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# Tristability in a non-equilibrium double-quantum-dot in Kondo regime

## Abstract

Electron tunneling through a non-equilibrium double quantum dot in the Kondo regime is studied. In the region of negative differential resistance, it is shown that this system possesses a complex response to the applied potential characterized by a tristable solution for the current. Increasing the applied potential or reducing the inter-dot coupling, the system goes through a transition from a coherent inter-dot regime to an incoherent one. The different nature of the solutions are characterized and it is shown that the effects of the asymmetry in the dot-lead coupling can be used to control the region of multistability. The mean-field slave-boson formalism is used to obtain the solution of the problem.

The Kondo effect in quantum-dots ($`QDs`$) has been extensively studied in the last years. The experimental evidence has confirmed that many of the phenomena that characterize strongly correlated metals and insulators, as it is the case of the Kondo effect, are present in $`QDs`$. The $`QDs`$ allow to study systematically the quantum-coherence many-body Kondo state, due to the possibility of continuous tuning of the relevant parameters governing the properties of this state, in equilibrium and non-equilibrium situations.

The electron tunneling through double-quantum-dots ( $`DQD`$) in the Kondo regime has received much attention in recent years. In comparison with a single quantum-dot, the double-quantum-dot has a richer physics. For example in $`DQDs`$ it is possible to study the competition between the inter-dot antiferromagnetic spin-spin correlation and the dot-conduction spin-spin correlation present in its ground state and also it can be investigated the inter-dot coherence effects that results from the Coulomb interaction. The type of coupling between the $`QDs`$ determines the character of the electronic states and the transport properties of the artificial molecule. In the tunneling regime, the electronics states are extended across the entire system and can be constructed from a coherent state based on the bonding or anti-bonding levels of the $`QDs`$. Some aspects of the non-equilibrium transport properties of a simplified $`DQD`$ in the Kondo regime, constituted by two identical $`QDs`$ has recently been studied . When the inter-dot coupling is greater than the level broadening, there is a region of voltage where this system shows a bistable behavior characterized by two solutions for the current. This behavior resembles the $`J`$-$`V`$ characteristic curve of a double barrier structure in the accumulation of charge regime and in doped superlattices. However, theoretical and experimental studies have confirmed that a double barrier structure possesses a more complex behavior than the one predicted by a bistability. The $`J`$-$`V`$ curve of this system has in many cases a Z-shape, indicating the existence of a tristable solution for the current.

In this work we analyze the new physics derived from the complex behavior that characterize the electron tunneling through a non-equilibrium $`DQD`$ in the Kondo regime. Although this system is essentially different from a double barrier heterostructure, we find that, in certain region of the parameter space, the $`JV`$ characteristic curve of both are similar. However, the problem we analyze has much richer physics. Increasing the asymmetry of the coupling of the dots with the leads or reducing the inter-dot coupling, the system goes through a transition from a coherent inter-dot regime to an incoherent one. The characteristic curve reflects this transition changing from a Z-shape in the incoherent region to a loop-shape when the dots behave coherently. The different nature of the solutions are characterized and it is shown that the effects of the asymmetry in the dot-lead coupling can be used to control the region of multistability.

We adopt the two-fold degenerate Anderson Hamiltonian in the limit $`U\mathrm{},`$ that is diagonalized using the mean-field slave-boson formalism. Although this mean-field approximation has, in certain region of the parameters that define the system, a non-physical solution it has been shown that the physics related to the negative differential resistance is not associated to it. The $`DQD`$ is driven out-of-equilibrium by means of a dc bias voltage $`V`$ at zero temperature.The double occupancy in each dot is forbidden and the inter-dot Coulomb interaction neglected. We introduce the slave-boson operator $`b_\alpha ^{}`$ that creates an empty state and a fermion operator $`f_{\alpha \sigma }`$ that annihilates a single occupied state with spin $`\sigma `$. To eliminate the possibility of double occupancy we impose the constraint $`Q_\alpha _\sigma f_{\alpha \sigma }^{}f_{\alpha \sigma }+b_\alpha ^{}b_\alpha =1`$. The annihilation operator of an electron in the dot $`\alpha `$ is $`c_{\alpha \sigma }=b_\alpha ^{}f_{\alpha \sigma }`$. In the mean field approximation the bosonic operators $`b_\alpha ^{}`$ and $`b_\alpha `$ are replaced by their expectation values, $`b_\alpha =\stackrel{~}{b}_\alpha \sqrt{2}=b_\alpha ^{}=\stackrel{~}{b}_\alpha ^{}\sqrt{2}.`$ Hence the Hamiltonian of the double quantum-dot connected to leads plus constraints is written as,

$`H`$ $`=`$ $`H_{lead}+{\displaystyle \underset{\alpha =0,1,\sigma }{}}\stackrel{~}{\epsilon }_\alpha n_{\alpha \sigma }`$ (1)
$`+`$ $`\stackrel{~}{V}_L{\displaystyle \underset{\sigma }{}}(c_{1\sigma }^{}f_{0\sigma }+f_{0\sigma }^{}c_{1\sigma })+\stackrel{~}{V}_R{\displaystyle \underset{\sigma }{}}(f_{1\sigma }^{}c_{2\sigma }+c_{2\sigma }^{}f_{1\sigma })`$ (2)
$`+`$ $`\stackrel{~}{t}_c{\displaystyle \underset{\sigma }{}}(f_{0\sigma }^{}f_{1\sigma }+f_{1\sigma }^{}f_{0\sigma })+{\displaystyle \underset{\alpha =0,1}{}}\lambda _\alpha (\stackrel{~}{b}_\alpha ^{}\stackrel{~}{b}_\alpha 1).`$ (3)
where $`\stackrel{~}{\epsilon }_0=\epsilon _0+\lambda _0`$, $`\stackrel{~}{\epsilon }_1=\epsilon _1+\lambda _1`$, $`\stackrel{~}{V}_L=V_L\stackrel{~}{b}_0`$, $`\stackrel{~}{V}_R=V_R\stackrel{~}{b}_1`$, $`\stackrel{~}{t}_c=t_c\stackrel{~}{b}_0\stackrel{~}{b}_1,`$the $`\lambda _\alpha `$ are Lagrangian multipliers which guarantee the constraint conditions on the $`Q_\alpha `$ and the parameters $`t_c,`$ $`V_L`$ and $`V_R`$ are the inter-dot connection and left and right dot connections with the leads respectively.

