text:
# Study of the electron-phonon interaction in metal diborides MeB2 (Me=Zr, Nb, Ta, Mg) by point-contact spectroscopy

## .1 Transition metal diborides

Representative examples of the d$`{}_{}{}^{2}I`$/d$`V^2(V)`$ dependencies for each compound averaged over both voltage polarities are shown in Fig. 1 (left panel). Reproducible phonon maxima are clearly resolved up to 100 mV (see ZrB2), while for TaB2 only low energy peak at 20 mV is seen. The spectra exhibit also a zero-bias anomaly, especially remarkable in NbB2 and TaB2. A common feature for all spectra is the presence of the main low-energy maximum placed at about 30, 28 and 20 mV for ZrB2, NbB2 and TaB2, respectively. This is in line with the general consideration that at fixed spring constants the phonon frequency decreases with increasing of atomic mass (see Fig. 1, right panel). Such a behavior suggests that the first peak corresponds to the vibration of the transition metal. On the other hand the neutron data peak position for MgB2 on Fig. 1 (right panel) at about 35 meVRenker  is far below the straight line connecting the MeB2 compounds. This might be considered as the consequence of a softening of the corresponding spring constants (i. e. metallic bonds in MgB2 instead of relatively strong Me$`d`$B$`2p`$ covalent bonds in the MeB2 series).

Fig. 2 presents the recovered PC EPI functions (top panel) for the investigated diborides ZrB2 and NbB2 calculated by Eq.(2) along with the High Resolution Electron-Energy-Loss Spectroscopy (HREELS) dataAizawa  for surface phonon dispersion (bottom panel). Details of the reconstruction of the PC EPI functions according to Eq.(2) are described in Ref.NaidyukPRB .

Because of the large mass difference between the transition metal and the boron atoms and strong covalent B-B bonds the boron modes are expected at much higher energy. For ZrB2 two additional maxima at 70 and 100 mV are well resolved, while for NbB2 the high energy part of the spectrum presents a broad maximum around 60 mV. For TaB2 the high energy phonon peaks were difficult to resolve, where according to a rough estimationRosner  the boron in-plane and out of plane displacement modes should have energies of 98 and 85 meV, respectively. No spectral features were found for the mentioned compounds above 100 meV. Our spectra are in line with the measured surface phononsAizawa  for ZrB2 and NbB2 although the surface phonons, in general, are softer. For both compounds phonon dispersion studyAizawa  (Fig. 2, bottom panel) demonstrates a gap between 30-50 meV which separates acoustic and optic branches. Close to this energy region a minimum in our PC spectra occurs. Comparing the high energy parts of the ZrB2 and NbB2 PC spectra, we may support the statementAizawa , that for NbB2 the boron surface phonon modes are softer and more stretched than in the case of ZrB2 giving rise to structureless maxima around 60-70 mV (see Fig. 1). Note that the upper boundaries of the ZrB2 and NbB2 PC spectra are at about 110 mV and 90 mV (see Fig. 1), what is much larger than their Debye temperatures of 280 K and 460 K, respectively, estimated from the Bloch-Grüneisen temperature dependence of the resistivityGaspa .

With the use of the EPI function the parameter $`\lambda =2\alpha ^2F(\omega )\omega ^1𝑑\omega `$ was calculated. For many superconductors it was foundKhot  that $`\lambda _{\mathrm{PC}}\lambda _{Eliashberg}`$. Table 2 shows that $`\lambda _{\mathrm{PC}}`$ is rather low for the investigated diborides what is in line with the small $`\lambda `$ values reported for PC studies of the transition metal silicides NbSi2 and TaSi2Balkas  ($`\lambda _{\mathrm{PC}}`$0.02). The possible reasons for a small $`\lambda `$ value are discussed in Ref.NaidyukPRB . Our results show that NbB2 has the largest $`\lambda _{\mathrm{PC}}`$ among the studied compounds, therefore existence of superconductivity in NbB2 with observable $`T_c`$ is more likely.

