# The local spectrum of a superconductor as a probe of interactions between magnetic impurities

## Abstract

Qualitative differences in the spectrum of a superconductor near magnetic impurity pairs with moments aligned parallel and antiparallel are derived. A proposal is made for a new, nonmagnetic scanning tunneling spectroscopy of magnetic impurity interactions based on these differences. Near parallel impurity pairs the mid-gap localized spin-polarized states associated with each impurity hybridize and form bonding and anti-bonding molecular states with different energies. For antiparallel impurity moments the states do not hybridize; they are degenerate.

preprint: submitted to Physical Review Letters   

The relative orientation of the moments of two magnetic impurities embedded nearby in a metallic nonmagnetic host will depend on the significance of several electronic correlation effects, such as direct exchange, double exchange, superexchange, and RKKY. Each of these effects produces characteristic moment orientation; the RKKY interactions can align moments either parallel or antiparallel depending on the impurity separation. Reliable experimental measurements of the moment orientation as a function of impurity separation could identify the origin of magnetism in alloys of technological significance, such as the metallic ferromagnetic semiconductor GaMnAs which may eventually play a crucial role in semiconductor-based magnetoelectronics. Such measurements should also clarify the interplay between metallic and magnetic behavior in layered oxides, such as the high-temperature superconductors. In this work we propose, based on theoretical calculations, a robust experimental technique for the systematic and unambiguous experimental determination of moment alignment as a function of impurity separation.

We demonstrate that in an electronic system with a gap there is a fundamental difference between the electronic states localized around parallel and antiparallel impurity moments. Around parallel impurity moments there are mid-gap molecular states (similar to bonding and antibonding states in a diatomic molecule). Around antiparallel impurity moments the states remain more atomic-like and are degenerate. This qualitative difference in the spectrum of an impurity pair provides a robust technique of determining the impurity-impurity interaction via nonmagnetic scanning tunneling spectroscopy (STS). The essential condition for practical application of this technique will be whether the splitting of the states around parallel impurity moments is large enough to be observed spectroscopically.

The gapped system we consider in detail is the superconductor NbSe<sub>2</sub>, which is chosen for its extremely favorable surface properties for STS and for its quasi-two-dimensional electronic structure. STS has already been used to examine the localized states which form near isolated magnetic impurities on the surface of superconducting niobium. We have calculated the energies and spatial structure of the electronic states near impurity pairs in NbSe<sub>2</sub> essentially exactly within mean-field theory. These calculations indicate that the size of the splitting of states around parallel impurity moments in NbSe<sub>2</sub> is measurable — they are split by a sizable percentage of the energy gap even for impurity moment separations of order 30Å.

A nonmagnetic spectroscopy of magnetic impurity interactions is also plausible in a much wider range of materials. The localized spin-polarized states upon which the technique is based occur near magnetic impurities in most systems where there is a gap in the single-particle density of states at the chemical potential, whether or not the gap originates from superconductivity. Even when there is no true gap, if the density of states is substantially reduced at the chemical potential sharp resonances similar to the localized states will form (this has been predicted and recently observed for $`d`$-wave superconductors). Resonances around parallel and antiparallel impurity pairs show similar qualitative features to localized states.

If the energy scales of moment formation and interaction are much greater than those responsible for creating the gap it is also possible to infer the impurity interaction within a material in its high-temperature metallic phase from spectroscopic measurements on the same material in a low-temperature superconducting phase. In this the STS procedure is similar to traditional “superconducting spectroscopy”, where the dependence on impurity concentration of the superconducting transition temperature $`T_c`$ or the specific heat discontinuity at $`T_c`$ is used to determine the presence and rough magnitude of a single impurity moment. However, whereas single-impurity information can often be extracted from such measurements in the dilute limit, pairwise impurity interactions are much more difficult to infer from macroscopic properties like $`T_c`$ which depend on an ensemble of local configurations.

We note that the technique described here is remarkably non-invasive compared to alternate methods. The use of a magnetic tip to probe the magnetic properties of a sample may distort the natural surface orientation of moments. An alternative nonmagnetic STS technique that has been proposed, which involves a superconducting tip in a Tedrow-Meservey geometry, requires either an external or surface-induced magnetic field to spin-split the superconducting DOS of the tip. Finally, the use of spin-polarized tunneling from a GaAs tip relies on a fixed orientation of the magnetic structure on the surface relative to that of the optically generated spin-polarized population in the tip.