The first term on the right-hand side of Eq.1 represents the electrons in the left and right leads;

$$H_{lead}=\underset{i0,1}{}\epsilon _in_{i\sigma }+t\underset{<ij0,1>\sigma }{}c_{i\sigma }^{}c_{j\sigma }.$$
(4)
where the operator $`c_{i\sigma }^{}`$ creates an electron in the site $`i`$ with spin $`\sigma `$, $`\epsilon _i`$ is the site energy and $`t`$ is first-neighbor hopping in the leads.

Here $`H_{lead}`$ corresponds to the free-particle Hamiltonian with eigenfunctions of the Bloch type,

$$|k,\sigma =\underset{j}{}e^{ikja}|j,\sigma $$
(5)
where $`|k,\sigma `$ is the momentum eigenstate with spin $`\sigma `$ and $`|j`$ is a Wannier state localized at site $`j`$ of spin $`\sigma `$. The dispersions relation associated with these Bloch states reads

$$\epsilon _k=2t\mathrm{cos}(ka)$$
(6)
The model has an energy band, extending from $`2t`$ to $`+2t`$, with the first Brillouin zone expanding the $`k`$ interval $`[\pi /a,\pi /a]`$.

The stationary state of the complete Hamiltonian $`H`$ with energy $`\epsilon _k`$ can be written as

$$|\psi _{k\sigma }=\underset{j}{}a_{j\sigma }^k|j,\sigma $$
(7)
where the coefficients $`a_{i\sigma }^k`$ are given by,

$$a_{j\sigma }^k=<j,\sigma |\psi _{k\sigma }>.$$
(8)
We obtain the following eigenvalues equations for the Wannier amplitudes $`a_{j\sigma }^k`$

$`\epsilon _ka_{j,\sigma }^k`$ $`=`$ $`j,\sigma \left|H\right|\psi _{k\sigma }`$ (9)
$`\epsilon _ka_{j,\sigma }^k`$ $`=`$ $`\epsilon _ja_{j,\sigma }^k+t(a_{j1,\sigma }^k+a_{j+1,\sigma }^k)(j1,0,1,2),`$ (10)
$`\epsilon _ka_{1(2),\sigma }^k`$ $`=`$ $`\epsilon _{1(2)}a_{2(2),\sigma }^k+\stackrel{~}{V}_{L(R)}a_{0(1),\sigma }^k+ta_{2(3),\sigma }^k,`$ (11)
$`\epsilon _ka_{0(1),\sigma }^k`$ $`=`$ $`\stackrel{~}{\epsilon }_{0(1)}a_{0(1),\sigma }^k+\stackrel{~}{V}_{L(R)}a_{1(2),\sigma }^k+\stackrel{~}{t}_ca_{1(0),\sigma }^k,`$ (12)
where $`a_{j,\sigma }^k`$ is the amplitude of probability to find the electron in the site $`j`$ and state $`k`$ with spin $`\sigma `$.

The four parameters ($`\stackrel{~}{b}_0`$, $`\stackrel{~}{b}_1`$, $`\lambda _0`$, $`\lambda _1`$) are determined minimizing the expectation values of the Hamiltonian (7). They satisfy the set of four equations:

$`\stackrel{~}{b}_{0(1)}^2+{\displaystyle \frac{1}{2}}{\displaystyle \underset{k,\sigma }{}}\left|a_{0(1),\sigma }^k\right|^2`$ $`=`$ $`{\displaystyle \frac{1}{2}},`$ (13)
$`{\displaystyle \frac{\stackrel{~}{V}_{L(R)}}{2}}{\displaystyle \underset{k,\sigma }{}}Re(a_{1(2),\sigma }^ka_{0(1),\sigma }^k)`$ $`+`$ (14)
$`{\displaystyle \frac{\stackrel{~}{t}_c}{2}}{\displaystyle \underset{k,\sigma }{}}Re(a_{1(0),\sigma }^ka_{0(1),\sigma }^k)+\stackrel{~}{\lambda }_{0(1)}\stackrel{~}{b}_{L(R)}^2`$ $`=`$ $`0.`$ (15)
The sum over the wave vector $`k`$ cover all the occupied states. The resulting equations are nonlinear because of the renormalization of the localized levels in the dots, the interdot coupling tunneling and the coupling tunneling between the $`QD`$s and the leads.

The stationary scattering problem is solved by finding the eigenstates with positive $`k`$. In order to study the solutions of equations (4) and (5) we assume a plane wave incident from the left with an amplitude $`I`$, with a partial reflection amplitude $`R`$. The waveform at the right is a simple plane wave with intensity given by the transmission amplitude $`T`$. Taking this to be the solution of the system, we can write,

$`a_j^k`$ $`=`$ $`Ie^{ikaj}+Re^{ika_j}\text{}j<0`$ (16)
$`a_j^k`$ $`=`$ $`Te^{ik_Raj},\text{ }j>1`$ (17)
and those with negative $`k`$

$`a_j^k`$ $`=`$ $`\stackrel{~}{I}e^{ikaj}+\stackrel{~}{R}e^{ika_j},j>1`$ (18)
$`a_j^k`$ $`=`$ $`\stackrel{~}{T}e^{ik_Laj},j<0`$ (19)
These functions describe plane-wave electron approaching the scattering potential from $`j=\mathrm{}`$ and $`j=+\mathrm{},`$ respectively, with transmission and reflections amplitudes $`T`$ and $`R`$ for $`k>0`$, and $`\stackrel{~}{T}`$ and $`\stackrel{~}{R}`$ for $`k<0`$.

The solution of equations (7) can be obtained through an adequate iteration from right to left for $`k>0`$, and from left to right for $`k<0`$. For a given transmitted amplitude, the associated reflected and incident amplitudes may be determined by matching the iterated function to the proper plane wave at the left lead for $`k>0`$ and at the right lead for $`k<0.`$ The transmission amplitude $`t(k)=T/I`$ and $`\stackrel{~}{t}(k)=\stackrel{~}{T}/\stackrel{~}{I}`$ are obtained from the iterative procedure.

The equations (7) and (8) are nonlinear and require a self-consistent solution that is obtained using a conjugate gradient algorithm. In this work, we are interested in analyzing all the stationary solutions for the current. As $`J(V)`$and $`V(J)`$ are multivalued functions, the multiple solutions for the quantities $`\stackrel{~}{b}_0`$, $`\stackrel{~}{b}_1`$, $`\lambda _0`$, $`\lambda _1`$are obtained by fixing, first the external potential $`V`$ and afterwards the current$`J`$ in the equations of motion of the system. This method permits us to obtain the complete $`J`$-$`V`$characteristic curve.

