# Phonon and Elastic Instabilities in MoC and MoN

## I Introduction

The transition metal carbides and nitrides, such as NbC and MoN, represent a technologically important series of materials, often revealing interplay between their interesting properties and the incipient instabilities that seem to drive those properties. The important features of these materials include extreme hardness and high melting temperatures, as well as superconductivity in many of them. In some of these materials, the atomistic properties (e.g. bonding properties) that drive particular macroscopic behaviors can also lead to instabilities that inhibit the stoichiometric B1 (sodium chloride) structure from forming. MoC and MoN are good examples of this circumstance. In this paper, we report new theoretical results for the MoC and MoN systems indicating that their lack of stability as stoichiometric compounds in the B1 structure is directly correlated with phonon instabilities. We also present electronic structure results for the B1-structure carbides and nitrides with zirconium, niobium and molybdenum. We discuss the trends related to variables such as the number of valence electrons per formula unit, as well as the effect of the particular non-metal atom (nitrogen or carbon). We discuss these results on the basis of the known properties of these materials.

Using results from first principles electronic structure calculations, Pickett et al. argued that MoN in the B1 structure was a prime candidate for a “high-temperature” superconductor with a predicted transition temperature of approximately $`30^{}`$ K. There were two aspects of the electronic structure that motivated this prediction for MoN—the high density of electronic states at the Fermi level, N(E<sub>F</sub>), and the large electron-phonon matrix elements associated with the strong bonding in this material. Both of these features are indicative of a potentially high T<sub>c</sub>, but they are also hallmarks of either structural instabilities that can frustrate the formation of stoichiometric structures, or of magnetic instabilities that can destroy superconductivity. Experimentally, it was found that these features lead instead to structural instabilities in B1 MoN that are manifested by the fact that only highly N deficient or vacancy/defect-rich B1 structures have been made in the laboratory. Alternatively, the more thermodynamically stable hexagonal phase of MoN is often formed close to stoichiometry. Similar systems, such as NbC and NbN, which exhibit superconductivity are also prone to poor stoichiometry and must be prepared carefully to obtain a ratio of niobium to carbon or nitrogen that is close to one-to-one. The substoichiometry in these systems normally occurs as a deficiency of carbon or nitrogen atoms.

Following the initial prediction of a potentially high T<sub>c</sub> in MoN, there was a flurry of unsuccessful experimental activity aimed at fabricating this compound close to stoichiometry. Subsequent theoretical work by Chen and coworkers shed light on the cause of the experimental difficulties, showing that perfectly stoichiometric MoN was elastically unstable in the B1 structure. They calculated the total energies for small strains away from the B1 structure and showed that the cubic elastic constant C<sub>44</sub> exhibited an instability (negative value) for MoN. In contrast, their calculations of the three cubic elastic constants for NbC showed that there were no elastic instabilities in that material.

Earlier studies related the experimentally observed phonon anomalies (dips in the phonon dispersion curves) in NbC and TaC to their Fermi surfaces. The so-called Fermi surface nesting effects refer to the fact that parallel sheets of the Fermi surface with (relatively) large areas provide a mechanism for enhancing the phonon renormalization (decrease in square frequency) resulting from the screening effects of the electron-phonon interactions. Enhanced screening effects can lead to anomalous structure in the phonon dispersion curves or, in the extreme case, to instabilities manifested by negative square frequencies at wave vectors related to the nesting vectors of the Fermi surface. In the extreme case of Fermi-surface-induced instabilities, a given phase is unstable and will not form at stoichiometry. Presumably, aspects of the instabilities in MoC and MoN are Fermi surface related, but as we mention below the quantitative manifestation of Fermi surface nesting in these materials is complicated and, unlike NbC, not amenable to a simple interpretation (e.g. matrix element effects are apparently key to triggering the instability).

Various experimental investigators attempted to form the metastable B1 phase of MoN, but most samples still suffered from large amounts of vacancies or defects, or a high pressure hexagonal phase formed. Attempts at forming a cubic metastable bulk phase have been unsuccessful to date. There was hope, however, that MoN might be metastable at high pressure in the B1 structure, with the elastic instabilities mitigated by the increased bonding that would result. However, our calculations demonstrate that, up to pressures well above 400 GPa, the C<sub>44</sub> instability for MoN actually increases, indicating that a metastable structure of B1-MoN is not possible even at the highest pressures attainable with novel experimental methods.

