# Exotic ground states and impurities in multiband superconductors

## Abstract

We consider the effect of isotropic impurity scattering on the exotic superconducting states that arise from the usual BCS mechanism in substances of cubic and hexagonal symmetry where the Fermi surface contains inequivalent but degenerate pockets (e.g. around several points of high symmetry). As examples we look at CeCo<sub>2</sub>, CeRu<sub>2</sub>, and LaB<sub>6</sub>; all of which have such Fermi surface topologies and the former exhibits unconventional superconducting behavior. We find that while these non $`s`$-wave states are suppressed by non-magnetic impurities, the suppression is much weaker than would be expected for unconventional superconductors with isotropic non-magnetic impurity scattering.

Recently it was shown that in substances with cubic or hexagonal symmetry, exotic superconducting states can arise from conventional BCS mechanisms . This can occur when these metals have Fermi surface (FS) pockets that are centered at or around some three-fold or higher degenerate symmetry points of the Brillouin zone (BZ). The resulting superconducting state is either a conventional $`s`$-wave state or corresponds to a multidimensional superconducting representation for which the ground state breaks time reversal symmetry. Such FS topologies exist in many superconductors. Examples are CeRu<sub>2</sub> , LaB<sub>6</sub> , and CeCo<sub>2</sub> ; the latter exhibits a low temperature behavior specific heat that appears to vary as a power law with temperature  which is consistent with unconventional superconductivity. Here we investigate the stability of these exotic superconducting states in the presence of non-magnetic isotropic impurity scattering. In particular we examine in detail a model that applies both to CeCo<sub>2</sub> and to the FS pockets centered at the six N-points of a body-centered cubic (BCC) lattice and discuss the results of the analogous theory for CeRu<sub>2</sub> and LaB<sub>6</sub>. We show that the exotic superconducting states are less susceptible to non-magnetic impurities than might be expected from earlier theories of isotropic impurity scattering in single band unconventional superconductors .

A BCS approximation for the multi-band case will be used (see e.g. ). The form of the interaction parameters describing the two electron scattering on and between the different degenerate pockets of the FS is fixed by symmetry. Consequently, the resulting superconducting state need not be $`s`$-wave when the interaction does not depend on the direction of the Fermi momenta of an individual pocket. In our earlier work  we considered three cases in detail a) three FS pockets centered about the X-points of a simple cubic lattice; b) three FS pockets at the M-points of the hexagonal lattice; c) four FS pockets at the L-points in the face-centered cubic (FCC) lattice. Case a) may describe the superconducting states in LaB<sub>6</sub> and in CeRu<sub>2</sub> since these materials both have FS pockets centered at the X-point.

It has recently been demonstrated that the specific heat exhibits a power law temperature dependence at low temperatures in CeCo<sub>2</sub> . For this reason we consider here FS pockets centered at the six N-points of the BCC lattice which is formally identical to that in FCC CeCo<sub>2</sub> for the FS pockets which are located along the $`(1,1,0)`$ and equivalent directions  (note that in this material there also exist FS sheets centered at the $`\mathrm{\Gamma }`$ point).

The Hamiltonian for several separate pieces of the FS can be written in the following form:

$$H=\underset{\alpha \sigma 𝐩}{}ϵ(𝐩)a_{\alpha \sigma }^{}(𝐩)a_{\alpha \sigma }(𝐩)+\frac{1}{2}\underset{𝐤,𝐤^{},𝐪}{}\underset{\alpha \beta \sigma \sigma ^{}}{}\lambda _{\alpha \beta }(𝐪)a_{\alpha \sigma }^{}(𝐤+𝐪)a_{\beta \sigma ^{}}^{}(𝐤^{}𝐪)a_{\alpha \sigma ^{}}(𝐤^{})a_{\beta \sigma }(𝐤),$$
(1)   
where $`\sigma `$ and $`\sigma ^{}`$ are spin indices, $`\lambda _{\alpha \beta }(𝐪)`$ includes the interaction for scattering two electrons from the pocket $`\alpha `$ into pocket $`\beta `$ which is due to both Coulomb and electron-phonon terms. For simplicity we will take $`\lambda _{\alpha ,\beta }(𝐪)`$ to be independent of the direction of $`𝐪`$. Scattering by impurities is described by the Hamiltonian