Once the amplitudes $`a_{j,\sigma }^k`$ are known, the current is numerically obtained from,

$$J=\frac{2e}{\mathrm{}}\stackrel{~}{V}_L\underset{k,\sigma }{}Im\{a_{1,\sigma }^ka_{0,\sigma }^k\}.$$
(20)
We study first a model which consists of two leads equally connected$`(V_L=V_R=V_0)`$ to two quantum dots with $`\mu _L=V/2`$ and $`\mu _R=V/2`$, $`t_\text{ }=30\mathrm{\Gamma }_0`$, $`V_0=5.48\mathrm{\Gamma }_0`$, $`\epsilon _0=\epsilon _1=3.5\mathrm{\Gamma }_0`$ (Kondo regime with $`T_K10^3\mathrm{\Gamma }_0`$ with $`\mathrm{\Gamma }_0=2\pi V_0^2\rho (0)`$).

The Fig 1 shows the $`J`$-$`V`$ characteristic curve for different values of $`t_c`$. Within a range of the external bias voltage values, there are three stationary solutions for the current. We can identify two regimes. One for $`\mathrm{\Gamma }_0<t_c<t_{c0}`$ ,( $`t_{c0}`$ is a constant to be analyzed below ), where the $`JV`$ characteristic curve has a Z-shape and another one for $`t_c>t_{c0}`$ where the curve becomes loop-shaped. An experiment that would consist in studying this system just by simply continuously modifying the applied potential $`V`$ would characterize the behavior of the current as bistable. At a critical value $`Vc_,`$ there would be a discontinuous reduction of the current when $`V`$ is increased and other $`Vc_{}(Vc_{}>Vc_{})`$ where the current would rise, ($`t_c<t_{c0}`$), or diminish , ($`t_c>t_{c0}),`$ discontinuously when $`V`$ is reduced. In this case the interior of the bistability remains inaccessible to the experiment. However, the internal shape could be reached, as it is for the case of double barrier heterostructrures, employing a load line in the experimental measurement that permits to go along all the points of the $`JV`$ characteristic curve.

When $`t_c>\mathrm{\Gamma }_0`$, the Kondo levels $`\stackrel{~}{\epsilon }_0`$ and $`\stackrel{~}{\epsilon }_1`$are splitted into two molecular states, corresponding to the bonding and antibonding levels. They are located in, $`\stackrel{~}{\epsilon }_\pm =\{(\stackrel{~}{\epsilon }_0+\stackrel{~}{\epsilon }_1)/2\pm \sqrt{(\stackrel{~}{\epsilon }_0\stackrel{~}{\epsilon }_1)^2+4\stackrel{~}{t}_c^2}\}/2`$. In the Fig. 2a and 2b we plot $`\stackrel{~}{\epsilon }_\pm `$, as a function of $`V,`$ for two values of $`t_c`$. The main features are: a) For $`V=0`$, the bonding and antibonding levels satisfies $`\stackrel{~}{\epsilon }_\pm `$ $`=`$ $`\pm \stackrel{~}{t}_c.`$ When the bias $`V`$ is increased of the order of $`T_k`$, $`\stackrel{~}{\epsilon }_\pm `$ are kept almost constant and the dots reacts to the external potential in a coherent way. For higher values of $`V`$ , $`\stackrel{~}{\epsilon }_{+\text{ }}`$and $`\stackrel{~}{\epsilon }_\text{ }`$approach each other and go through the multistable region. The right dot is connected to the left reservoir by the mediation of the left one through an effective interaction $`V_L^{eff}`$ that for energies in the vicinity of the Fermi level of the order of $`T_k`$, is approximately given by $`V_L^{eff}=`$ $`\stackrel{~}{t}_c/2\pi \stackrel{~}{V}_L\rho (0)`$. The effective levels have a clear different behavior whether the right dot is interacting stronger with the left than with the right $`V_L^{eff}>\stackrel{~}{V}_R`$ or the contrary, $`V_L^{eff}<\stackrel{~}{V}_R`$ . For the case we are analyzing, $`(V_L=V_R=V_0)`$, this can be controlled manipulating the value of $`t_c`$. Defining $`t_{c0}`$as the frontier between these two situation, in the case when $`t_c<t_{c0},`$ increasing the potential beyond the mutistable region, the coherence between the dots is lost and $`\stackrel{~}{\epsilon }_{+\text{ }}`$and $`\stackrel{~}{\epsilon }_\text{ }`$converge towards their own chemical potential $`\mu _{L(R)}`$, as display in Fig.2a. The interactions of the dots with the leads $`\stackrel{~}{V}_L`$ and $`\stackrel{~}{V}_R`$ are equally renormalized as can be seen in Fig 2c. The system possesses an splitted Kondo peak. One sub-peak with its weight essentially located at the left dot with energy at the neighborhood of $`\mu _L`$ and the other located at the right dot near $`\mu _R.`$ For $`t_c>t_{c0}`$ by the contrary, due to the stronger interaction between the dots, they maintain their coherence and result to be partially disconnected from the right lead. This is reflected in the behavior of the renormalized interaction of each dot with its respective lead as shown in Fig.2d and in their localized levels $`\stackrel{~}{\epsilon }_{+\text{ }}`$and $`\stackrel{~}{\epsilon }_\text{ }`$, that both follow $`\mu _L`$ as $`V`$ increases presented in Fig2b. The Kondo peak, almost pinned at $`\mu _L,`$ is in this case equally distributed among the two dots.

Next we will discuss the effect of the asymmetric site energies case, $`\epsilon _0\epsilon _1`$. We model the asymmetric site energies by setting $`\epsilon _0=(1\kappa )e_{0,}\epsilon _1=(1+\kappa )e_0,`$ where $`\kappa `$ is the asymmetry parameter and $`e_0=3.5\mathrm{\Gamma }_0`$ . Figs 3 shows the $`J`$-$`V`$ characteristics for various values of $`\kappa `$ at $`t_c=1.3\mathrm{\Gamma }_0`$ and $`t_c=2.5\mathrm{\Gamma }_0`$. It is seen that the region of multistability is very sensitive to the change of $`\kappa `$ and in particular it disappears for sufficiently large values of it. The coherent or incoherent behavior of the dots discussed above can be controlled in this case changing the asymmetry parameter $`\kappa .`$ Fig 4 shows a map with the regions of multistability depending on the bias voltage $`V`$ and $`\kappa `$. It is seen that the width of the multistability region has lower and upper limits, which depend upon the asymmetry in the dot-lead coupling. Similar results were obtained for an asymmetric dot-lead coupling case, $`V_LV_R`$.

In this paper we have studied the $`J`$-$`V`$ characteristic curve of a double-quantum-dot in the Kondo regime. It exhibits a multistable behavior that enhances as the interdot coupling tunneling increases. It becomes Z-shaped or loop-shaped depending on the various coupling tunneling parameters, which control wether the dots respond coherently or incoherently to the external applied potential. Moreover, we show that it is possible to manipulate the multistability in a sample by changing the asymmetry in the dot-lead coupling.

