# Evidence of structural instability near 𝑇^∗∼250 K in the resistivity of Bi2Sr2CaCu2O8 whiskers

## Abstract

We report anomalous features in the normal-state resistivity of single crystalline Bi<sub>2</sub>Sr<sub>2</sub>CaCu<sub>2</sub>O<sub>8</sub> whiskers near $`T^{}250`$ K. From these varied oxygen-doping samples, the resistance ($`R`$) was found to deviate upward from the linear-$`T`$ relation for $`T<T^{}`$, while $`R`$ keeps decreasing with $`T`$. The deviation, $`\mathrm{\Delta }RR(a+bT)`$, reaches a maximum in a temperature range of $`25`$ K, just before $`RT`$ follows the well-known descent associated with the pseudogap opening in underdoped samples. A second kink was also found in some samples immediately following the first one, resulting in an S-shaped feature in the $`RT`$ curve. The resistance then resumes nearly linear-$`T`$ decrease below the anomalies in contrast to the first case. We interpret these features as being related to crystal structure transformation (or lattice distortion), as was evidenced in thermal and elastic property measurements. These structural instabilities seem to be connected to the subsequent dynamics as $`T`$ is further lowered.

74.25.Fy, 74.72.Hs, 75.30.Kz

The normal state of high-$`T_c`$ cuprates provides rich information for an understanding of superconducting mechanism. Two of the many interesting normal-state properties are the so-called pseudogap opening and crystal structural transformation. In resistivity ($`\rho `$) measurement, the former was believed to manifest itself as a downturn deviation from the linear $`\rho T`$ relation below some characteristic temperature $`T^{}>T_c`$ in underdoped samples. Evidence for crystal structure transformation (or lattice distortion) is more difficult to detect because of such factors as crystal quality and the weakness of its physical effects. Structural transformations are generally studied by elastic and acoustic methods . In most of the cuprates, anomalous features corresponding to structural instabilities in the normal state have been observed. In La<sub>2-x</sub>Sr<sub>x</sub>CuO<sub>4</sub>, a tetragonal to orthorhombic structure transition upon cooling occurred at 220 K . Around the same temperature for YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7-δ</sub>, the sound velocity shows a step-like change and was associated with the instability corresponding to a structural order-disorder transition . A step-like change in Young’s modulus (hysteresis) also appeared in elastic measurements of single crystals at 200 - 240 K . In Bi cuprates, similar evidence was also accumulated. Dominec et al.  reported sound velocity deviations around 240 K in Bi<sub>2</sub>Sr<sub>2</sub>CuO<sub>6</sub> (Bi-2201). Acoustic studies revealed sound velocity softening along the $`a`$\- axis around 250 K in Bi<sub>2</sub>Sr<sub>2</sub>CaCu<sub>2</sub>O<sub>8</sub> (Bi-2212) samples . In elastic property measurements of similar Bi-2212 whiskers as studied in the present work, Tritt et al.  found anomalous peaking of Young’s modulus and stress-strain hysteresis near 270 K, and interpreted it as evidence for a phase transition. Similar results were also obtained for Bi<sub>2</sub>Sr<sub>2</sub>Ca<sub>2</sub>Cu<sub>3</sub>O<sub>10</sub> (Bi-2223) . More directly, by using acoustic and x-ray diffraction methods, Titova et al.  consistently found a small increase of lattice dimensions at $`T190270`$K for the cuprates: YBCO (123 and 124), Bi-2201, 2212, and 2223, and Ti-series compounds. The structural instabilities of the cuprates observed at comparable temperature ranges (about 200 to 300 K) demonstrate common features consistent with their similar crystalline structures. Obviously, structural transformation affects transport properties of the material and should be detectable by resistivity measurement. Indeed, resistivity jumps were observed above $`T_c`$ in La<sub>2-x</sub>Sr<sub>x</sub>CuO<sub>4</sub>, which are caused by a structural phase transition . However, few results were reported for other cuprates in the temperature regions where lattice instabilities were found by mechanical methods described above. This situation can be understood in two ways. First, the influence of structural instabilities on sample resistivity is small, because at such structural transformation, the crystal symmetry usually remains the same, only the lattice parameters change (distortion), leaving weak traces on electron scattering. Secondly, the small change in resistivity can be easily covered up by effects such as percolation, and is undetectable unless the crystal is of very high quality. Therefore, in the present work on pure single crystalline Bi-2212, it is interesting that we observed unusual features in the normal-state resistivity in temperature regions where x-ray and mechanical studies had revealed anomalous structural properties. This is a clear indication for a correlation between these features probed by different methods. Moreover, drastically different temperature dependence of resistivity appeared below these anomalies, showing crucial connections between the phenomena in these temperature regimes.