In contrast to the situation for B1-MoN, we show below that MoC does not have an elastic instability in C<sub>44</sub> (or any of the cubic elastic moduli, for that matter) despite the fact that experimentally MoC is nearly as unstable as MoN with regard to the limits on obtainable stoichiometry or defect/vacancy-free crystals. We show instead that the instabilities in MoC are driven by unstable phonons near the X point in the Brillouin zone (BZ) and not by elastic instabilities (long wavelength acoustic phonon instabilities) as in MoN. Moreover, we show that MoN also has phonon instabilities in addition to its elastic instabilities that have already been demonstrated. We discuss these instabilities in MoC and MoN in terms of their electronic structure, including their densities of states and Fermi surfaces.

## II computational details

Our calculations were performed using the full-potential linear-augmented-plane-wave (LAPW) method within the local density approximation (LDA). The core states were treated fully relativistically and the valence states were treated semi-relativistically (without spin-orbit interaction). No shape approximations were made for the potential or the charge density. The exchange-correlation potential used was that of Ceperley and Alder as parameterized by Perdew and Zunger.

For the lattice constant and bulk modulus calculations, 47 k-points (after the method of Blöchl) were used in the irreducible wedge of the Brillouin Zone (BZ) (equivalent to 1000 points in the entire BZ). Approximately 270 LAPW basis functions were used per atom.

A set of monoclinic strains was used to calculate the cubic elastic constant C<sub>44</sub> using the method outlined by Mehl et al. Because the energy differences in these types of calculations are very small, great care was taken in selecting k-point meshes to ensure convergence. For the results shown here, 1088 k-points in the irreducible wedge were used.

Phonon frequencies were calculated using a supercell approach (frozen phonons). Calculating the energy as a function of several different well-chosen distortions allows the phonon frequencies at high symmetry points to be determined. Calculations for X point phonons were done by calculating the energy differences for three different sets of displacements which were determined using the program ISOTROPY. The energy versus distortion results were fitted to polynomial expansions and the phonon frequencies were then determined. When the square of the frequency of an unstable phonon is negative, this indicates that the B1 structure is unstable with respect to that particular set of atomic displacements.

## III Results and discussion

### A Bonding in the carbo-nitrides

As discussed below, the B1 carbides and nitrides of zirconium, niobium, and molybdenum have very similar density of states (DOS) profiles, the main difference being a systematic increase in the DOS at the Fermi level. The same systematic trends can be seen in the lattice constants and bulk moduli. Fig. 1 shows the bulk moduli of these materials as a function of the lattice constant. There is a general trend of decreasing lattice constant as the number of valence electrons increases, with the nitrides having the smaller lattice constants in the case of the isoelectronic systems (ZrN & NbC, NbN & MoC). Despite the smaller lattice constants of the nitride systems, the corresponding increases in the bulk moduli are smaller than expected compared to the isoelectronic carbide system (compare ZrN and NbC or NbN and MoC in Fig. 1). In a strict rigid-band view, the bulk moduli would be purely a function of volume, leading to one smooth curve in Fig. 1 rather than separate curves for the carbides and the nitrides. This circumstance demonstrates the subtle differences in the bonding characteristics between the carbide and nitride systems despite very similar densities of states. In the carbide systems, the covalent bonding charge between the carbon atoms is more localized and closer to the atoms than the corresponding bonding charge in the nitrides. Thus, the more itinerant, less tightly bound charge in the nitrides is more easily deformed than the covalent bonding charge in the carbides, leading to a smaller than expected increase in the bulk modulus of the nitrides relative to the carbides.

The above considerations illustrate that, although the major contributions to the bonding and resultant properties of the carbo-nitride systems can be accounted for by general considerations of atom size and overall valence of the formula unit, the chemical composition is also important for understanding differences in the physical properties of these materials. For example, although the B1 compounds NbN and MoC have the same number of valence electrons per formula unit and very similar DOS profiles, the former can be made close to stoichiometry while the latter cannot.