Work supported by grants Milenio ICM P99-135-F, FONDECYT 1990443, Cátedra Presidencial en Ciencias, Fundación Antorchas/Vitae/Andes , FINEP and CNPq.


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# Universality of delocalization in unconventional dirty superconducting wires with broken spin-rotation symmetry

## Abstract

In dirty superconducting wires, quasiparticle states at the Fermi level need not be exponentially localized if spin-rotation symmetry is broken \[Brouwer et al., Phys. Rev. Lett. 85, 1064 (2000)\]. Here we present evidence that not-localized states are generic in the thick-wire limit, while for wires of finite thickness delocalization requires fine tuning of the disorder, consistent with earlier results of Motrunich et al. \[Phys. Rev. B 63, 224204 (2001)\]. The thick-wire limit is defined as the simultaneous limit where the length $`L`$ of the wire and the number $`N`$ of propagating channels at the Fermi energy are both taken to infinity with their ratio held fixed.

Localization properties of weakly disordered normal-metal wires depend first and foremost on the fundamental symmetries of the wire: presence or absence of time-reversal symmetry and spin-rotation symmetry. In addition to these, two more symmetries can play an important role in the characterization of quantum wires: chiral symmetry and particle-hole symmetry. The former is relevant for lattice models with randomness in the hopping amplitudes only, while the latter applies to superconducting wires or normal-metal wires in the proximity of a superconductor.

Is symmetry the only player determining the localization properties? For normal-metal wires, it is generally agreed on that this is the case when the disorder is weak. For superconducting wires, different views have been published in the literature. Advocates of field-theoretic, random-matrix, or Fokker-Planck approaches have mostly considered the symmetry classification as sufficient, thus arriving at a division of superconducting wires into four universality classes.AltlandZirnbauer ; HigherD ; Bundschuh ; Senthil ; classD ; Bocquet ; BFGM  These are labeled C, CI, D, and DIII, and are characterized by the presence or absence of time-reversal symmetry and spin-rotation symmetry.AltlandZirnbauer  For the classes D and DIII, where spin-rotation symmetry is broken, it was found that wave functions are “critical” if disorder is weak, rather than exponentially localized, on length scales beyond a characteristic crossover scale $`Nl`$, where $`N`$ is the number of propagating channels in the wire and $`l`$ is the mean free path. Here “critical” indicates algebraic decay of the average conductance, opposed to exponential decay if wave functions are localized. Disorder is “weak” if $`k_Fl1`$, $`k_F`$ being the Fermi wave vector. On the other hand, using a numerical transfer matrix method to calculate localization lengths in single-channel wires and strong-disorder renormalization-group arguments, Motrunich et al. found that, if spin-rotation symmetry is broken, the localization length only diverges if the disorder is fine tuned.Motrunich  They concluded that symmetry alone is not sufficient to characterize disordered wires with particle-hole symmetry. Such a finding is consistent with the expectation that, in a single-channel wire, weak spin-orbit scattering or weak superconducting correlations cannot destroy the localized phase that exists in the presence of spin-rotation symmetry and without superconductivity.

In this paper we take a more detailed look at this apparent contradiction for the case of class D where, in addition to spin-rotation symmetry, time-reversal symmetry is broken as well. We consider both regimes $`LNl`$ and $`LNl`$. For thick wires ($`N1`$), the regime $`lLNl`$ corresponds to the diffusive regime. For thin wires ($`N`$ of order unity), one has $`Nll`$, and there is no diffusive regime. Our main conclusion — to be supported by numerical and analytical arguments below — is that, as argued in Ref. Motrunich, , for quantum wires of finite thickness and broken spin-rotation symmetry, fine tuning of the disorder is required in order to obtain a diverging localization length. However, we shall also argue that in the limit $`N\mathrm{}`$ of “thick” quantum wires symmetry alone is sufficient to determine the localization properties.foot1  We note that this criterion is not different from that in normal wires.foot2  Thus, as far as the classification based on symmetry is concerned, superconducting disordered wires are no less universal than ordinary normal-metal wires. In the final analysis, realization of the quasi-one-dimensional critical behavior of class D demands fine tuning of microscopic parameters for a wire of finite thickness but becomes generic in the thick-wire limit provided the disorder is sufficiently weak. We reach this conclusion by studying the competition between localization in the standard unitary class (no superconductivity) and criticality in class D that occurs upon increasing the strength of superconducting correlations in the wire. However, the same scenario applies to the crossover between the localized phase of class C and the critical phase of class D upon breaking of the spin-rotation symmetry.

As in Ref. BFGM, , our starting point is the Hamiltonian

$$=𝒦+𝒱,𝒦=\sigma _0\gamma _0\tau _3𝟙_{}𝕚𝕧_𝔽_𝕩,$$
(1)
where $`\sigma _0`$ is the $`2\times 2`$ unit matrix in the spin grading, $`\gamma _0`$ is the $`2\times 2`$ unit matrix in particle-hole grading, and $`\tau _3`$ is the Pauli matrix in left/right mover grading. The kinetic energy $`𝒦`$ describes the propagation of right and left moving quasiparticles in $`N`$ channels at the Fermi level. The “potential” $`𝒱(x)`$ is an $`8N\times 8N`$ matrix that accounts for the presence of both disorder and superconducting correlations. In particle/hole ($`\gamma `$) grading it reads

$$𝒱=\left(\begin{array}{cc}v& \mathrm{\Delta }\\ \mathrm{\Delta }^{}& v^\mathrm{T}\end{array}\right),$$
(2)
where $`v`$ ($`\mathrm{\Delta }`$) is a Hermitian (antisymmetric) $`4N\times 4N`$ matrix, representing the impurity potential (superconducting order parameter). The form (2) of the potential $`𝒱`$ ensures that the Hamiltonian $``$ obeys particle-hole symmetry: $`=\gamma _1^\mathrm{T}\gamma _1`$.AltlandZirnbauer  In addition, $``$ (and hence $`𝒱)`$ may obey time-reversal invariance $`=𝒯^{}𝒯^1`$, with $`𝒯=i\tau _1\sigma _2`$.

In Ref. BFGM,  it was assumed that the potentials $`\mathrm{\Delta }`$ and $`v`$ in Eq. (2) are Gaussian white-noise potentials with the same variance. It was for this choice of disorder that the “critical” conductance statistics was found. Motrunich et al. have argued that this choice is special: As soon as the variances of $`\mathrm{\Delta }`$ and $`v`$ are no longer equal, the conductance will decay exponentially with length $`L`$. In addition, they showed that if a term proportional to $`v_F\tau _2/2l_s`$ is added to the Hamiltonian, which corresponds to a staggering of the hopping amplitude in a lattice version of the problem,BMSA  the localization length is finite even if $`v`$ and $`\mathrm{\Delta }`$ have the same variance.

