# Structural instability associated with the tilting of CuO6 octahedra in La2-xSrxCuO4

## I Introduction

Number of experimental results accumulated for a decade have shown that spin fluctuations, appearing as incommensurate peaks around $`(\pi ,\pi )`$, play a significant role in the high-$`T_\mathrm{c}`$ superconductivity. In particular, a recent neutron-scattering work on high-quality La<sub>2-x</sub>Sr<sub>x</sub>CuO<sub>4</sub> (LSCO) single crystals by Yamada et al. has clearly demonstrated that there exists a linear relationship between the incommensurability and $`T_\mathrm{c}`$ in a wide hole concentration range. On the other hand, a primary contribution of phonon to high-$`T_\mathrm{c}`$ superconductivity has not been seriously considered because electrical resistivity measurements suggest that the electron-phonon (e-ph) interaction is not as large as that of BCS superconductors such as A15-type compounds.

It is known that the structural properties of LSCO is closely related to the tilting pattern of CuO<sub>6</sub> octahedra. Birgeneau et al. and Böni et al. clarified that the tetragonal X-point phonon mode, associated with tilting of CuO<sub>6</sub> octahedra along the \[$`\mathrm{1\; 1\; 0}`$\] or \[$`\overline{1}\mathrm{1\; 0}`$\] tetragonal axis, goes soft at the high-temperature tetragonal (HTT) to the low-temperature orthorhombic (LTO) structural phase transition. Thurston et al. studied temperature dependence of the $`\mathrm{\Gamma }`$\- and Z-point modes in the LTO phase, which are split from the degenerated X-point mode in the HTT phase. They have shown that the Z-point mode first hardens below the HTT-LTO transition, then softens again with further decreasing temperature, indicating incipient structural transition from LTO to the low-temperature tetragonal (LTT) phase. The structural phase transitions and soft phonons in this system are summarized in Appendix A.

Recently, Lee et al. have discovered that the softening of Z-point phonon breaks at $`T_\mathrm{c}`$ in the optimally doped La<sub>1.85</sub>Sr<sub>0.15</sub>CuO<sub>4</sub> sample. This new finding, suggesting a competition between the LTO-LTT transition and the appearance of superconductivity, is contrary to the conventional view that the e-ph interaction in LSCO is weak thus not essential. Therefore it is now increasingly important to revisit structural properties of LSCO and elucidate their relation to the high-$`T_\mathrm{c}`$ superconductivity. In the present study, we have carried out comprehensive inelastic neutron-scattering measurements of the Z-point phonon using $`x=0.10`$, 0.12 and 0.18 single crystals. Sample characterizations and neutron-scattering measurements are described in Sec. II. To study the phonon softening in detail, we utilized a new technique for optimizing resolution function of neutron scattering, which is described in Appendix B. In the course of studying the soft phonons, we discovered incommensurate structural diffuse signals around $`(0k\pm \delta l)_{\mathrm{LTO}}`$ $`(k=odd,l=even)`$ in the HTT phase for both $`x=0.12`$ and 0.18. The newly found diffuse signals as well as the soft phonons are reported in Sec. III, and discussed in Sec. IV. @

## II Experimental Details

In order to grow a LSCO single crystal which is large, highly crystalline and homogeneous in the Sr distribution, Traveling-Solvent-Floating-Zone (TSFZ) method has been utilized and improved over past few years. In the present study, we have grown $`x=0.10`$, 0.12 and 0.18 single crystals by using the TSFZ method; all the crystals have a volume of about 1 cm<sup>3</sup> with the mosaicness of 0.4 full-width at half-maximum (FWHM). To make these crystals stoichiometric, i.e., oxygen deficiency free, as-grown samples were annealed under pure oxygen gas flow at 900 C for 50 hours, then cooled down to 500 C with a cooling rate of 10 C per hour and kept there for 50 hours, and finally cooled down slowly to room temperature.

Bulk magnetic susceptibilities were measured with a SQUID magnetometer. All the samples show superconductivity with shielding signal $`100`$ % and the onset of $`T_\mathrm{c}`$’s were determined to be 28.5 K, 31.5 K and 36.5 K for $`x=0.10`$, 0.12 and 0.18, respectively. The transition width defined as the temperature range between 5 % and 95 % of the maximum shielding signal is about 3 K for all the samples, which sharpness suggests that doped Sr are homogeneously distributed. The c-axis lengths of all the samples, measured at room temperature by using X-ray powder diffractometer, are in good agreement with previous report. The HTT-to-LTO transition temperatures, defined as $`T_{\mathrm{s1}}`$ in this paper, were determined to be 240 K and 125 K for $`x=0.12`$ and 0.18 by neutron diffraction.

