# A study of the superconducting gap in 𝑅Ni2B2C (𝑅 = Y, Lu) single crystals by inelastic light scattering

## I Introduction

The rare-earth borocarbides are believed to be conventional BCS-type superconductors with a number of interesting properties that are not fully understood. Borocarbides are similar to intermetallic superconductors such as V<sub>3</sub>Si and Nb<sub>3</sub>Sn in that they have a relatively strong electron-phonon coupling constant and a moderately large density of states at the Fermi level. While it is generally agreed that the electron-phonon interaction is the underlying mechanism for superconductivity in these systems, the responsible phonons are claimed to be either a high-energy phonon (boron A<sub>1g</sub> near 850 cm<sup>-1</sup>)  or a low-energy soft-mode phonon. Additionally, the borocarbides have relatively simple tetragonal crystal structure, yet they show a variety of physical properties that have been active research topics over the past years. For example, some of the borocarbides exhibit magnetic ordering and superconductivity at around the same temperature, offering the possibility of studying the interplay between superconductivity and magnetism.

Even the non-magnetic rare-earth borocarbides $`R`$Ni<sub>2</sub>B<sub>2</sub>C ($`R`$ = Y, Lu) show rich superconducting phenomena, such as anisotropic upper critical fields and angular dependence of in-plane magnetization, a hexagonal-to-square vortex lattice transition, and phonon-softening at a finite wave vector where strong Fermi-surface nesting is suggested. The results of inelastic neutron scattering measurements are on soft $`q0`$ phonons, which would not be detected using Raman spectroscopy.

A study of the low-energy excitation spectra would clearly lead to a more complete understanding of the electronic interaction in these systems. The superconducting gap has been a major subject of research in superconductivity. Up to now, the gap in borocarbides has been studied by tunneling spectroscopy and infra-red (IR) reflectivity which are insensitive to the wave vector-space dependence of the gap. Electronic Raman spectroscopy is sensitive to the wave vector dependence of the gap. When the optical penetration depth exceeds the superconducting coherence length, it yields a susceptibility for two quasi-particles of essentially zero total wave vector. The quasi-particles that contribute to the response are those with wave vectors close to the Fermi surface for which the Raman vertex has a large modulus squared. This vertex equals the projection onto the polarization vectors of the incident and scattered photons of a tensor closely related to the inverse effective mass tensor. Manipulation of the polarization vectors changes the Raman symmetry and selectively probes the gap near certain regions of the Fermi surface. Raman spectroscopy studies have played an important role in understanding superconductivity of conventional and exotic superconductors. For example, superconductivity-induced redistribution of the electronic continua of the high-T<sub>c</sub> superconductors led to important clues as to the d-wave nature of the order parameter. However, there remain unsolved puzzles regarding different values of the 2$`\mathrm{\Delta }`$ peak positions in different scattering geometries, the power-law behavior of the scattering response below 2$`\mathrm{\Delta }`$ and its relation to the d-wave nature of the order parameter, and to the role of impurities.

Until now there has been only one kind of “conventional” superconductors ($`A15`$) whose gap was measured by electronic Raman, while there are numerous oxide superconductors measured by the same technique. In other words, we do not really know how the conventional superconductors behave in the electronic Raman studies. Without a sound background for comparison, many of the studies of “unconventional” behavior of the exotic superconductors would be meaningless. From number of aspects (including our own measurements), borocarbides seem to behave conventionally. Thus borocarbides would be suitable choice of superconductor for investigation usingelectronic Raman spectroscopy.

In this paper, we report an observation of clear redistribution of the electronic continua in different scattering geometries in the $`R`$Ni<sub>2</sub>B<sub>2</sub>C ($`R`$ = Y, Lu) borocarbides in the superconducting state. 2$`\mathrm{\Delta }`$-like peaks were observed in the superconducting state in A<sub>1g</sub>, B<sub>1g</sub>, and B<sub>2g</sub> Raman symmetry from single crystals. The peaks in A<sub>1g</sub> and B<sub>2g</sub> symmetries are significantly sharper and stronger than the peak in B<sub>1g</sub> symmetry. The temperature dependence of the frequencies of the peaks shows typical BCS-type behavior of the superconducting gap, but the apparent values of the $`2\mathrm{\Delta }`$ gap are strongly anisotropic for both systems. In contrast to what we normally expect from conventional superconductors, we find reproducible scattering strength below the 2$`\mathrm{\Delta }`$-like peak in all the scattering geometries. This is the first Raman measurement that shows finite scattering below the gap-like peaks of the “conventional” superconductors. Previous measurements on $`A15^{}s`$ were too noisy to detect any finite scattering below the gap.