Below we shall analyze the effects of a different variance of $`\mathrm{\Delta }`$ and $`v`$ and of staggering on the localization length, and discuss how these effects change with the thickness of the wire. We will first address the diffusive regime, where an analytical treatment is possible, and then the localized regime, where we support our arguments with numerical simulations.

Different variances of $`\mathrm{\Delta }`$ and $`v`$. For simplicity, we assume that time-reversal symmetry and spin-rotational symmetry are completely broken. Hence we take the potentials $`v`$ and $`\mathrm{\Delta }`$ as Gaussian white-noise, with vanishing means and with variances

$`v_{ij}^{}(x)v_{kl}^{}(y)`$ $`=`$ $`{\displaystyle \frac{v_F^2}{8Nl_v}}\delta _{ik}^{}\delta _{jl}^{}\delta (xy),`$ (3)
$`\mathrm{\Delta }_{ij}^{}(x)\mathrm{\Delta }_{kl}^{}(y)`$ $`=`$ $`{\displaystyle \frac{v_F^2}{8Nl_\mathrm{\Delta }}}\left(\delta _{ik}^{}\delta _{jl}^{}\delta _{il}^{}\delta _{jk}^{}\right)\delta (xy).`$
Here $`l_v`$ and $`l_\mathrm{\Delta }`$ are the mean free paths for scattering from potential disorder and from (fluctuations of) the superconducting pair potential $`\mathrm{\Delta }`$, respectively. When $`l_\mathrm{\Delta }=l_v`$, the exact solution of Ref. BFGM,  applies. We will refer to this special case as the pure class D and consider the generic case $`l_\mathrm{\Delta }l_v`$ as a point in the crossover between the standard unitary ensemble and class D. (The standard unitary ensemble corresponds to the absence of superconducting correlations, $`l_\mathrm{\Delta }=\mathrm{}`$.) The combined mean free path $`l`$ for scattering from either $`v`$ or $`\mathrm{\Delta }`$ is $`l^1=l_v^1+l_\mathrm{\Delta }^1`$. In the special case $`l_\mathrm{\Delta }=l_v`$, i.e., in the pure class D, the ensemble average dimensionless conductance $`g`$ in the diffusive regime $`LNl`$ readsBFGM

$$g=\frac{4Nl}{L}+\frac{1}{3}+𝒪\left(\frac{L}{Nl}\right).$$
(4)
For $`LNl`$, the average conductance decays algebraically, whereas the “typical conductance” $`\mathrm{exp}(\mathrm{ln}g)`$ decreases proportional to $`\mathrm{exp}[(2L/\pi Nl)^{1/2}]`$,BFGM

$`g=\sqrt{{\displaystyle \frac{8Nl}{\pi L}}},\mathrm{ln}g=\sqrt{{\displaystyle \frac{2L}{\pi Nl}}}.`$ (5)
For the standard unitary ensemble $`l_\mathrm{\Delta }=\mathrm{}`$ one has $`g=4Nl/L+𝒪(L/Nl)`$ in the diffusive regime, while in the localized regime $`ge^{L/8Nl}`$, $`\mathrm{ln}g=L/2Nl+𝒪(1)`$.BeenakkerReview

Let us now consider the generic case $`l_vl_\mathrm{\Delta }<\mathrm{}`$, i.e., a point in the crossover between the standard unitary ensemble and the pure class D. At a fixed but large $`l_\mathrm{\Delta }l_v`$, this same crossover can also take place as a function of the wire length $`L`$. In that case, short $`L`$ corresponds to the standard unitary ensemble, while class D statistics might be found for large $`L`$. To find the relevant length scale for that crossover we calculate the average conductance in the diffusive regime. Following the method of Ref. MBF,  we derive scaling equations for the averages of certain traces of transmission and reflection matrices $`t`$ and $`r`$ of the wire. For $`l_\mathrm{\Delta },Ll`$ and up to corrections of relative order $`(L/Nl)`$ the relevant scaling equations read

$`4Nl_L\text{tr}t^{}t=\text{tr}t^{}t^2`$
$`+2\left[\text{tr}\left(r^{}rt^{}t\gamma _3r^{}\gamma _3rt^{}t\right)\right],`$
$`4Nl_L\text{tr}\left(1\gamma _3r^{}\gamma _3r\right)=\text{tr}(1\gamma _3r^{}\gamma _3r)^2`$
$`+(\xi _\mathrm{\Delta }/l)^2,`$ (6)
$`4Nl_L\text{tr}\gamma _3r^{}\gamma _3rt^{}t=2\text{tr}\left(1\gamma _3r^{}\gamma _3r\right)`$
$`\times \text{tr}\gamma _3r^{}\gamma _3rt^{}t,`$
$`4Nl_L\text{tr}r^{}rt^{}t=2\text{tr}t^{}t\text{tr}r^{}rt^{}t,`$
where we abbreviated $`\xi _\mathrm{\Delta }=\sqrt{ll_\mathrm{\Delta }/8}`$ and $`\gamma _3`$ is the Pauli matrix in particle-hole grading. Solving Eqs. (6) we find the average conductance $`g=\text{tr}t^{}t`$ for $`l_\mathrm{\Delta },Ll`$,ballistic

$`g`$ $`=`$ $`{\displaystyle \frac{4Nl}{L}}+{\displaystyle \frac{1}{3}}+{\displaystyle \frac{\xi _\mathrm{\Delta }^2}{L^2}}{\displaystyle \frac{\xi _\mathrm{\Delta }}{L}}\mathrm{coth}{\displaystyle \frac{L}{\xi _\mathrm{\Delta }}}+𝒪\left({\displaystyle \frac{L}{Nl}}\right).`$ (7)
The length scale $`\xi _\mathrm{\Delta }`$ marks the crossover between the standard unitary class and class D: For $`L\xi _\mathrm{\Delta }`$ we recover the result $`g=4Nl/L+𝒪(L/Nl)`$ of the standard unitary ensemble, while for $`L\xi _\mathrm{\Delta }`$ Eq. (7) simplifies to the class D result (4). As Eq. (7) is only valid in the diffusive regime $`LNl`$, one can only expect to observe the class D result (4) if $`\xi _\mathrm{\Delta }`$ is smaller than $`Nl`$. In the thick-wire limit this poses no real constraint, and we conclude that, in the thick-wire limit, any finite mean free path $`l_\mathrm{\Delta }`$ will eventually give rise to a weak localization correction to the conductance according to class D if the wire is sufficiently long.