Neutron scattering experiments were performed on the triple-axis spectrometer TOPAN installed at the JRR-3M research reactor in the Japan Atomic Energy Research Institute (JAERI). The final energy of neutrons was fixed at $`E_\mathrm{f}=14.1`$ meV. The $`(\mathrm{0\; 0\; 2})`$ Bragg reflection of Pyrolytic Graphite (PG) was used in order to monochromatize and analyze neutron beam. A typical horizontal collimation is Blank-60-S-60-Blank. PG filter was inserted into scattered beam to reduce higher-order contaminations. All the single crystals have twined domains in the LTO phase. Therefore, we should consider that all the measurements were performed in the superposed $`(h0l)_{\mathrm{LTO}}`$ / $`(0kl)_{\mathrm{LTO}}`$ zone. Throughout this paper, the reciprocal space is described by using reciprocal lattice unit (r.l.u.) in the LTO (Bmab) coordinate system. A crystal was put into an Aluminum container filled with He gas then attached to the cold finger of a closed-cycle <sup>4</sup>He cryostat. Temperature was measured by using Si-diode thermometers attached to the cold finger and the bottom part of the Al container.

## III Results

### A Soft phonons

The Z-point phonons on $`x=0.10`$, 0.12 and 0.18 around $`𝐐_0=(\mathrm{3\; 0\; 2})`$ were studied as a function of temperature. Constant-$`Q`$ scans were carried out at $`𝐐^{}=𝐐_0+𝐪`$ where the instrumental resolution matches most effectively with the dispersion of phonon (focusing). The procedure we employed to determine the most effective focusing point $`𝐐^{}`$ is described in Appendix B. The phonon spectra for $`x=0.10`$ and 0.12 were measured at $`𝐐^{}=(\mathrm{3.09\; 0\; 1.88})`$, while for $`x=0.18`$ the scan was carried out at $`𝐐^{}=(\mathrm{3.10\; 0\; 1.96})`$. Well-defined phonon spectra were obtained for all the samples, indicating that the resolution ellipsoid at $`𝐐^{}`$ sufficiently focuses with the slope of dispersion. To quantitatively analyze the phonon spectra, data were fitted with the following scattering function $`S(Q,\omega )`$ convoluted with a proper instrumental resolution:

$`S(Q,\omega )`$ $`=`$ $`{\displaystyle \frac{\omega }{1\mathrm{exp}(\omega /k_BT)}}\left\{{\displaystyle \frac{1}{\pi }}{\displaystyle \frac{A}{\mathrm{\Gamma }_{\mathrm{ph}}/2}}{\displaystyle \frac{1}{1+\left(\frac{\omega \omega _{\mathrm{ph}}}{\mathrm{\Gamma }_{\mathrm{ph}}/2}\right)^2}}\right\},`$   
$`A`$ $`=`$ $`\chi (Q)={\displaystyle _{\mathrm{}}^+\mathrm{}}{\displaystyle \frac{\chi (Q,\omega )}{\omega }}𝑑\omega ,`$   
where $`\omega _{\mathrm{ph}}`$ and $`\mathrm{\Gamma }_{\mathrm{ph}}`$ are the phonon energy and the intrinsic line-width at $`𝐐^{}`$, respectively. Fitting thus carried out quite well reproduce all the observed data.

Temperature dependences of the soft phonon energy $`\omega _{\mathrm{ph}}`$ for $`x=0.10`$, 0.12 and 0.18 are shown in Fig. 1. All the data exhibit the softening of phonons with decreasing temperature toward $`T_\mathrm{c}`$, which confirms that the phonons at $`𝐐^{}`$ indeed reflect the behaviors of Z-point phonons. As a reference, the Z-point ($`𝐐_0=(\mathrm{1\; 0\; 4})`$) phonon for $`x=0.15`$ reported by Lee et al. is also shown in Fig. 1(c). For $`x=0.18`$, the softening of phonon breaks with the appearance of superconductivity as seen in $`x=0.15`$. In contrast, the softening continues even below $`T_\mathrm{c}`$ for $`x=0.10`$ and 0.12. These results indicate that the structural instability for the LTT phase persists even in the superconducting phase for $`x=0.10`$ and 0.12.