In our extensive resistivity measurements of both Bi-2212 and Bi-2223 whiskers, we often noticed the data were fluctuating in a temperature region between 180 and 270 K. Outside this window, the signal is much more stable. Since this temperature range corresponds to the important regime where the resistivity shows dramatic changes and is central in the normal-state theory, we were motivated to check the region more closely. In this work we report five samples selected from many others which exhibit anomalous behavior in this temperature window.

Samples of Bi-2212 whiskers were grown by a sintering method . They are rectangular needle-like tapes with typical dimensions: 3 mm $`\times `$ 10 $`\mu `$m $`\times `$ 0.5 $`\mu `$m. The three crystalline axes ($`a`$, $`b`$ and $`c`$) are along these directions, respectively. Various characterization by scanning and transmission electron microscopy, and energy dispersive x-ray analysis indicate that the whiskers are good single crystals with perfect surface morphology throughout the whole length ($``$3 mm). The as-grown whiskers are usually oxygen overdoped. Before making the first measurements, some samples were annealed in flowing nitrogen, making them slightly underdoped. The resistivity was measured by the standard four-wire method. The electrical leads were made by magnetron sputtering of silver through a mask. A dc current (0.5 $`\mu `$ A) was driven along the $`a`$-axis and voltage was also measured in this direction.

Figure 1a shows the resistance ($`R`$)data of one whisker (sample A, as-grown), together with a segment of $`R`$ above 200 K. At high temperature, $`RT`$ is well fitted to a linear line (fitting range: 260 - 308 K) with $`R(\mathrm{\Omega })=129.62+2.475T`$. As the temperature is further lowered, $`R`$ shows a clear upward curving just before it follows the well-known downward deviation. To examine the curve in more detail, we plotted the temperature dependence of the resistance deviation $`\mathrm{\Delta }RR(a+bT)`$, where $`(a+bT)`$ is the high temperature fit as described. The sharp turning point and the slope change are more evident in the plot of $`\mathrm{\Delta }R`$ as shown in Fig. 1b. We can see that, while $`R`$ keeps decreasing with $`T`$, $`\mathrm{\Delta }R`$ starts to deviate upward at $`T_0260`$ K and reaches a maximum at $`T^{}=236`$ K, it then falls and becomes negative, i.e. $`R<a+bT`$. The peak $`\mathrm{\Delta }R/R`$(300 K) is about 0.5%. Although the choice of fitting range of temperature may slightly affect the kink, the two major features that $`R`$ curves upward from linear-$`T`$ dependence and reaches a sharp turning point are clearly identifiable. Such small bumps could be easily smeared out in samples with defects such as grain boundaries, where percolation is not negligible, to yield a fully linear-$`T`$ resistance. In our twined samples, which have a two-step superconducting transition, linear-$`T`$ dependence was observed without any feature in the normal state. This agrees with the studies by Gorlova and Timofeev  who made combined electron diffraction and resistivity measurement on the same sample, and showed that a wider portion of linear-$`T`$ resistivity appears in twinned whiskers or samples covered with a polycrystalline film than in purer samples. This explains the often-observed discrepancy in bulk materials between transport and other measurements in which the sample’s polycrystalline nature is not important. The smallness in the change of resistivity puts high requirement on sample quality to observe these anomalies. The features were identified only after more significant kinks around this temperature region were found in our Bi-2223 single crystal samples . The kink in $`\mathrm{\Delta }R`$ seems to follow a power-law relation $`(1T/T_0)^2`$ (dotted line in Fig. 1b, where $`T_0=260`$ K). However, it could also fit to a weak exponential increase of the form: $`R_0=\mathrm{exp}[c(T_0T)]`$, with $`c=0.1`$ to 0.2.