To find what happens in the localized regime we now compare the crossover length scale $`\xi _\mathrm{\Delta }`$ derived above and the localization length $`4Nl`$ in the standard unitary class. If $`\xi _\mathrm{\Delta }Nl`$, the wave functions are still governed by the unitary class on the scale $`Nl`$, not by class D, when localization sets in. Hence there is no room for class D physics to play a role and the localization length is that of the standard unitary class. On the other hand, if $`\xi _\mathrm{\Delta }Nl`$, the statistics of wave functions and conductance is given by that of class D at scales $`\xi _\mathrm{\Delta }`$ and beyond. Therefore if $`\xi _\mathrm{\Delta }Nl`$ we expect that the wave function and conductance statistics for $`LNl`$ is critical, as in class D. If $`Nl`$ and $`\xi _\mathrm{\Delta }`$ are comparable, the conductance statistics in the localized regime is best characterized as in the “crossover” between the two universality classes: The localization length is expected to be larger than $`4Nl`$, but still finite.

In order to make these statements more precise, we look at the normalized inverse localization length,

$$\chi (\sigma )=\frac{\mathrm{ln}g}{\sigma },\sigma =\frac{L}{2Nl}.$$
(8)
In the standard unitary ensemble, one has $`\chi 1`$ as $`L\mathrm{}`$ with $`N`$, $`l_\mathrm{\Delta }`$, and $`l_v`$ held fixed; critical conductance statistics implies $`\chi (\mathrm{})=0`$. A finite value $`0<\chi (\mathrm{})<1`$ corresponds to exponentially localized wave functions, but with a localization length that is larger than in the standard unitary ensemble. Taking the limit $`L\mathrm{}`$ at fixed values of $`N`$, $`l_\mathrm{\Delta }`$, and $`l_v`$ corresponds to a point somewhere in the crossover between the standard unitary ensemble and class D if $`l_\mathrm{\Delta }l_v`$. As such a choice of parameters corresponds to a finite distance from the pure class D, we expect $`\chi (\mathrm{})>0`$ in this case, corresponding to exponentially localized wave functions. This agrees with the claim of Motrunich et al.,Motrunich  who found critical statistics at the point $`l_\mathrm{\Delta }=l_v`$ only.

In the thick-wire limit, however, the picture is different. The thick-wire limit is defined as the simultaneous limit $`L\mathrm{}`$ and $`N\mathrm{}`$, keeping $`\sigma =L/2Nl`$ fixed. The limit $`N\mathrm{}`$ arises as a semiclassical limit, when the Fermi wavelength is much smaller than the diameter of the wire, or by increasing wire diameter. In the latter case, the diameter should not exceed the transverse localization length. Based on our calculation for the diffusive regime, we surmise that in the thick-wire limit the crossover between the standard unitary class and class D is described by a two-parameter scaling function $`\chi ^{}(\sigma ,\alpha )`$, which is obtained from $`\chi `$ by taking the limit $`L,N\mathrm{}`$, at fixed values of the scaling variables $`\sigma `$ and $`\alpha =2Nl/\xi _\mathrm{\Delta }`$.foot3  The second scaling variable $`\alpha `$ is the ratio of the localization length $`4Nl`$ in the standard unitary class and twice the diffusive crossover length scale $`\xi _\mathrm{\Delta }`$ (the proportionality constant is arbitrary as long as it is of order 1). As a function of $`\alpha `$, $`\chi ^{}`$ interpolates between the standard unitary ensemble for $`\alpha =0`$ and the critical conductance statistics of class D if $`\alpha \mathrm{}`$. Note that taking the thick-wire limit at any finite and fixed ratio of $`\xi _\mathrm{\Delta }`$ and $`l`$ (or, alternatively, of $`l_\mathrm{\Delta }`$ and $`l`$) corresponds to the case $`\alpha =\mathrm{}`$, i.e., automatically realizes class D. Thus, in the sense of the scaling limit defined above, the standard unitary fixed point is “unstable,” whereas the class D fixed point is “attractive.” It is only by allowing $`\xi _\mathrm{\Delta }/l`$ to scale at least as fast as $`N`$ that one can probe non-class-D physics in the thick-wire limit.

We verified the above scenario with numerical simulations of $`\chi `$ as a function of $`\sigma `$ for a discretized version of the model (1). The discretized model is obtained from Eq. (1) by the replacement of the continuous potential $`𝒱(x)`$ by the sum $`_j𝒱_j\delta (xaj)`$, where $`a`$ is a microscopic length scale. The delta functions $`\delta (xy)`$ in Eq. (3) are replaced by Kronecker deltas $`a^1\delta _{jj^{}}`$. In Fig. 1, results are shown for different values of $`l_\mathrm{\Delta }/l`$ and for different $`N`$. We took an average over $`>2000`$ realizations of the disorder potential. Our conclusions are confirmed by the numerical data: First, curves for the same value of $`\alpha =2Nl/\xi _\mathrm{\Delta }=4N(2l/l_\mathrm{\Delta })^{1/2}`$ approach a well-defined limit for large $`N`$, confirming that $`\alpha =2Nl/\xi _\mathrm{\Delta }`$ is indeed the true crossover parameter. Second, in the crossover between the two classes, one still observes localized behavior, but with a significantly enhanced localization length, which increases as $`\alpha `$ is increased.

Staggering. Staggering is described by the addition of a term $`v_F\tau _2/2l_s`$ to the Hamiltonian (1). Without the potential term $`𝒱`$ in Eq. (1), the effect of staggering would be to create a gap of size $`v_F/l_s`$ around the Fermi energy $`\epsilon =0`$. The effect of a random potential $`𝒱`$ is to create states inside this gap. Below we address the localization properties of such states at the Fermi level $`\epsilon =0`$ if the random potential $`𝒱`$ is of the form (2) with nonzero superconducting correlations $`\mathrm{\Delta }`$ and without spin-rotational invariance and time-reveral symmetry. Based on a combination of analytical and numerical arguments, we argue that eigenstates at the Fermi level remain critical (as in the absence of staggering), provided that the staggering is sufficiently weak \[see Eq. (10) below\] and the thick-wire limit is taken.