## II Experiment

All the samples measured in this work were single crystals grown by the flux- growth method. Samples were characterized by various measurements, including resistivity versus temperature, magnetization versus temperature, and neutron scattering. The crystal structure of $`R`$Ni<sub>2</sub>B<sub>2</sub>C is tetragonal body-centered space group $`I4/mmm`$, and phononic Raman analyses have been made earlier. Raman spectra were obtained in a pseudo-backscattering geometry using a custom-made subtractive triple-grating spectrometer designed for very small Raman shifts and ultra low intensities. 3 mW of 6471 Å Kr-ion laser light was focused onto a spot of $`100\times 100`$ $`\mu `$m<sup>2</sup>, which results in heating of the spot above the temperature of the sample environment. The temperature of the spot on the sample surface was estimated by solving the heat-diffusion equation. $`\mathrm{\Delta }`$T, the rise in temperature is proportional to the inverse of the thermal conductivity of the sample. $`\mathrm{\Delta }`$T is largest at lowest temperature because the thermal conductivity is smaller at lower temperatures. The estimated $`\mathrm{\Delta }`$T is 2.7K at 4K and 0.9K at 14K for the case of YNi<sub>2</sub>B<sub>2</sub>C single crystal. The ambient temperature at which the Raman continua begin to show the redistribution was determined to be 14K, which is in agreement with this estimation. All the spectra have been corrected for the Bose factor. They therefore are proportional to the imaginary part of the Raman susceptibility.

## III Results and Discussion

Superconductivity-induced changes in the B<sub>2g</sub> and B<sub>1g</sub> spectra of YNi<sub>2</sub>B<sub>2</sub>C taken at different temperatures are shown in Fig. 1. The quality of the sample surfaces was good enough that Raman spectra could be taken down to $``$10 cm<sup>-1</sup>. Sharp drops of the spectra below 10 cm<sup>-1</sup> (for B<sub>2g</sub> and B<sub>1g</sub>) or 20 cm<sup>-1</sup> (for A<sub>1g</sub>) are due to cutoff of the filtering stage, and the sharp rises near zero frequency are due to the laser line (6471 Å). The relative strengths of the spectra in different scattering geometries are meaningful although the absolute values of the scattering strength are in arbitrary units in all the figures. In the superconducting state (T $``$ 7 K), the spectra show a clear redistribution of the scattering weight: depletion of the weight at low frequencies ($``$ 40 cm<sup>-1</sup>) and the accumulation of the weight above $``$ 40 cm<sup>-1</sup>, resulting in sharp gap-like peaks in both B<sub>2g</sub> and B<sub>1g</sub> symmetries. The gap-like feature is more prominent and sharper in B<sub>2g</sub> symmetry than in B<sub>1g</sub> symmetry. The sharpness of the B<sub>2g</sub> peak suggests that its origin may be different from that of B<sub>1g</sub>.

The peak at 200 cm<sup>-1</sup> is the Ni B<sub>1g</sub> phonon mode, the height of which (1250 on the same scale) is much stronger than the B<sub>1g</sub> electronic Raman peaks. Previous Raman measurements on borocarbides concentrated mainly on phononic peaks, and the gap features were not observed in earlier electronic Raman measurements. Electronic Raman spectra from borocarbides are so weak that a sensitive spectrometer with good stray-light rejection is required.