In Fig.2 we plotted $`\mathrm{\Delta }R/R`$(300) vs. $`T`$ for four more samples plus sample A from Fig. 1b. The annealing status of these samples are as follows: A and B: as-grown in ambient pressure; C: annealed in flowing N<sub>2</sub> ($`450^{}`$C, 8 h); D: flowing N<sub>2</sub> annealing ($`450^{}`$C, 4 h); and E: flowing O<sub>2</sub> annealing ($`450^{}`$C, 10 h). The doping level may not solely depend upon the annealing conditions because the sample size varies. Nevertheless, data from long-time annealed samples are reliable. Two cases in the temperature dependence of $`\mathrm{\Delta }R`$ can be classified, as shown in the separate panels of Fig. 2. In the lower panel, $`\mathrm{\Delta }R`$ reveals one kink as discussed. $`\mathrm{\Delta }R`$ falls steeply right after the sharp peak, which gives rise to the well-known downward turning $`RT`$ in underdoped cuprates. Our identification of this transition temperature is much clearer than the data available in the literature . The curves in the top panel show another kink following the first one (samples B and C), which resulted in an S-shaped feature in the $`RT`$ curve. At the end of this curving, $`R`$ nearly resumes the previous linear-$`T`$ descent. The origin of this anomaly is unclear. It does not show up in the underdoped cases. For the sample annealed in oxygen (E), the kink around 250 K is absent, but the kink at lower temperature ($``$ 220 K) is consistent with the second kinks in the other two samples. A very similar single kink was also found in the as-grown data of sample C (refer to the inset of Fig. 3), which is also oxygen overdoped. These features in the normal state thus seem to be intrinsic to the Bi-2212 samples. This result joins our previous results from Bi-2223 samples to give a consistent picture about the anomaly around this characteristic temperature region in Bi-series cuprates. The peaking temperature $`T^{}`$ shows a trend to increase with the extent of underdoping. $`T^{}=254`$ K is the highest for sample C which experienced the longest N<sub>2</sub> annealing, whereas the oxygen-annealed sample E showed the lowest $`T^{}`$ (220 K). The temperature $`T_0`$, at which $`\mathrm{\Delta }R`$ starts to climb up, also shows the similar dependence. The detailed characteristic temperatures for the samples are listed in Table I. In light of the thermal and elastic measurement results in the literature, which showed evidence of structural phase transformation around the same temperature region as is reported here, we interpret such upward deviation as due to structural transformation or lattice distortion. Similar kinks in resistivity had been observed in La-214 due to structural transformation . The signal is often fluctuating immediately following the kink, in the region around 200 K as shown by the oscillating $`\mathrm{\Delta }R`$. This is obviously correlated to the $`\mathrm{\Delta }R`$ jump, and may well mean an influence on electron scattering due to structural instabilities.

The peak temperature $`T^{}`$ clearly separates two regions in which different mechanisms are switched on. Especially for the noisy region below $`T^{}`$, if it is caused by the opening of a pseudogap in the spin excitation, the initial fluctuating $`R`$ data may be a clue for this mechanism, when the antiferromagnetic correlation is gradually frozen out. In the scenario of stripe phase formation, on the other hand, the stripe phase may be triggered by the lattice distortion. Charge or spin excitation following a structure transformation (or lattice distortion) was established by neutron scattering studies . Bianconi et al.  have shown for Bi-2212 that 1D modulation of the CuO<sub>2</sub> plane is formed by alternating stripes of low temperature orthorhombic and low temperature tetragonal lattices. However, our $`T^{}(3T_c)`$ is higher than their data ($`1.4T_c`$). Whatever the model will be, the present result shows that the lattice structure undergoes some change in all the samples, which initiates new resistive mechanisms. However, the subsequent dynamics depends on the oxygen doping level, not on this structural change.

The upward deviation is not due to thermal stress in the sample, which is anchored onto the glass substrate by silver leads. We estimate the thermal stress to be a small value $``$ 0.018 GPa at 250 K, by taking the Young’s modulus $`Y=20`$ GPa , the thermal expansion coefficient along the $`a`$-axis $`\alpha =14.4\times 10^6`$ K<sup>-1</sup> , and a length between voltage leads of about 0.3 mm at room temperature. Chen et al.  had measured the effect of uniaxial stress (strain) on the resistivity of similar whiskers, and found that the influence is very small ($`1/12000`$ at room temperature). Moreover, the pressure generally causes a decrease in resistivity.