To study the effect of staggering on the $`\epsilon =0`$ eigenstates of the Hamiltonian (1), we first investigate the conductance in the diffusive regime. Following the method of Ref. MBF, , we construct scaling equations for the moments $`R_{n,m}=\text{tr}r^nr^m`$. To leading order in $`N`$, they read

$`_LR_{n,m}`$ $`=`$ $`{\displaystyle \frac{n}{l_s}}(R_{n+1,m}R_{n1,m})+{\displaystyle \frac{m}{l_s}}(R_{n,m+1}R_{n,m1}){\displaystyle \frac{2(n+m)}{l}}R_{n,m}`$ (9)
$`+{\displaystyle \frac{1}{4Nl}}{\displaystyle \underset{p=0}{\overset{n1}{}}}{\displaystyle \underset{q=0}{\overset{m1}{}}}\left[R_{p,q}(R_{n1p,m1q}+R_{np,mq})+R_{np,mq}(R_{p+1,q+1}+R_{p,q})\right]`$
$`{\displaystyle \frac{1}{Nl}}{\displaystyle \underset{p=1}{\overset{n1}{}}}(np)R_{p,0}R_{np,m}{\displaystyle \frac{1}{Nl}}{\displaystyle \underset{q=1}{\overset{m1}{}}}(mq)R_{0,q}R_{n,mq}.`$
Although the scaling equations (9) do not form a closed set, a solution can be constructed as a series expansion in $`l/l_s`$. For sufficiently weak staggering,

$$l_s>l,$$
(10)
and for lengths $`Ll`$, the perturbation series in $`l/l_s`$ truncates after the second order, and one finds the simple solution

$$g=\text{tr}(1R_{1,1})=\frac{2}{\sigma }+𝒪(1),$$
(11)
where $`\sigma `$ is now defined as

$$\sigma =\frac{L}{2Nl[1(l/l_s)^2]}.$$
(12)
Hence, in the thick-wire limit, staggering causes a renormalization of the scaling length $`\sigma `$, but does not remove the existence of a diffusive regime. If staggering exceeds the critical strength (10), there is no diffusive regime in which $`g`$ is inversely proportional to wire length at $`\epsilon =0`$. The existence of a critical staggering strength is consistent with numerical simulations of periodic-on-average single-channel quantum wires by Deych et al.Deych

Based on this result for the diffusive regime, we propose that in the simultaneous limit $`N\mathrm{}`$, $`L\mathrm{}`$ the normalized inverse localization length $`\chi =\mathrm{ln}g/\sigma `$ approaches the same scaling limit $`\chi ^{}(\sigma )`$ as in the absence of staggering, if $`\sigma `$ is given by Eq. (12). In Fig. 2 we show the result of numerical simulations for the discretized version of Eq. (1) with staggering. We have compared the cases $`l_v/l_\mathrm{\Delta }=1`$ or $`0`$, with or without (weak) staggering and find that for sufficiently large $`N`$ all curves $`\chi `$ versus $`\sigma `$ with the same symmetry of the Hamiltonian collapse. That is, curves with $`l_v/l_\mathrm{\Delta }=1`$ (or, in fact, any finite ratio $`l_v/l_\mathrm{\Delta }`$) approach the class D result, while curves with $`l_v/l_\mathrm{\Delta }=0`$ approach the result of the standard unitary class. Small $`N`$ curves are slightly different, which again indicates the absence of universality when a diffusive regime is absent.

In conclusion, our analytical and numerical results confirm the claim of Motrunich et al. that the conductance statistics in the localized regime is not determined by symmetry alone for a superconducting quantum wire with a small number $`N`$ of propagating channels at the Fermi level.Motrunich  Such universality is only achieved for “thick” quantum wires with $`N1`$. Which situation is relevant depends on the physical system at hand. For quasiparticle states at the edges of superconducting planes in high-$`T_c`$ superconductors, the nonuniversal scenario of small $`N`$ may be more applicable, while we expect that the universal scenario of large $`N`$ is more appropriate for dirty unconventional superconducting wires or normal-metal wires in the proximity of a superconductor. Possible relevant perturbations to the critical behavior in the thick-wire limit of the superconducting class D are disorder sufficiently strong to induce transverse localization, restoration of the spin-rotation symmetry, or breaking of the particle-hole symmetry (e.g., by tuning the chemical potential away from the the Fermi level or by electron-electron interactions). All of these perturbations are expected to restore the localized phase at large length scales.

We would like to point out that the universality — or lack thereof — for the localization properties in superconducting quantum wires is not different from the case of normal-metal wires. In both cases, universality is expected in the thick-wire limit only. Or, in the language of scaling flow: In both cases, the fixed point with less symmetry is attractive, but the flow towards the fixed point is only complete if the thick-wire limit is taken. In that respect, note that for the crossover between the standard unitary class and the superconducting class D considered in this paper, the superconducting class is the class of less symmetry. That fact constitutes a qualitative difference between class D and the three chiral classes, which also may exhibit critical conductance statistics for wire length $`LNl`$.BMSA  In contrast to the superconducting class D, the chiral classes have very high symmetry, which makes them rather unstable and which will render observation of the critical conductance statistics in these classes more difficult.

We would like to thank K. Damle and I. A. Gruzberg for discussions. This work was supported in part by the NSF under Grant No. DMR 0086509, by the Sloan and Packard foundations (P.W.B.), and by a Grant-in-Aid for Scientific Research on Priority Areas (A) from the Ministry of Education, Culture, Sports, Science and Technology (No. 12046238) (A.F.). P.W.B. and A.F. thank the Institute for Theoretical Physics in Santa Barbara for its hospitality during the final stages of this work. C.M. thanks the Yukawa Institute for Theoretical Physics in Kyoto for its hospitality during the final stages of this work.


text:
# Study of Normal and Superconducting States of MgCNi3 upon Fe and Co Substitution and External Pressure