### B Densities of states

The DOS for isoelectronic pairs of these compounds are qualitatively very similar, the quantitative difference being the total DOS at the Fermi level. (A representative DOS plot is shown in Fig. 2.) By definition, in a purely rigid band picture, the isoelectronic pairs (ZrN & NbC, NbN & MoC) would be identical. While the DOS profiles look very similar and the Fermi level occurs at similar places on the DOS profile, the DOS at the Fermi level is higher in the nitride systems compared to the isoelectronic carbide systems. The DOS at the Fermi level increases systematically with the number of valence electrons (ZrC, which has only 8 valence electrons per unit cell, has the lowest DOS at the Fermi level and the highest is for MoN which has 11 valence electrons per unit cell.)

The increase in the DOS at the Fermi level as the valence is increased is a rigid-band-like effect resulting from the positive slope of the DOS as a function of energy in this energy range, while the increase between isoelectronic pairs is a chemical effect due to the bonding differences between a nitride and its isoelectronic carbide. This increase in N(E<sub>F</sub>) is reflected in the superconducting transition temperatures in the series up to NbN. (NbN has the highest T<sub>c</sub> \[17 K\] of the B1 superconductors.) Using simple BCS arguments, it is expected that T<sub>c</sub> will increase with electron count due to the larger values of N(E<sub>F</sub>), resulting in T<sub>c</sub> being higher for the nitrides. However, in B1-MoC and B1-MoN samples, the stoichiometry is poor and/or there are a large number of defects. Consequently, the superconducting transition temperatures in MoC and MoN are much lower than predicted from the perfect crystal DOS arguments using quantitative rigid-muffin-tin calculations.

### C Elastic instability of MoN

The systematic increase in the DOS at the Fermi level led to the proposal of MoN and MoC as good candidates for “high temperature” superconductors. However, efforts to make high quality, stoichiometric B1-MoN crystals were unsuccessful. In most samples, the defects are primarily nitrogen substitutional defects on the molybdenum sites, nitrogen atoms in the interstitial regions, and vacancies on the nitrogen sites. Some workers tried to improve the crystals by applying pressure in an attempt to drive nitrogen defects from interstitial sites into the nitrogen sites of the ideal crystal. Unfortunately, this results in a hexagonal structure less favorable for high T<sub>c</sub>. In an effort to explain the experimental “instability” of B1-MoN, Chen et al. performed theoretical studies of the cubic elastic constants for MoN. They found that the cubic elastic constant C<sub>44</sub> for MoN was negative. This result clearly shows that B1-MoN is unstable at zero pressure, and is in good agreement with the experiments in this regard.

It is perhaps not unreasonable that a metastable state might exist, however, given the successes in forming metastable phases of other carbo-nitride compounds, and others have suggested that the C<sub>44</sub> instability may be mitigated in MoN by applying high pressures. To test this, we calculated the change in energy as a function of a monoclinic strain at various pressures. The results are shown in Fig. 3. As is evident from the figure, the instability persists and even increases at pressures high enough (above 400 GPa) to contract the lattice constant by 3%. This indicates that any attempts at fabricating a metastable phase, even at the highest available laboratory pressures using novel techniques, will be unsuccessful.

### D Phonon instabilities of MoC and MoN

Because the stability of MoC samples is not much better than that of MoN, and the predicted superconductivity transition temperature is smaller than expected, it is natural to suspect that C<sub>44</sub> for MoC also reveals the same instability observed in MoN. However, our calculations show that for MoC the C<sub>44</sub> elastic constant is large and positive. The other two elastic constants, C<sub>11</sub> and C<sub>12</sub>, are also relatively large and positive, indicating an elastically stable structure.

Given that the elastic constants for MoC are stable, the question arises: why can stoichiometric B1-structure MoC not be made? In particular, is B1-MoC a possible metastable phase, or is it intrinsically unstable for some reason other than elastic behavior? As a first step toward answering this question, we examined the phonon frequencies of MoC at selected points in the Brillouin Zone. Using the frozen phonon approach, we first determined the phonon frequencies of MoC and MoN at the $`\mathrm{\Gamma }`$ point, and NbC at the X point to compare with experiment and previous calculations. The results within a few percent of the experimental results as well as Savrasov’s calculations for NbC. The frequency of the calculated zone center optical phonon in MoC shows no indication of a phonon anomaly and is very close to that of NbC (as one might expect). On the other hand, the frequency of the calculated zone center optical phonon in MoN is less than half that of MoC and NbC. (Of course, zone center acoustic modes in MoN are unstable as shown by the C<sub>44</sub> calculation.)