The peak frequency $`\omega _p`$, read from graphs, of the peak feature taken at 7 K is normalized in such a way that its normalized value is the same as the value of the reduced superconducting gap $`\mathrm{\Delta }`$(T=7K)/$`\mathrm{\Delta }_0`$ (= 0.95) in the BCS theory, where $`\mathrm{\Delta }_0`$ = $`\mathrm{\Delta }`$(T = 0), at the reduced temperature of 0.45 (= 7/15.5). $`\omega _p`$(0), the values of the peak frequency in the limit of 0 K thus obtained are 40.1 cm<sup>-1</sup> for B<sub>2g</sub> and 48.9 cm<sup>-1</sup> for B<sub>1g</sub>. $`\omega _p`$/$`\omega _p`$(0), the normalized frequencies of the peaks of the peak features as functions of the reduced temperatures follow the curve for $`\mathrm{\Delta }`$(T)/$`\mathrm{\Delta }_0`$ predicted by the BCS theory as shown in the insets of the figure. This suggests that the peak features arise due to opening of the superconducting gap and provides some evidence that borocarbides are conventional BCS-type superconductors.

One of the advantages of the borocarbide superconductors is that their upper critical fields ($`H_{c2}6T`$ at 6 K) can be easily reached by using commercial superconducting magnets. We applied strong magnetic fields (up to 7 T) parallel to c-axis and investigated the effects on these gap-like features of both YNi<sub>2</sub>B<sub>2</sub>C and LuNi<sub>2</sub>B<sub>2</sub>C crystals at low temperatures. The gap-like features were completely suppressed by the strong magnetic fields, confirming that these features are indeed induced by superconductivity. (See Fig. 2 a.) Full analysis of the dependence on magnetic fields of the peak frequencies and the features below the gap will be presented in an additional manuscript.

Unlike other gap-probing measurements such as tunneling experiments and x-ray photoemission spectroscopy (XPS), Raman spectroscopy is able to measure the anisotropy of the gap at a high resolution of a few $`meV`$. In addition, electronic Raman spectroscopy has an advantage over infra-red spectroscopy in studying the gap of superconductors in their clean limit. Figure 2 shows Raman spectra in A<sub>1g</sub>, B<sub>1g</sub>, and B<sub>2g</sub> geometries of YNi<sub>2</sub>B<sub>2</sub>C and LuNi<sub>2</sub>B<sub>2</sub>C in superconducting states and in normal states. Spectra in E<sub>g</sub> geometry were difficult to acquire from either fractured or polish-then-etched ac surfaces, even if those surfaces were optically flat. The A<sub>1g</sub> spectra reflect weighted average of the Fermi surface with a weighting function of $`k_x^2+k_y^2`$ symmetry; the B<sub>1g</sub> spectra, $`k_x^2k_y^2`$ symmetry; and the B<sub>2g</sub> spectra, $`k_xk_y`$ symmetry. The polarizations used were such that a contribution of A<sub>2g</sub> symmetry is possible in all three cases; however, the A<sub>2g</sub> spectrum is expected to be negligible. The most apparent phenomenon is the anisotropy in the intensity and sharpness of the gap-like features. The A<sub>1g</sub> and B<sub>2g</sub> peaks are significantly stronger and sharper than the B<sub>1g</sub> peak. Together with the smaller values of the positions of the A<sub>1g</sub> and B<sub>2g</sub> peaks than that of B<sub>1g</sub> peak as detailed below, this suggests that the sharp A<sub>1g</sub> and B<sub>2g</sub> peaks might be a reflection of collective modes. Further investigation is necessary to clarify the origin of the peaks.