$$H_{imp}=\underset{\sigma }{}\underset{k,q}{}\underset{\alpha ,\beta }{}\underset{j}{}\mathrm{exp}[i(𝐪𝐤)𝐑_j]V_{\alpha ,\beta }(𝐤,𝐪)a_{\beta \sigma }^{}(𝐤)a_{\alpha \sigma }(𝐪).$$
(2)   
Introducing the anomalous Green’s function $`\widehat{}_\alpha (xx^{})`$ for each FS sheet $`\alpha `$, the corresponding Gor’kov equations can be found for the case of singlet pairing in exactly the same manner as in Ref . Including the isotropic impurity scattering within the Born approximation the following Gor’kov equations are found

$`[i\omega _nϵ_\alpha (𝐤)\overline{𝒢}_\alpha (\omega )]𝒢_\alpha (𝐤,i\omega _n)[\mathrm{\Delta }_\alpha ^{}+\overline{_\alpha ^{}}(\omega )]_\alpha (𝐤,i\omega _n)=1`$ (3)   
$`[i\omega _n+ϵ_\alpha (𝐤)+\overline{𝒢}_\alpha (\omega )]_\alpha ^{}(𝐤,i\omega _n)[\mathrm{\Delta }_\alpha ^{}+\overline{_\alpha ^{}}(\omega )]𝒢_\alpha (𝐤,i\omega _n)=0`$ (4)   
where

$`\overline{𝒢}_\alpha (\omega )=n_i{\displaystyle \underset{𝐤,\beta }{}}|u_{\alpha ,\beta }|^2𝒢_\beta (𝐤,i\omega _n)`$ (5)   
$`\overline{}_\alpha (\omega )=n_i{\displaystyle \underset{𝐤,\beta }{}}|u_{\alpha ,\beta }|^2_\beta (𝐤,i\omega _n)`$ (6)   
$`\mathrm{\Delta }_\alpha ^{}=T{\displaystyle \underset{𝐤,\beta }{}}{\displaystyle \underset{n}{}}\lambda _{\beta \alpha }_\beta ^{}(\omega _n,𝐤)`$ (7)   
$`|u_{\alpha ,\beta }|^2=\frac{d\mathrm{\Omega }}{4\pi }\frac{d\mathrm{\Omega }^{}}{4\pi }|V_{\alpha ,\beta }(𝐤_F,𝐤_F^{})|^2`$ and $`n_i`$ is the concentration of impurities. Introducing $`\stackrel{~}{\mathrm{\Delta }}_{\alpha ,n}=\mathrm{\Delta }_\alpha +\overline{_\alpha ^{}}(\omega )`$ and $`i\stackrel{~}{\omega }_{\alpha ,n}=i\omega _n\overline{𝒢}_\alpha (\omega )`$, the gap and self-energy equations can be expressed as

$$\mathrm{\Delta }_\alpha =T\pi \underset{\beta ,n}{}\frac{N_0\lambda _{\alpha ,\beta }\stackrel{~}{\mathrm{\Delta }}_{\beta ,n}}{\sqrt{\stackrel{~}{w}_{n,\beta }^2+|\stackrel{~}{\mathrm{\Delta }}_{\beta ,n}|^2}},$$
(8)   
$$\stackrel{~}{w}_{n,\alpha }=w_n+\underset{\beta }{}\frac{\mathrm{\Gamma }_{\alpha ,\beta }\stackrel{~}{w}_{n,\beta }}{\sqrt{\stackrel{~}{w}_{n,\beta }^2+|\stackrel{~}{\mathrm{\Delta }}_\beta |^2}},$$
(9)   
and

$$\stackrel{~}{\mathrm{\Delta }}_{n,\alpha }=\mathrm{\Delta }_\alpha +\underset{\beta }{}\frac{\mathrm{\Gamma }_{\alpha ,\beta }\stackrel{~}{\mathrm{\Delta }}_{n,\beta }}{\sqrt{\stackrel{~}{w}_{n,\beta }^2+|\stackrel{~}{\mathrm{\Delta }}_{\beta ,n}|^2}}$$
(10)   
where $`\mathrm{\Gamma }_{\alpha ,\beta }=\pi N_0|u_{\alpha ,\beta }|^2`$, and $`N_0`$ is the normal density of states on a single pocket. Equations (8, 9), and (10) have been studied in the context of multi-band superconductivity by a variety of authors (see, e.g., ).