Even when a high density of states at the Fermi level does not indicate a structural or magnetic instability, it may indicate anomalous phonons. Though NbC is quite stable and samples can be fabricated with good stoichiometry, the phonon spectrum contains a very distinct anomalous region near $`k=.7(2\pi /a)`$ along $`\mathrm{\Gamma }\mathrm{X}`$ that is related to Fermi surface nesting as shown by Gupta and Freeman and Klein et al. In the rigid band picture, NbN is similar to NbC but with an extra valence electron per unit cell. Adding an extra electron to the system (NbC $``$ NbN) causes more hybridized niobium-d/non-metal p-states to be occupied which leads to an increase in the density of states at the Fermi level. The anomalous region in the phonon spectrum becomes more pronounced and shifts toward the X point. (See Fig. 4.) If the phonon spectra of these carbo-nitride systems also follow systematic trends as for the lattice constants, bulk moduli, and DOS at the Fermi level, then it is reasonable to expect that the anomalous region of the phonon spectrum may become even more pronounced in MoC—perhaps even to the point that some phonon modes become unstable causing the crystal to spontaneously distort at finite temperatures. A schematic of this idea is shown in Fig. 4. Given these ideas, a good candidate BZ region for phonon instabilities in MoC would be that near the X point.

To test this hypothesis, we calculated the frequencies of the optical and acoustic longitudinal phonons at the X point for NbC and MoC. The calculated frequencies for NbC agree within a few percent of the experimental values of Smith and Gläser and frequencies calculated using other methods. Our NbC calculation is simply a “proof of principle” check for the frozen phonon calculations. For MoC, our calculations show a frequency for optical longitudinal phonons that is nearly half that of NbC, and the calculated frequency for acoustic longitudinal phonons is imaginary (367 cm<sup>-1</sup>) indicating that these latter phonons are unstable at the X point. It can be reasonably surmised, then, that there exists a finite region of the spectrum near the X point for which the acoustic phonons are unstable. This is consistent with the experimental instability that exists despite the fact that LDA-based calculations of the elastic constants indicate that B1-MoC is elastically very stable. While the Fermi surfaces of MoC and MoN which we calculated (not shown here) show indications of nesting effects with a wave vector at or near the X-point, the nesting features are not as pronounced as those found in NbC and TaC. The phonon anomalies cannot be explained as simple nesting effects; They are a complicated combination of nesting (phase space considerations) and bonding (the strength of the electron-phonon matrix elements).

## IV Conclusions

We discussed systematic trends in some of the physical properties in the series of compounds TMC and TMN, TM = Zr, Nb, Mo. Lattice constants, bulk moduli, DOS at the Fermi level, etc. change systematically through the series. Corresponding to these systematic changes, the superconducting transition temperatures of the materials increase with increasing numbers of electrons per unit cell, but the compounds become increasingly unstable through the series.

While Chen et al. showed that perfectly stoichiometric B1-MoN was unstable, we have also shown that these instabilities are not mitigated by increased pressure—that is, the C<sub>44</sub> instability actually is enhanced by the application of hydrostatic pressure.

Unlike MoN, there is no indication of a similar elastic instability in B1-structure MoC despite the fact that fabrication of high quality MoC crystals is also very difficult. We have shown that this experimental instability is related to an extreme phonon softening near the X point. Consequently, as with MoN, a stable state of B1-MoC cannot be expected.

## ACKNOWLEDGMENTS

The authors would like to thank the Campus Laboratory Collaboration Program of the University of California for financial support. Generous computer resources were also provided by Lawrence Livermore National Laboratories. One of us, G. L. W. H., would like to thank H. T. Stokes of Brigham Young University for providing his program ISOTROPY, part of which was used in determining the symmetries of distortions for the frozen phonon calculations reported here.