The intrinsic line-widths of the soft phonons $`\mathrm{\Gamma }_{\mathrm{ph}}`$ for $`x=0.10`$, 0.12 and 0.15 are shown as a function of temperature in Figs. 2(a)-(c). The data for $`x=0.15`$ is also after Lee et al.. Down to 40 K, the line-widths for all the samples decrease with decreasing temperature, corresponding to increase of phonon life-time. However, this narrowing suddenly stops, i. e. breaks, around 40 K ($`T_d`$) and the line-widths become constant at lower temperatures. On the other hand, in La<sub>2</sub>CuO<sub>4</sub> studied by Lee et al., the narrowing continues down to the lowest temperature, indicating that the break of the line-width narrowing is a characteristic phenomenon of 

the Sr-doped samples. As for $`x=0.18`$, it is difficult to estimate the accurate value of $`\mathrm{\Gamma }_{\mathrm{ph}}`$ because the two phonons, i.e., $`\mathrm{\Gamma }`$ and Z-point modes, were so close that the phonon spectra were superposed with each other.

### B Incommensurate diffuse peak in the HTT phase

Upon cooling, the $`(0kl)`$ $`(k=odd,l=even)`$ superlattice reflections emerge at the HTT-LTO transition temperature $`T_{\mathrm{s1}}`$. As briefly described in Sec. II, $`T_{\mathrm{s1}}`$ values of $`x=0.12`$ and $`x=0.18`$ were determined to be 240 K and 125 K from the temperature dependence of the

$`(\mathrm{0\; 3\; 2})`$ peak intensity. Note that we inserted a PG filter between sample and analyzer as well as between monochromator and sample, which almost completely eliminates higher-order contaminations. In the course of studying the soft-mode phonons and superlattice reflections, we found that there remains a weak diffuse peak centered at $`(\mathrm{0\; 3\; 2})`$ and $`\omega =0`$ even above $`T_{\mathrm{s1}}`$. Since this peak is associated with the softening of X-point phonon and diverges at $`T_{\mathrm{s1}}`$, we have noticed that this is a so-called “central peak” as studied in SrTiO<sub>3</sub> and many other systems.

At higher temperature, we found that this central peak starts splitting into two incommensurate components at $`(\mathrm{0\; 3}\pm \delta 2)`$ or more generally $`(0k\pm \delta l)`$ $`(k=odd,l=even)`$. This phenomenon was first reported by Shirane et al. in their preliminary experiment for $`x=0.15`$. As shown in Fig. 3(a), the incommensurate “central” peaks are clearly seen in $`x=0.12`$ at 315 K, temperature much higher than $`T_{\mathrm{s1}}`$. Similar incommensurate peaks were also observed for $`x=0.18`$. The peak profiles for both samples were well fitted with a double Lorentzian. The sharp peak in Fig. 3(a) shows the $`(\mathrm{0\; 3\; 2})`$ superlattice peak

at $`T=13.5`$ K, of which the line-width corresponds to the instrumental resolution at $`(\mathrm{0\; 3\; 2})`$. By fitting with a double Lorentzian convoluted with the resolution, the intrinsic line-widths of central peaks were estimated to be $`0.06`$ Å<sup>-1</sup> for both the samples and for all the temperature range above $`T_{\mathrm{s1}}`$, indicating short range in-plane correlations ($`\xi 17`$ Å).

The temperature dependence of the splitting $`\delta `$ for $`x=0.12`$ and 0.18 were also measured. As shown in Fig. 3(b), the $`\delta `$ value of $`x=0.18`$ (open diamonds) increases with increasing temperature and is saturated around $`\delta 0.12`$ (r.l.u.). Upon cooling, on the other hand, $`\delta `$ approaches zero at $`T_{\mathrm{s1}}`$, suggesting that the central peak indeed starts splitting just at $`T_{\mathrm{s1}}`$. It is remarkable that the $`\delta `$ values for both $`x=0.12`$ (closed circles) and 0.18 can be scaled using each $`T_{\mathrm{s1}}`$ value. Note that the saturated value $`\delta 0.12`$ is very close to the incommensurability $`ϵ`$ of elastic and inelastic magnetic scattering peaks seen in La<sub>2-x</sub>Sr<sub>x</sub>CuO<sub>4</sub> at $`(\pi (1\pm 2ϵ),\pi )`$ and $`(\pi ,\pi (1\pm 2ϵ))`$. In the $`x=0.25`$ sample, which has no HTT to LTO structural phase transition, the central peak was also searched around $`(\mathrm{0\; 3\; 2})`$ at room temperature. However, no signature was found.