## .2 MgB2

In Fig. 3 the $`V_2\left(eV\right)d^2V/dI^2\left(eV\right)`$ and $`dV/dI(V)`$ (in the inset) characteristics are shown in the superconducting state at zero field. In the energy-gap region the two gap features are clearly seen with $`\mathrm{\Delta }_1=2.4`$ and $`\mathrm{\Delta }_2=5.7`$ meV (see inset). Further on, we simply denote by $`\mathrm{\Delta }`$ the position of a $`dV/dI`$ minimum. In Fig. 3 the $`V_2(V)`$ d$`{}_{}{}^{2}V`$/d$`I^2`$ dependence after subtracting of linear background in comparison to the phonon density of states (PDOS)Renker  is shown. Some accordance is seen between the positions of PDOS peaks and maxima in $`V_2(V)`$ dependence.

The reproducibility of this kind of PC spectrum for different contacts is seen in Fig. 4(b). Here, the contact resistance varies from 43 to 111 $`\mathrm{\Omega }`$ with gap minima at $`\mathrm{\Delta }=`$ 2.1, 2.6, and 4.9 meV, respectively. The larger gap for curve 3 equals 7.0 meV. All the PC spectra (b) correlate with PDOS. The slight variation is probably due to the anisotropy and different scattering rates in the contacts. Compared with the theoretical EPI function for an isotropic one-band model (see, for example, Ref.Kong ; Yildirim ; Bohnen ), the peak at eV=60$`÷`$70 meV of $`E_{2g}`$ boron mode is not too much higher in intensity, in accord with our earlier observationBobrov . For the two-band model in clean limit, we expect an information mostly from the 3D band keeping in mind that we measure the c-axis oriented films. In this case, the theory predicts, that the EPI spectral function has the $`E_{2g}`$-peak intensity of the same order of magnitude as the other peaks of PDOS (see Fig. 1 in Ref.Golubov )

According to our classification of the energy gap structureNaidyuk , it is due to the random orientation of the contact axis and scattering of charge carriers between two-band of Fermi surface, having gaps $`\mathrm{\Delta }_1`$ and $`\mathrm{\Delta }_2`$ mixed. With an increase of interband scattering the magnitude of $`\mathrm{\Delta }_1`$ ($`\mathrm{\Delta }_2`$) moves to the higher (lower) value, respectively. For dirty contacts, where the admixture of the 2D band is essential, only one gap maximum remains with a broad distribution around $`3.5`$ meVNaidyuk . In this case $`l`$ is smaller than $`d`$ (where $`l`$ and $`d`$ are the electron mean free path and the size of the contact, respectively), and the inelastic backscattering contribution to the phonon structure, proportional to $`l/d`$KulYan , is small. Therefore, in the superconducting state, the observed phonon structure presents mainly the elastic contribution to the excess currentYansonSC . The elastic term is proportional to the energy dependent part of the excess current $`I_{exc}\left(eV\right)`$, similar to the phonon structure in the quasiparticle DOS for tunneling spectroscopyYansonSC ; Beloborod'ko :

$$\frac{dI_{exc}}{dV}(eV)=\frac{1}{R_0}\left|\frac{\mathrm{\Delta }_{in}\left(eV\right)}{eV+\sqrt{\left(eV\right)^2\mathrm{\Delta }_{in}^2\left(eV\right)}}\right|^2,$$
(3)
where $`\mathrm{\Delta }_{in}\left(eV\right)`$ is the gap parameter in the 3D band, induced by the 2D-band EPI. As seen in Fig. 4 (a), if the $`\mathrm{\Delta }`$ value increases (curves 1-3), then the intensity of the phonon structure in the units of $`d(\mathrm{ln}R)/dV=2\sqrt{2}V_2/V_1^2`$ increases too (Fig. 4(b)). That is because the modulation voltage $`V_1`$ decreases, whereas the amplitudes in $`V_2(eV)`$-units remain approximately the same. Note, that for curve 3 in Fig. 4(a) one has to take the lower gap $`\mathrm{\Delta }_1`$, because the current is mainly determined by 3D band, as mentioned above.