The B<sub>1g</sub> gap energy is considerably larger than the B<sub>2g</sub> gap energy signifying perhaps that the gap parameters are anisotropic for both YNi<sub>2</sub>B<sub>2</sub>C and LuNi<sub>2</sub>B<sub>2</sub>C. The apparent gap anisotropy is more pronounced in YNi<sub>2</sub>B<sub>2</sub>C than in LuNi<sub>2</sub>B<sub>2</sub>C. The values extrapolated at T = 0 are $`\mathrm{\Delta }_0`$ (A<sub>1g</sub>) = 2.5 meV (2$`\mathrm{\Delta }_0`$/kT<sub>c</sub> = 3.7), $`\mathrm{\Delta }_0`$ (B<sub>1g</sub>) = 3.0 meV (2$`\mathrm{\Delta }_0`$/kT<sub>c</sub> = 4.5), and $`\mathrm{\Delta }_0`$ (B<sub>2g</sub>) = 2.5 meV (2$`\mathrm{\Delta }_0`$/kT<sub>c</sub> = 3.7) for YNi<sub>2</sub>B<sub>2</sub>C, while $`\mathrm{\Delta }_0`$ (A<sub>1g</sub>) = 3.0 meV (2$`\mathrm{\Delta }_0`$/kT<sub>c</sub> = 4.4), $`\mathrm{\Delta }_0`$ (B<sub>1g</sub>) = 3.3 meV (2$`\mathrm{\Delta }_0`$/kT<sub>c</sub> = 4.8), and $`\mathrm{\Delta }_0`$ (B<sub>2g</sub>) = 3.1 meV (2$`\mathrm{\Delta }_0`$/kT<sub>c</sub> = 4.5) for LuNi<sub>2</sub>B<sub>2</sub>C. These values are different from the values from other measurements. For instance, an IR reflectivity measurement reports $`\mathrm{\Delta }_0`$ = 3.46 meV for polycrystalline YNi<sub>2</sub>B<sub>2</sub>C and $`\mathrm{\Delta }_0`$ = 2.68 meV for single crystal LuNi<sub>2</sub>B<sub>2</sub>C.

There is reproducible spectral weight below the $`2\mathrm{\Delta }`$ peak in both symmetries for both YNi<sub>2</sub>B<sub>2</sub>C and LuNi<sub>2</sub>B<sub>2</sub>C systems. Special care was taken in studying the features below the gap: Samples with high-quality surfaces were selected; higher resolution and longer exposure times were employed Figure 3 shows Raman spectra of YNi<sub>2</sub>B<sub>2</sub>C(B<sup>10</sup> isotope) in B<sub>2g</sub> and B<sub>1g</sub> symmetries. In this particular case, the cutoff of the filter state in the spectrometer was 6 cm<sup>-1</sup>. As far as the spectral weight below the $`2\mathrm{\Delta }`$ peak is concerned, samples with different boron isotopes give the same results. Both B<sub>2g</sub> and B<sub>1g</sub> spectra show finite Raman scattering below the gap and it appears to be roughly linear to the Raman frequency below 30 cm<sup>-1</sup>. For the B<sub>2g</sub> spectrum, there is an abrupt slope change at about 30 cm<sup>-1</sup>. Similar linear-in-frequency behavior was observed in the spectra of LuNi<sub>2</sub>B<sub>2</sub>C below 35 cm<sup>-1</sup>. The possibility of instrumental broadening is ruled out by measuring the spectral widths of Kr-ion plasma lines, which are about 2.5 cm<sup>-1</sup> in the spectral range of these measurements.

Such a feature below the gap could rise from different causes. We eliminate the possibilities of a) an extrinsic phase on the sample surfaces and b) inhomogeneity of the probing laser beam, and argue that this sub-gap feature is intrinsic to the borocarbide superconductors. This would constitute the first, definitive experimental observation of finite Raman scattering below the gap feature for the “conventional” superconductors. Previous measurements on $`A15`$ compounds were simply too noisy to detect any finite scattering below the gap. 

a) The borocarbide single crystals do have extrinsic phases, mostly from the flux. In our measurements, we were able to avoid such flux phases. If the sub-gap feature were due to an extrinsic phase, the intensity of the sub-gap feature would be dependent on the measurement conditions, e.g., dependent on the fraction of flux under the exciting focussed laser spot.All the spectra showed the same intensity, independent of where the spot was located. X-ray photoemission spectroscopy (XPS) analyses show that the flux phase on the surface of the single crystals is Ni<sub>3</sub>B or Ni<sub>3</sub>BC. Scanning electron microscopy (SEM) did not reveal any small-grained structures on the surface or edges of the single crystals. Auger analyses did not show any fine structures either. Furthermore, they showed that chemical compositions did not vary significantly from point to point on the surface. All these analyses suggest that there is no fine-grained extrinsic phase contributing to the Raman spectra. In addition, we actually measured the Raman spectra of the flux phase itself (Fig. 3 a). Even if all the Raman intensity above the gap feature is assumed to be due to the flux (over-estimation of the flux contribution), a finite Raman intensity below the peak feature is always obtained (under-estimation of the intrinsic contribution), as shown in Fig. 3 b.