The incommensurate central peak was also measured around $`(\mathrm{0\; 1\; 4})`$ at 315 K for $`x=0.12`$. The intrinsic line-width is almost same as that of $`(\mathrm{0\; 3\; 2})`$. The width of the central peak along the $`l`$ direction, which corresponds to the out-of-plane correlation, was measured at $`(\mathrm{0\; 1\; 4})`$. The peak-width along l is almost identical to that along k, indicating short-range isotropic correlations for the in-plane and out-of-plane directions. The intensity ratio of the $`(\mathrm{0\; 3\; 2})`$ and $`(\mathrm{0\; 1\; 4})`$ central peaks is 2.9, which is close to the ratio of $`Q^2`$ values for these two peaks, 2.7, indicating that the central peak originates from atomic displacement. The intensity ratio between the central peak and the fundamental Bragg peak is about 10<sup>-3</sup> in the present neutron-scattering measurement. We found a similar diffuse peak in X-ray diffraction measurements. However, this diffuse peak intensity in X-ray diffraction is 10<sup>-5</sup> times weaker than that of the fundamental reflection. This difference between neutron and X-ray measurements suggests that the central peaks are mainly contributed from the displacement of oxygen atoms.

## IV Discussion

### A Soft phonons

The present study, combined with the work by Lee et al. , has established that the softening of Z-point phonon suggesting incipient LTO-LTT transition breaks at $`T_\mathrm{c}`$ for optimally and overdoped LSCO and that the softening persists even below $`T_\mathrm{c}`$ in the underdoped region. This breaking found in optimally and overly doped LSCO is consistent with previous results obtained by other techniques suggesting competition between the structural phase transition and the superconductivity in LSCO and related compounds. Such a competition is also seen in other systems such as the A15 superconductors. On the contrary, it appears that the behaviors of soft phonons in the underdoped region are qualitatively different from those in the overdoped region. Note also that the persistence of phonon softening below $`T_\mathrm{c}`$ is not a characteristic feature for the 1/8-doping. The change in behaviors of phonon softening across the optimum hole concentration might be related to the incommensurate elastic magnetic peaks in the underdoped region and/or the energy-gap in the spin fluctuations near the optimally doped region. It is intriguing to relate the appearance of elastic magnetic signals to the LTO-to-LTT instability persisting below $`T_\mathrm{c}`$ in underdoped LSCO. It is clear, however, that even more systematic investigation is required to elucidate the origin of soft-phonon breaking and its influence to other properties.

Another remarkable feature is that the narrowing of soft-phonon line-width breaks below $`T_\mathrm{c}`$, which is confirmed in underdoped and optimally doped LSCO. This phenomenon is contrary to that observed in BCS superconductors,  where e-ph scattering disappears because of the BCS gap opening. It is thus suggested that the intrinsic phonon line-width is not owing to e-ph interactions, though the origin of the breaking of soft-phonon narrowing is still not clear.

### B Incommensurate diffuse peaks

Residual week diffuse peak observed above $`T_{\mathrm{s1}}`$ at the LTO superlattice position is very similar to the central peak associated with R-point phonon softening in SrTiO<sub>3</sub>. Interestingly, the central peak in LSCO splits into incommensurate peaks and the incommensurability $`\delta `$ saturates around $`\delta 0.12`$ r.l.u., which value is close to the splitting of incommensurate magnetic signals. This implies that the incipient lattice modulation starts appearing at very high temperature. It has been reported that the averaged (long-ranged) structure is different from local (short-ranged) structures in the LSCO cuprates. Quantitative comparison between the experimental results and structural models including local distortions is required. Further neutron scattering along this line is planned in the near future.

## Acknowledgments

We thank Y. Endoh, N. Toyota, R. J. Birgeneau, T. Imai, and H. Fukuyama, for several stimulating discussions. We also acknowledge M. Onodera and K. Nemoto for their technical supports on neutron scattering experiments. This work was supported in part by a Grant-In-Aid for Scientific Research from the Japanese Ministry of Education, Science, Sports and Culture, and by a Grant for the Promotion of Science from the Science and Technology Agency and also supported by CREST and the US-Japan cooperative research program on Neutron Scattering. Work at Brookhaven National Laboratory was carried out under contact No. DE-AC02-98CH10886, Division of Material Science, U. S. Department of Energy.