In Fig. 5, the normal state spectrum above $`T_c`$ is displayed together with the differential resistances in the superconducting state (see inset), showing the energy gap structure. In spite of an increase of the temperature smearing above 20 mV at 41 K the residual phonon structure is still visible (curve 1 in Fig. 5). The smeared phonon features are superimposed on the rising linear background. For curve 2, we see an increase in scattering at $`35`$ mV, where the acoustic phonon peak occurs, and the saturation around 100 mV, where the phonon spectrum ends. In the normal state, only those nonlinearities remain, which are due to the inelastic processesKOS . We stress that judging from the larger superconducting gap value ($`3.5`$ meV for curve 2 in the inset) the essential contribution is expected from the $`\mathrm{\Delta }_2(E)`$ of 2D band for normal-state spectrum No.2. This spectrum should contrast with curve 6 in Fig. 6 (see below), where the direct contribution from the 2D band is small, due to lower value of $`\mathrm{\Delta }`$. Thus, the backscattering processes from the 3D band are mostly essential for spectrum 6 and the phonon features are not resolved at high energies. The shape of spectrum 1 in Fig. 5 presents the behavior intermediate between these two extremes, although its energy gap is approximately equal to curve 6 in Fig. 6. Beside the visible phonon features in the range $`30÷100`$ mV, it possesses a low energy bump at about 20 mV.

The phonon spectra of PC with a small value of energy gaps are characterized by the presence of low frequency phonon peaks. The small peak at energy of about 25 mV (Fig. 6, curves 1, 2) is visible, where a tiny knee exists on the PDOSRenker  (see PDOS in Fig. 3). In the normal state (at $`TT_c`$), these low frequency peaks transform into the S-shape structure in d$`{}_{}{}^{2}V/`$d$`I^2(V)`$ spectra (curve 6), corresponding to the wide minimum of d$`V/`$d$`I(V)`$ near zero bias. This low-frequency structure is hardly due to the remnants of superconducting quasigap at $`T>T_c`$, since it is absent in junction No. 2, whose characteristic is shown in Fig. 5. Rather, it could be thought of as strong interaction in the 3D band with very low-frequency excitations, whose origin is not clear yet. On increasing the temperature, the low frequency peak broadens further like common spectral features do in the normal state.

Fig. 6 shows (compare curves 1 and 2) that the field smears out the intensity of the high energy peaks, which are induced in the 3D band by EPI of the 2D band. The disappearance of phonon peaks at field and temperature rise proves that they do not belong to the inelastic backscattering processes, which should have the same intensity both in the superconducting and in normal states. It seems more plausible that the high energy phonon peaks are due to the elastic contribution in the excess current (3) induced by EPI from the 2D band, as was already stated above.

Conclusion. We have measured the PC spectra in transition metal diborides: ZrB2, NbB2 and TaB2. For all compounds the main phonon peak position was established, the PC EPI function was recovered, and the EPI parameter $`\lambda `$ was determined. The obtained small $`\lambda `$ values question strongly the reported bulk superconductivity in these compounds with remarkable $`T_c`$. To draw a more weighty conclusion about details of EPI and the $`\lambda `$ values in the presented MeB2 family, a theoretical calculation of $`\alpha _{\mathrm{PC}}^2F(\omega )`$ with the mentioned $`K`$-factor and their comparison with experimental data is very desirable.

The PC EPI spectra of the superconducting MgB2 differ even qualitatively from those measured for the mentioned transition-metals diborides. For MgB2 the reproducible peaks on $`d^2V/dI^2(V)`$ are seen in the superconducting state, which disappear in the normal state. It proves that they are due to the energy dependence of the superconducting order parameter. The superconductivity here is presumably due to the 2D-band EPI, which induces the $`\mathrm{\Delta }(E)`$ structure in the 3D band. At a small value of the superconducting gap the phonon structure is weak, and its intensity begins to increase with growing $`\mathrm{\Delta }`$. The robustness against the magnetic field also grows notably with increasing $`\mathrm{\Delta }`$.

In the normal state the intensity of the inelastic spectrum also correlates with the value of the superconducting gap. The tendency is observed that the high energy phonon contribution to the PC spectra becomes more prominent for a larger gap. This is supported also by our recent data on MgB2 single crystalsmgbphon . For a smaller gap, the low-frequency bump appears in the spectra. It might be due to EPI with some unknown low-frequency excitationLampakis , but further work is needed to exclude that it is not caused simply by phonon peaks of the normal-metal counter electrode.