We consider here FS pockets centered at the six N points of the BCC lattice. This situation is formally identical to that describing the FS pockets in FCC CeCo<sub>2</sub> located along the (110) and equivalent directions. The N points of the BCC lattice lie at $`\frac{1}{2}𝐛_i`$ and $`\frac{1}{2}(𝐛_i𝐛_j)`$ with $`i>j`$ where the $`𝐛_i`$ are the reciprocal lattice basis vectors \[$`𝐛_1=\frac{2\pi }{a}(0,1,1)`$, $`𝐛_2=\frac{2\pi }{a}(1,0,1)`$, and $`𝐛_3=\frac{2\pi }{a}(1,1,0)`$\]. The interaction between the electrons forming a Cooper pair on Fermi pockets centered at these points takes the form

$$V=\left(\begin{array}{cccccc}\lambda & \nu & \mu & \nu & \nu & \nu \\ \nu & \lambda & \nu & \mu & \nu & \nu \\ \mu & \nu & \lambda & \nu & \nu & \nu \\ \nu & \mu & \nu & \lambda & \nu & \nu \\ \nu & \nu & \nu & \nu & \lambda & \mu \\ \nu & \nu & \nu & \nu & \mu & \lambda \end{array}\right)$$
(11)   
where $`\lambda `$ is the interaction on the same pocket, $`\mu `$ couples two pockets connected by a $`\frac{4\pi }{a}(1,0,0)`$, $`\frac{4\pi }{a}(0,1,0)`$, or a $`\frac{4\pi }{a}(0,0,1)`$ translation, and $`\nu `$ characterizes the remaining couplings between nearest neighbor N points. The matrix for the impurity scattering (with elements $`\mathrm{\Gamma }_{\alpha ,\beta }`$) has the same form and will be described by elements $`\mathrm{\Gamma }_0,\mathrm{\Gamma }_1`$, and $`\mathrm{\Gamma }_2`$ replacing $`\lambda `$, $`\nu `$, and $`\mu `$ respectively.

Consider the clean limit, the linearized gap equation is

$$\mathrm{\Delta }_\alpha ^{}=\underset{\beta }{}N_0\lambda _{\alpha \beta }\mathrm{\Delta }_\beta ^{}\mathrm{ln}\left(\frac{2\gamma \omega _D}{\pi T_c}\right).$$
(12)   
The six $`\mathrm{\Delta }_\alpha `$ transform among each other under cubic symmetry transformations forming a 6D reducible representation of the cubic group $`O_h`$, which is split into a $`1D`$ $`A_{1g}`$, a $`2D`$ $`E_g`$, and a $`3D`$ $`F_{2g}`$ irreducible representation. These three representations correspond to different order parameters with three critical temperatures:

$`T_{c0,A}`$ $`=`$ $`{\displaystyle \frac{2\gamma \omega _D}{\pi }}\mathrm{exp}\left[{\displaystyle \frac{1}{N_0(\lambda +\mu +4\nu )}}\right]`$ (13)   
$`T_{c0,E}`$ $`=`$ $`{\displaystyle \frac{2\gamma \omega _D}{\pi }}\mathrm{exp}\left[{\displaystyle \frac{1}{N_0(\lambda +\mu 2\nu )}}\right]`$ (14)   
$`T_{c0,F}`$ $`=`$ $`{\displaystyle \frac{2\gamma \omega _D}{\pi }}\mathrm{exp}\left[{\displaystyle \frac{1}{N_0(\lambda \mu )}}\right]`$ (15)   
where the factors in the exponentials must be negative for a non-zero transition temperature. When $`\nu >0`$ or $`2\nu +\mu >0`$ (i.e. for repulsive inter-pocket interactions) the higher dimensional representations have the higher $`T_c`$. The basis wave function for 1D $`A_{1g}`$ identical representation is

$$l=(\mathrm{\Delta }_1+\mathrm{\Delta }_2+\mathrm{\Delta }_3+\mathrm{\Delta }_4+\mathrm{\Delta }_5+\mathrm{\Delta }_6)/\sqrt{6},$$
(16)   
the basis wave functions for the 2D $`E_g`$ representation can be chosen as