## A Structural phase transitions and soft phonons in LSCO

As shown in Fig. 4(a), all the structural phases of LSCO can be characterized by two order parameters $`Q_1`$ and $`Q_2`$, which correspond to the rotation of the CuO<sub>6</sub> octahedron along \[$`\mathrm{1\; 0\; 0}`$\] and \[$`\mathrm{0\; 1\; 0}`$\] in Bmab notation. In the high-temperature tetragonal (HTT) phase, no static tilting exists and the structure has a tetragonal symmetry with the space group of I4/mmm; $`|Q_1|=|Q_2|=0`$. With decreasing temperature, coherent tilting which rotation axis is parallel to \[$`\mathrm{1\; 0\; 0}`$\] develops below $`T_{\mathrm{s1}}`$ and it leads to the low-temperature orthorhombic phase (LTO) with the space group Bmab; $`|Q_1|0,|Q_2|=0`$. $`T_{\mathrm{s1}}`$ changes from 520 K for $`x=0.00`$ to 0 K for $`x>0.21`$. In some doped LaCuO<sub>4</sub> such as La<sub>2-x</sub>Ba<sub>x</sub>CuO<sub>4</sub>, with further lowering temperature, a low-temperature tetragonal (LTT) phase appears with the space group P4<sub>2</sub>/ncm; $`|Q_1|=|Q_2|0`$. An intermediate phase

between LTO and LTT, which is written in the Pccn orthorhombic symmetry, is also known; $`|Q_{1,2}|0,|Q_1||Q_2|`$.

The HTT-to-LTO structural phase transition in LSCO is driven by softening of the zone-boundary optical phonon at X-point $`𝐪=\frac{1}{2}(1\pm \mathrm{1\; 0})`$. The temperature dependence of the soft phonon energy is shown schematically in Fig. 4(b), which is based on the Landau free energy expanding to eighth order for {$`Q_1`$, $`Q_2`$}. At $`T_{\mathrm{s1}}`$ the doubly degenerate X-point phonons freeze, resulting in the HTT-to-LTO phase transition. In the LTO phase, due to the crystal symmetry, the degenerate phonon branches split into $`\mathrm{\Gamma }`$\- and Z-point phonon of which amplitudes correspond to $`Q_1`$ and $`Q_2`$, respectively. The $`\mathrm{\Gamma }`$-point phonon hardens with decreasing temperature suggesting the stability of coherent $`|Q_1|`$ tilting, while the Z-point phonon softens at lower temperature, indicating the instability toward the LTT phase. If the Z-point phonon completely freezes, a further transition from the LTO to Pccn or LTT phase occurs. As for LSCO, no Pccn or LTT phase exists but the softening of the Z-point phonon is observed, indicating incipient transition to these phases. Note that since the present study cannot distinguish a qualitative difference between the Pccn and LTT, we define a structural phase below LTO as the LTT phase in this paper for convenience.

## B Experimental techniques in phonon measurements

For the present study, it is essential to precisely measure the frequency and intrinsic width of phonon. As shown in the inset of Fig. 5(a), the instrumental resolution of neutron triple-axis spectrometer has a slope in the $`Q\omega `$ space. Therefore, there exist focusing and defocusing side for the phonon dispersion. Instead of performing a constant-$`Q`$ scan at the zone-boundary $`X`$-point $`𝐐_0`$, we looked for the most effective focusing point in the vicinity of $`Q_0`$. We made constant-$`Q`$ scans at several different position $`𝐐^{}`$ on the arc $`𝐐^{}=𝐐_0+𝐪`$ as shown in Fig. 5(a), making a natural assumption that the phonon dispersion is isotropic near $`𝐐_\mathrm{𝟎}`$. Figure 5(b) shows the $`\theta `$ dependence of the line-width of the phonon spectrum for $`x=0.12`$ at $`T=315`$ K, where $`\theta `$ is defined as shown in Fig. 5(a). It is clearly seen that the line-width has a minimum at $`\theta 37^{}`$. We have thus chosen $`𝐐^{}=(\mathrm{3.09\; 0\; 1.88})`$ for $`x=0.10`$ and 0.12. The well-defined phonon spectrum for $`x=0.12`$ obtained at $`𝐐^{}`$ is shown in the inset of Fig. 5(b). As for $`x=0.18`$, $`𝐐^{}`$ was determined to be $`(\mathrm{3.10\; 0\; 1.96})`$ by using the same procedure.

Note that this method is based upon the assumption that, in the formula of phonon dispersion $`\omega _{\mathrm{ph}}^2(q)=\omega ^2(Q_0)+Aq^2`$, the coefficient $`A`$ is weakly temperature dependent. This assumption was justified by the work done by Birgeneau et al..

<sup>1</sup><sup>1</sup>footnotetext: Present address: Research Institute for Scientific Measurements, Tohoku University, Aoba-ku, Sendai 980-8577, Japan.