To understand the origin of the non-degeneracy of states around parallel moments and the degeneracy of states around antiparallel moments consider a heuristic picture of the two-impurity system in an isotropic-gap superconductor. For parallel alignment of the impurity moments only quasiparticles of one spin direction (assumed to be spin up) will be attracted to the impurity pair. Any localized state will thus be spin up. If the two impurities are close their two spin-up atomic-like states will hybridize and split into molecular states just as atomic levels are split into bonding and antibonding states in a diatomic molecule. Thus there will be two non-degenerate states apparent in the spectrum. This is shown schematically in the top section of Fig. 1, where the potential for spin up quasiparticles is shown on the left (Fig. 1A) and for spin down quasiparticles is shown on the right (Fig. 1B). The potential for spin-down quasiparticles is everywhere repulsive, so no spin-down localized states will form.

The situation for antiparallel aligned spins, shown on the bottom of Fig. 1, is quite different. The effect of the second impurity on the state around the first is repulsive and so does not change the state energy much unless the impurities are very close. Furthermore the Hamiltonian has a new symmetry in this case: it is unchanged under the operation which both flips the quasiparticle spin and inverts space through the point midway between the two impurities. This operation changes the potential of Fig. 1C into that of Fig. 1D. Thus instead of split states we find two degenerate atomic-like states of opposite spin, localized around each of the two impurities.

Detailed results for NbSe<sub>2</sub> are obtained by solving the following lattice-site mean-field Hamiltonian self-consistently:

$$H=\underset{ij,\sigma }{}t_{ij}c_{i\sigma }^{}c_{j\sigma }+\underset{i}{}\left[\mathrm{\Delta }_ic_i^{}c_i^{}+\mathrm{\Delta }_i^{}c_ic_i\right]+V_{S1}(c_1^{}c_1c_1^{}c_1)+V_{S2}(c_2^{}c_2c_2^{}c_2),$$
(1)   
where $`c_{i\sigma }^{}`$ and $`c_{i\sigma }`$ create and annihilate an electron at lattice site $`i`$ with spin $`\sigma `$. The impurities reside at lattice sites $`1`$ and $`2`$, the $`t_{ij}`$ are the hopping matrix elements and the $`\mathrm{\Delta }_i`$ are the values of the superconducting order parameter. NbSe<sub>2</sub> has a triangular lattice, and the normal-state band structure can be modeled with an on-site energy of $`0.1`$ eV and with nearest-neighbor and next-nearest-neighbor hopping matrix elements of $`0.125`$ eV. These are determined from a tight-binding fit to ab initio calculations of the electronic structure. The superconducting pairing interaction is modeled with an on-site attractive potential which yields the experimental order parameter $`\mathrm{\Delta }=1`$ meV. The inhomogeneous order parameter $`\mathrm{\Delta }_i`$ is determined self-consistently from the distorted electronic structure in the vicinity of the impurities. We consider equivalent parallel ($`V_{S1}=V_{S2}`$) or antiparallel ($`V_{S1}=V_{S2}`$) impurity moments.

This model assumes the impurity spins behave as classical spin (see Refs. ). Classical spin behavior has been seen, for example, for Mn and Gd impurities on the surface of niobium. The electronic structure in this model, including quasiparticle state energies and spatial structure, can be found rapidly and accurately by inverting the Gor’kov equation in a restricted real-space region including the two impurities, as described in Ref. . Measurements of the spatial structure of these states and of the values of the splitting between states can serve as a sensitive test of the model of the electronic structure of this material and of the impurity potential for a given atom.

Figure 2A shows the energies of the localized states in NbSe<sub>2</sub> for parallel spins (red) and antiparallel spins (black) for a sequence of impurity spacings which are multiples of the in-plane nearest-neighbor vector of the NbSe<sub>2</sub> lattice. The splitting of the bonding and antibonding states oscillates over a distance scale comparable to the Fermi wavelength of NbSe<sub>2</sub> along this direction. The splitting is proportional to the probability of a quasiparticle at one impurity propagating to the other, which is a measure of the coupling of the two atomic-like states. At large distances state energies for parallel and antiparallel moments approach the single impurity state energy, indicated on the right side of Fig. 2A. Figure 2BC shows the spatially integrated change in density of states due to the impurity pair for these impurity separations. The density of states (DOS) of a quasiparticle of energy $`E`$ in a superconductor has an electron component at energy $`E`$ and a hole component at energy $`E`$, so a single state will produce two peaks in the DOS unless it is closer to $`E=0`$ than the linewidth. That linewidth is determined by thermal broadening in the metallic probe tip, which for these plots is assumed to be $`0.05`$ meV$`=0.6`$K. The gap in the homogeneous DOS extends from $`1`$ meV to $`1`$ meV in NbSe<sub>2</sub>, so the variation in state energies is a substantial fraction of this gap. The clear distinction between parallel and antiparallel impurity moments in the DOS is only limited by the linewidth of the states.