$`\eta _1`$ $`=`$ $`(\mathrm{\Delta }_1+ϵ\mathrm{\Delta }_2+\mathrm{\Delta }_3+ϵ\mathrm{\Delta }_4+ϵ^2\mathrm{\Delta }_5+ϵ^2\mathrm{\Delta }_6)/\sqrt{6}`$ (17)   
$`\eta _2`$ $`=`$ $`(\mathrm{\Delta }_1+ϵ^2\mathrm{\Delta }_2+\mathrm{\Delta }_3+ϵ^2\mathrm{\Delta }_4+ϵ\mathrm{\Delta }_5+ϵ\mathrm{\Delta }_6)/\sqrt{6}`$ (18)   
where $`ϵ=\mathrm{exp}(2\pi i/3)`$, and the basis wave functions for the 3D $`F_{2g}`$ representation can be chosen as

$`\eta _x`$ $`=`$ $`(\mathrm{\Delta }_5\mathrm{\Delta }_6)/\sqrt{2}`$ (19)   
$`\eta _y`$ $`=`$ $`(\mathrm{\Delta }_1\mathrm{\Delta }_3)/\sqrt{2}`$ (20)   
$`\eta _z`$ $`=`$ $`(\mathrm{\Delta }_2\mathrm{\Delta }_4)/\sqrt{2}.`$ (21)   
Following Refs. , the Ginzburg Landau functional for the 2D and 3D representations are found to be

$$\delta F_E/N_0=\frac{TT_{c0,E}}{T_{c0,E}}(|\eta _1|^2+|\eta _2|^2)+\frac{7\zeta (3)}{96\pi ^2T_{c0,E}^2}(|\eta _1|^4+|\eta _2|^4+4|\eta _1|^2|\eta _2|^2)$$
(22)   
$$\delta F_F/N_0=\frac{TT_{c0,F}}{T_{c0,F}}(\stackrel{}{\eta }\stackrel{}{\eta }^{})+\frac{7\zeta (3)}{32\pi ^2T_{c0,F}^2}(|\eta _x|^4+|\eta _y|^4+|\eta _z|^4).$$
(23)   
Eq. (22) for the $`E_g`$ representation implies $`(\eta _1,\eta _2)=(1,0)`$ is a stable ground state. Following the notation of Ref.  this corresponds to the superconducting class $`O(D_2)`$. The properties of such a ground state are the same as those found for the analogous calculation for FS pockets centered at the three X points in a simple cubic lattice and this is also the situation that applies to both LaB<sub>6</sub> and CeRu<sub>2</sub> (we refer to Ref.  for more details). Eq. (23) for the $`F_{2g}`$ representation implies the ground state solution $`(\eta _x,\eta _y,\eta _z)=[1,\mathrm{exp}(i\varphi _1),\mathrm{exp}(i\varphi _2)]`$ where $`\varphi _1`$ and $`\varphi _2`$ are arbitrary phase factors. The degeneracy arising from the phases $`\varphi _1`$ and $`\varphi _2`$ is an artifact of the BCS theory and is not lifted by higher order terms in free energy functional. In the notation of Ref.  the free energy of Eq. (23) places the system on boundary of two phases with superconducting classes $`D_3\times R`$ and $`D_3(E)`$. A similar situation arose for FS pockets centered at the four L points of a face centered cubic lattice where a degeneracy was found between solutions corresponding to the classes $`D_4^{(2)}(D_2)\times R`$ and $`D_4(E)`$ of the $`F_{2g}`$ representation . The presence of a FS centered at the $`\mathrm{\Gamma }`$ point lifts this degeneracy. As a result the solution $`(\eta _x,\eta _y,\eta _z)=(1,ϵ,ϵ^2)`$ corresponding to the magnetic class $`D_3(E)`$ is likely. This class allows ferromagnetism and it will have point nodes on the $`\mathrm{\Gamma }`$-centered FS (the N point centered FS pockets will have no nodes) .