To further study the influence of doping on $`T^{}`$, we annealed one sample (C) successively in flowing nitrogen. The resistance data from this sample are as shown in Fig. 3. The result from the as-grown sample shows a slope change near 200 K, $`RT`$ is linear above this temperature. After one annealing, a new feature appeared around $`T^{}220`$ K, while the slope change around 200 K remains. After the second annealing, $`T^{}`$ shifted to 245 K, as indicated by the arrows, showing the tendency that $`T^{}`$ increases with further underdoping, which agrees with the widely observed behavior of resistivity anomaly and the pseudogap.

All the above discussion is based upon crystal structure instability in the normal state. In light of the magnetic structure of the CuO<sub>2</sub> planes, an alternative interpretation may come from the competition between quasiparticle scattering and the increasing correlation with antiferromagnetic (AF) ordering as the temperature is decreasing. It is interesting to compare the present results with the anomalous resistivity of magnetic materials . In fact, resistivity kinks were commonly found near magnetic phase transitions in the latter. For example, in dysprosium single crystals , a kink in the linearly decreasing $`\rho T`$ appears near the Néel point when the sample transforms from the paramagnetic into the AF state. Similar anomalies were also reported in europium chalcogenides . It is surprising that the Néel temperature of perovskite KNiF<sub>3</sub> is about 253 K , very close to the anomalous temperatures in the present work. This may point to a common origin of the resistivity kinks for the materials with similar crystal structures.

In the scenario of free electron scattering with spin excitations, the total resistivity consists of three additive terms: the $`T`$-independent residual resistivity $`\rho _0`$ due to elastic impurity scattering, the lattice contribution (phonon) $`\rho _LT`$, and the spin-disorder resistivity $`\rho _M`$. The resistivity kink (exponentially increasing with decreasing $`T`$ ) is associated with the spin-disorder resistivity ($`\rho _M`$). In the critical region of magnetic transition, the behavior of $`\rho _M`$ reflects the strongly temperature dependent short-range spin-spin correlation. This is in the regime of spin-disorder due to the large long-range magnetic fluctuations near the transition temperature . The resistivity thus takes the form:

$$\rho (T)=\rho _0b|t1|\mathrm{ln}|t1|^1,$$
(1)   
where $`t=T/T_c`$. For $`b>0`$, $`\rho (T)`$ shows a concave cusp at the magnetic transition temperature $`T_c`$. If this idea is valid, then the observed anomaly near $`T^{}250`$ K must come from the antiferromagnetic ordering in the CuO<sub>2</sub> planes. Especially, the sharp turning point in all the curves may well signify a similar magnetic phase transition. Currently only the spin fluctuation theory  is a close approach to this picture.

In conclusion, an upward deviation from the linear-$`T`$ dependence were observed around $`T^{}250`$ K in the normal-state resistivity of Bi-2212 single crystals. This is usually followed by a fluctuating region near 200 K. We interpret such behavior as due to structural instabilities in accordance with many results from other measurement techniques (thermodynamic, elastic, acoustic, and x-ray). A peak in the resistance deviation ($`\mathrm{\Delta }R`$) is clearly identifiable. Below this sharp turning point, the resistivity drops more steeply, signifying a new mechanism in underdoped samples. This turning in resistivity had been widely identified as pseudogap opening. However, the scenario of stripe formation preceded with lattice instabilities was also proposed . The result shows that the lattice instability exists in all the samples regardless of their doping level. The same result was also found in our Bi-2223 samples. This gives a consistent picture intrinsic to similar crystal structures of Bi-cuprates. Although the structural transformation seems to trigger new mechanism, it is the oxygen doping that controls the subsequent behavior of $`RT`$. It is noticeable that our $`T^{}`$ data are consistently higher than the literature values (typically 120 -165 K, with the highest for Bi-2212 being 220 K ). There is no identifiable feature (smooth $`dR/dT`$) in our $`RT`$ curves below 180 K. An alternative interpretation of the resistance kinks is the correlation between electrons and AF spin fluctuations. Similar mechanisms in magnetic materials are known to give rise to the kinks in the resistivity curves at magnetic phase transition. Our work should stimulate theoretical interest in this direction.