A tunneling measurement of the DOS using a broad-area contact would yield the spectrum of an ensemble of impurity separations, hence STS (which measures the local DOS, or LDOS) is the ideal method for examining a single configuration of impurities. Before describing the distinct spatial differences in LDOS measurements between parallel and antiparallel alignments of impurity pairs we show the single impurity result in Fig. 3. The spatial structure of the electron and hole components of the LDOS are independently measurable by STS and can be quite different in detail. In this work we will show only the spatial structure of the hole component — similar gross structure is seen in the electron-like LDOS. Figure 3 shows the six-fold symmetric LDOS for NbSe<sub>2</sub> for $`V_S=200`$ meV at an energy of $`0.19`$ meV. The units are Angstroms and the nearest-neighbor spacing is 3.47Å.

The details of the spatial structure can be traced directly to the normal-state electronic structure of NbSe<sub>2</sub>. We note that the local hopping matrix elements and the local nonmagnetic potential will differ near the impurity atoms. We find that moderate changes in these quantities do not significantly change the magnitude of the splitting of the even and odd parity states. This relative insensitivity occurs because the splitting is largely dependent on the amplitude for a quasiparticle to propagate from one impurity site to the other. Careful comparison of a measured LDOS and Fig. 3 would allow the determination of the changes in the local hopping and the nonmagnetic potential for this case.

Plots of the LDOS for two impurities in NbSe<sub>2</sub> separated by four lattice spacings (13.88Å) are shown in Fig. 4A-D. They demonstrate via their spatial structure the qualitative differences among different types of molecular states possible around an impurity pair. Figure 4A is the bonding state (energy $`0.10`$ meV) and Fig. 4B shows the antibonding state ($`0.26`$ meV). The impurities are at the same sites in each of Fig. 4A-D, labeled $`1`$ and $`2`$ in Fig. 4B. As expected from the symmetry of these states, the antibonding state has a nodal line along the mirror plane (indicated in red) between the two impurities. No such nodal line occurs in Fig. 4A — in contrast the state is enhanced along the nodes.

The nonmagnetic STS probe cannot resolve the spin direction of the electronic states around the impurities, so around antiparallel impurity moments it detects both states. The sum of the LDOS for the two atomic-like states is symmetric around the mirror plane. Figure 4C is the LDOS at the energy for the two degenerate states around antiparallel impurity spins ($`0.28`$ meV). The states are much more diffuse than the bonding state in Fig. 4A due to the repulsive nature of one impurity. Figure 4D shows the experimentally inaccessible spin-resolved LDOS, showing the LDOS of holes with the spin direction attracted to the impurity on the left. The spin-resolved LDOS at the impurity on the left is two orders of magnitude greater than at the impurity on the right. Thus the individual localized states are quite atomic-like.

We have assumed throughout that the impurity moments are locked either parallel or antiparallel. If the alignment is intermediate between the two cases then the spectrum shows non-degenerate states split less than in the parallel case. If there is some flipping of moments between parallel and antiparallel alignment on a timescale longer than the time required for the quasiparticle states to realign with the moments then the spectrum would be a linear superposition of the antiparallel and parallel spectra. If this is an activated process, this energy of activation of moment flipping could be easily distinguished by examining the temperature dependence of the spectrum.

This work describes a robust technique for determining the alignment of two impurity moments in a gapped system. The details of the expected results around magnetic impurities in the quasi-two-dimensional superconductor NbSe<sub>2</sub> have been calculated. Energies and spatial structure of bonding and antibonding states around parallel moments, and of localized atomic-like states around antiparallel moments, indicate the two cases should be distinguishable with nonmagnetic scanning tunneling spectroscopy. This technique should be broadly applicable to a wide range of correlated electronic systems.

We would like to acknowledge the Office of Naval Research’s Grants Nos. N00014-96-1-1012 and N00014-99-1-0313. This research was supported in part by the National Science Foundation under Grant No. PHY94-07194.