b) An experimental situation where part of the measured spot is normal (or close to the normal state) and another part is deep in the superconducting state due to inhomogeneity of the laser spot could lead to finite scattering intensity below the gap. This senario is excluded as follows: 1. In the measurements, spatial filtering the excitation laser source was used to make the incident beam as homogeneous as possible. 2. We used several different laser intensities and confirmed the same feature below the gap. The overall intensity scaled with the incident power as long as the heating effect was small, so that the temperature of the measured spot remained well below T<sub>c</sub>. 3. The sharpness of the B<sub>2g</sub> peak itself indicates that the actual temperature of the measured spot is quite uniform and well below T<sub>c</sub>. Otherwise, we should not be able to see such a steep slope below the B<sub>2g</sub> peak. Therefore, we believe that the finite Raman intensity below the peak feature is intrinsic.

Cuprate superconductors show finite Raman response below the 2$`\mathrm{\Delta }`$-like peak even in the superconducting state. The lack of the complete suppression of the Raman response below the 2$`\mathrm{\Delta }`$ peak has been regarded as evidence that the superconducting gap function of cuprates has nodes where the gap vanishes. In simple BCS picture no density of states is allowed below the superconducting gap; thus, no Raman scattering beyond small smearing effects is expected below the gap in BCS-type superconductors. However, in this work, finite Raman scattering is observed below the gap of borocarbides.

It is interesting to note that Kim finds finite low-energy states below the gap in s-wave superconductors by considering a finite-ranged pairing interaction energy. The quasiparticle density of states calculated numerically resembles the B<sub>2g</sub> Raman spectra shown in Fig. 3. The underlying mechanism that gives rise to the linear-in-frequency behavior below the 2$`\mathrm{\Delta }`$ gap for the borocarbides, which are believed to be conventional BCS-type superconductors, needs to be clarified further.

## IV Conclusion

In conclusion, sharp redistributions of the continuum of Raman spectra were observed in different geometries for the $`R`$Ni<sub>2</sub>B<sub>2</sub>C ($`R`$ = Y, Lu) systems upon going into the superconducting states. 2$`\mathrm{\Delta }`$-like features were observed in the A<sub>1g</sub>, B<sub>1g</sub>, and B<sub>2g</sub> spectra of the $`R`$Ni<sub>2</sub>B<sub>2</sub>C ($`R`$= Y, Lu) single crystals in the superconducting states. The peak features in A<sub>1g</sub> and B<sub>2g</sub> geometry are sharper and stronger than those in B<sub>1g</sub> geometry. The features are suppressed by applied magnetic fields, suggesting that they are indeed closely related to the gap parameter 2$`\mathrm{\Delta }`$. The temperature dependence of the peaks of the 2$`\mathrm{\Delta }`$-like features shows typical BCS-type behavior of the gap values as a function of temperature. However, the apparent values of the gap are anisotropic, and the anisotropy is more pronounced in YNi<sub>2</sub>B<sub>2</sub>C than in LuNi<sub>2</sub>B<sub>2</sub>C. Finite Raman scattering below the gap was experimentally observed in these “conventional” superconductors. The finite scattering is intrinsic and it appears to be linear in the Raman frequency. The lack of complete suppression of the Raman response below the 2$`\mathrm{\Delta }`$ peak of apparent BCS-type superconductors needs to be further addressed.

###### Acknowledgements.

We thank G. Blumberg, T. P. Devereaux, H.-L. Liu, K.-S. Park, and M. Rübhausen for help and valuable discussions. ISY and MVK were partially supported under NSF 9705131 and through the STCS under NSF 9120000. ISY was also supported by KOSEF 95-0702-03-01-3. SLC was supported by DOE under grant DEFG02-96ER45439. ISY, BKC, and SIL were supported by the Creative Research Initiative Project of the Ministry of Science and Technology, Korea. Ames Laboratory is operated by the U.S. Department of Energy by Iowa State University under Contract No. W-7405-Eng-82.   
Current address: Department of Material Science and Technology, K-JIST, Kwangju, 500-712, Korea