Now consider the effect of including impurity scattering on $`T_{c,A},T_{c,F},T_{c,E}`$. It is convenient to define the following relaxation times

$`(2\tau _A)^1=`$ $`\mathrm{\Gamma }_0+4\mathrm{\Gamma }_1+\mathrm{\Gamma }_2`$ (24)   
$`(2\tau _E)^1=`$ $`\mathrm{\Gamma }_0+\mathrm{\Gamma }_22\mathrm{\Gamma }_1`$ (25)   
$`(2\tau _F)^1=`$ $`\mathrm{\Gamma }_0\mathrm{\Gamma }_2`$ (26)   
The lifetime $`\tau _A`$ determines the elastic mean free path while the lifetimes $`\tau _E`$ and $`\tau _F`$ cannot be easily measured. Solution of the linearized equations indicate that the transition temperatures $`T_{c,i}`$ are given by

$$\mathrm{ln}\frac{T_{c0,i}}{T_{c,i}}=\psi (\frac{1}{2}+\frac{\tau _A^1\tau _i^1}{4\pi T_{c,i}})\psi (\frac{1}{2})$$
(27)   
where $`\psi (x)`$ is the digamma function. From this expression it is clear that $`T_{c,A}`$ is not suppressed by non-magnetic impurities while $`T_{c,E}`$ and $`T_{c,F}`$ are suppressed. Note that if $`\mathrm{\Gamma }_1=\mathrm{\Gamma }_2=0`$ (there is only intra-pocket impurity scattering) then all three transition temperatures are not suppressed by impurities. It is only inter-pocket scattering that reduce $`T_{c,E}`$ and $`T_{c,F}`$ from $`T_{c0,E}`$ and $`T_{c0,F}`$. Consequently, the suppression of $`T_c`$ as the impurity concentration is increased is not as rapid as might be expected from previous analysis of unconventional single band superconductors . Furthermore an impurity induced transition is possible from the non $`s`$-wave superconducting states to the $`s`$-wave superconducting states when $`\lambda <4\nu \mu `$ where negative $`\lambda `$ corresponds to an attractive intra-pocket interaction and either $`\nu >0`$ or $`2\nu +\mu >0`$. The observation of an abrupt change in the $`T_c`$ dependence on impurity concentration corresponding to this phase transition (i.e. $`T_c`$ initially decreasing with impurity concentration in the exotic state and then becoming impurity independent in the $`s`$-wave state) may help to identify such exotic superconducting states.

The results of the above analysis may be directly applied to CeCo<sub>2</sub> and predicts that due to the presence of the the $`\mathrm{\Gamma }`$-centered FS sheet, the low temperature specific heat will vary as $`T^3`$ for the exotic states considered (with superconducting classes $`O(D_2)`$ or $`D_3(E)`$). Note that initial measurements appear more consistent with a $`T^2`$ behavior however these measurements only exist down to $`T/T_c0.13`$  which may not yet be sufficiently low to extract the low temperature behavior reliably. For the materials LaB<sub>6</sub> and CeRu<sub>2</sub> the FS pockets are centered at the X points for which the exotic superconducting state belongs to the 2D $`E_g`$ representation which is described in detail in Ref. . Impurity scattering will have qualitatively the same effect on this state as on the exotic states examined above.

In conclusion we have considered the effect of isotropic non-magnetic impurity scattering on the exotic superconducting states that arise in a BCC lattice when the FS forms pockets centered at the six N-points. We have found that increasing the impurity concentration does not suppress these non $`s`$-wave states as rapidly as would be expected from earlier studies of impurity scattering in unconventional superconductors. These results are not specific to FS pockets centered at the reciprocal lattice N points of a BCC lattice but will apply to any degenerate set of FS pockets.

We would like to thank Z.Fisk, D. Khokhlov, J.R. Schrieffer, and the members of the NHMFL condensed matter theory group seminar for useful discussions and comments. This work was supported by the National High Magnetic Field Laboratory through NSF cooperative agreement No. DMR-9527035 and the State of Florida.