opens; this is opposite to the effect on $`\tau _{tr}^1`$, which is reduced below $`T^{}`$. Therefore, we cannot simply conclude that the change in $`\mathrm{cot}\theta _H`$ is caused by a reduced electron-electron scattering, which is the natural consequence of a pseudogap in the low-energy electronic excitations. One possibility to understand this apparently confusing fact is to attribute the change at $`T_0`$ to the effective mass, rather than to attribute it to the scattering rate; remember that $`\mathrm{cot}\theta _H`$ = $`1/(\omega _c\tau _H)`$ $`m_H/\tau _H`$, where $`m_H`$ is the effective mass of the particle responsible for the Hall channel , so an increase in $`\mathrm{cot}\theta _H`$ is expected when the effective mass is enhanced. For example, if the pseudogap is related to the formation of a dynamical charged stripes , a modification in the FS topology, which leads to a change in the effective mass, is expected. This picture is also consistent with the observed robustness of the pseudogap feature in $`\mathrm{cot}\theta _H`$ upon Zn doping, because the change in the FS topology is rather insensitive to a small amount of impurities. One might question why there is little trace of the effective-mass change in the $`T`$ dependence of $`\rho _{ab}`$. If $`\mathrm{cot}\theta _H`$ and $`\rho _{ab}`$ reflect different parts of the FS (as is conjectured in the hot/cold spots scenario ), it is possible that the modification of the FS topology alters the band mass for the Hall channel while leaving that of the diagonal channel relatively unchanged.

Finally, we note that the peak in the $`T`$ dependence of $`R_H`$ is not always caused by the pseudogap. For example, in overdoped Tl<sub>2</sub>Ba<sub>2</sub>CuO<sub>6+δ</sub> (Tl-2201), it has been reported  that $`\mathrm{cot}\theta _H`$ shows a good $`T^2`$ dependence down to near $`T_c`$ (which implies that the pseudogap does not open), and yet the peak in $`R_H(T)`$ is observed at a temperature well above $`T_c`$. In this case, the peak in $`R_H(T)`$ is just a result of the two different $`T`$ dependences of $`\tau _{tr}^1T^n+A`$ (1$``$$`n`$$``$1.9) and $`\tau _H^1T^2+B`$ (note that in Tl-2201 both $`\tau _{tr}^1`$ and $`\tau _H^1`$ have somewhat large offsets even in pure crystals ). Mathematically, $`R_H(T^n+A)/(T^2+B)`$ has a peaked $`T`$-dependence and thus $`R_H(T)`$ can show a peak well above $`T_c`$ for some combination of $`A`$ and $`B`$, even when both $`\rho _{ab}`$ and $`\mathrm{cot}\theta _H`$ do not show any deviation from the power laws. On the other hand, as is demonstrated in the inset to Fig. 2, the peak in $`R_H(T)`$ of underdoped YBCO cannot be accounted for by the above origin and therefore is clearly caused by the pseudogap. This argument tells us that one should always look at the $`T`$ dependence of $`\mathrm{cot}\theta _H`$, not just the peak in $`R_H(T)`$, to determine whether the pseudogap is showing up through $`(\omega _c\tau _H)^1`$.

In summary, we observed that $`\mathrm{cot}\theta _H`$ of pure and Zn-doped YBCO ($`y`$=6.78) crystals shows an upward deviation from the $`T^2`$ behavior below a temperature $`T_0`$ that is notably higher than $`T_c`$ but is much lower than $`T^{}`$. The onset temperature $`T_0`$ for this deviation, which is found to be unaffected by Zn doping, is close to the lower temperature scale for the pseudogap $`T_g`$ (probed by the Cu NMR relaxation rate, for example). The fact that $`\mathrm{cot}\theta _H`$ tends to be enhanced below $`T_0`$ suggests that the effect of the pseudogap is not to reduce the Hall scattering rate; we therefore propose that the effect is more likely to be originating from a change in the Fermi surface topology, which causes a change in the effective mass. Also, we demonstrated that the peak in $`R_H(T)`$ of underdoped YBCO is not just a result of two different scattering times, but is actually a result of the pseudogap effect on $`\mathrm{cot}\theta _H`$.

We thank A. N. Lavrov and I. Tsukada for fruitful discussions, and J. Takeya for technical assistance.