## I Introduction

The recent discoveryHe2001  of superconductivity in the intermetallic compound MgCNi3 has initiated a number of studies aimed at elucidating the nature of its normal and superconducting states. Apart from the fact that it is the first known superconducting compound which has a perovskite structure without oxygen, the interest is mainly due to the preference of superconductivity over ferromagnetism which is rather unexpected in a compound whose main ingredient is Ni. By proposing an electronic analogy with the superconducting oxide perovskites, He et. al.He2001  suggested that holes in the Ni d-states might be responsible for electrical conduction in this compound. The signs of the measured Hall constantLi2001a  and thermoelectric power Li2001b  are, however, consistent with normal state transport occurring mainly due to electron-like carriers. Most of the normal state transport properties, like the electrical resistivity $`\rho (T)`$, Hall coefficient $`R_H(T)`$ and thermoelectric power $`S(T)`$, show unusual temperature dependence. They are not amenable to a single unified description encompassing the low and high temperature regimes. For example, the Hall coefficient is almost temperature independent below 140K, but, its magnitude decreasesLi2001a  with increase in temperature above 140K. Even though the conventional Bloch-Gruneisen expression provides a good fit above 70K, a power law seemsLi2001a  to be better for $`\rho (T)`$ below 70K. An electronic crossover occurring at T $``$ 50K was proposedLi2001b  to account for these anomalies. The normal state NMR properties of MgCNi3 are also anomalousSinger2001  and similar to what is seen in the exotic superconductor Sr2RuO4. ObservationMao2001  of a zero bias conductance peak in the tunneling spectrum is argued to be a signature of unconventional pairing (like in the case of Sr2RuO4) in this compound. The NMR measurementSinger2001  below Tc, on the other hand, shows a coherence peak whose magnetic field dependence is consistent with s-wave pairing. The temperature dependence of the electronic specific heat below Tc is consistentLin2002  with the conventional electron-phonon mechanism for superconductivity. AnalysisHe2001  of the specific heat data suggests that this compound is a moderately strong-coupled (electron-phonon coupling constant $`\lambda `$ $``$ 0.77) superconductor. The observedLi2001a  temperature dependence of Hc2 is typical of a conventional superconductor in the dirty limit. Thus a complete understanding of the superconducting and normal states of this compound is yet to emerge.

There have been a number of first principle electronic structure calculations using Tight Binding Linear Muffin Tin Orbital (TB-LMTO)valsa ; Dugdale2001 ; Shim2001 , Full Potential Linear Muffin Tin Orbital (FP-LMTO)Shein2001  and Full Potential Linear Augmented Plane Wave (FP-LAPW)Singh2001 ; Kim2002 ; Rosner2002  methods, within the Local Density Approximation (LDA), to understand the electronic and magnetic properties of MgCNi3 and related compounds. LDA+U calculationsShim2001b  on MgCNi3 with U = 5 eV yields essentially the same band structure as that of the LDA, indicating that electron-correlation effects of Ni-3d electrons are unimportant in this compound. This is consistent with the fact that the measured value of the Wilson ratioWilsonratio  is only 1.15, typical of a system with modest electron-correlation effects. The results of these calculations are quite sensitive to the methods employed and also to the numerical values of the parameters. The general features of the band structure (which, however, are essentially the same in all these calculations) can be briefly summarised as follows: There is a strong hybridisation between the Ni-3d electrons and the C-2p electrons and thus carbon plays the crucial role of the mediator of electron hopping. Two of the bands cross the Fermi level $`E_f`$ and hence both of them contribute to conduction. The density of states at the Fermi level ($`N(E_F)`$) is predominantly due to Ni-3d electrons. One of the distinguishing features of the density of states of this compound is a sharp peak around 50 meV (its location is very sensitive to the method of calculation) below $`E_F`$ arising from the $`\pi `$ anti-bonding states of Ni-3d and C-2p states. The Stoner enhancementStoner  is moderately strong to cause ferromagnetic spin fluctuations, but, not strong enough to obtain a ferromagnetic ground state.

It is well known that the perovskite structure is conducive to a variety of interesting physical phenomena like superconductivity, magnetism, colossal magnetoresistance, etc. Soon after the announcementHe2001  of the discovery of superconductivity in MgCNi3, TB-LMTO calculations were performed valsa  to obtain guidelines for synthesis of related compounds with interesting physical properties. The results of the calculations for the pristine MgCNi3 are consistent with the reports now available in the literatureDugdale2001 ; Shim2001 ; Shein2001 ; Singh2001 ; Kim2002 ; Rosner2002 . Our calculations showed that MgCMn3, MgCFe3 and MgCCo3 may form, but they would be magnetic. Replacement of Mg with other alkaline-earth elements Ca, Sr and Ba would be interesting. For example, CaCNi3, CaCFe3 and SrCCo3 would be magnetic, whereas SrCNi3, BaCNi3 and CaCCo3 would be nonmagnetic. As mentioned earlier, band structure calculations showed that the Fermi level in MgCNi3 lies towards the right side of a peak in the Density of States (DOS) $`N(E)`$. Removal of half an electron per formula unit would shift the Fermi level to the peak in the DOS. Within the rigid band approximation (RBA), this can be achieved by substitution of Ni3 by Ni5/2Co1/2 or Ni11/4Fe1/4. Our spin-polarised supercell calculations for MgCNi3-xMx showed an increase (but much less than the RBA estimate) in $`N(E_F)`$, and more importantly, absence of a magnetic moment, for x=1/4 and 1/2 (M = Co) and x=1/4 (M = Fe). Hence an increase in Tc is expected until x=1/2 for M = Co and x=1/4 for M = Fe. Furthermore, our calculations suggest a structural instability when the lattice parameter is changed either way. In particular, a lattice instability is conspicuous (in the calculation) at a modest estimated pressure of $``$ 2 GPa. Hence effect of application of pressure in this system would also be interesting. In what follows, we present the results of our analysisgeethadae ; awadheshdae  of the normal state resistance, the variation in superconducting properties upon Fe and Co substitution, and the effect of pressure on the superconducting transition temperature and normal state resistance of MgCNi3.

## II Sample Preparation and characterization

In addition to the pure MgCNi3, a series of compounds MgCNi3-xMx ( x = 0.05, 0.15 and 0.30 for M = Fe; x=0.05, 0.10, 0.20 and 0.40 for M=Co) were prepared in order to investigate the effect of hole doping. The samples were prepared by following the solid state reaction route described by He et. al.He2001 . Starting materials used were Mg(99.8%), Ni(99.99%), Fe(99.999%), Co(99.99%) and amorphous carbon(99%), all in the form of powder. 20% excess of Mg is taken in the starting mixture in order to compensate for the loss of Mg due to evaporation. Also an excess of 50% C is taken to obtain the optimum carbon stoichiometryHe2001  in the compound. The raw materials were mixed thoroughly and were pressed into pellets. The pellets were subjected to the heating schedule described by He et. al.He2001 , in an atmosphere of 92% Ar and 8% H2.

The crystal structure of all the samples are characterized by x-ray diffraction. Ac susceptibility and four-probe dc resistance have been measured in the range 4.2K -300K using home-made dip-sticks. The high pressure resistance measurement has been carried out for the pristine MgCNi3 using a pressure locked opposed Brigman anvils apparatusawadesh  using the four-probe method. A superconducting Pb manometer is used for pressure calibration. We have also characterized the microstructure of MgCNi3 with SEM.

## III Results and Discussion

The x-ray patterns of the undoped and doped samples are consistent with a perovskite structure with the space group Pm$`\overline{3}`$m. Small amounts of unreacted Ni (2-5%) and MgO impurity ($`<`$2%) were present in some of the samples. Except for these blemishes, all the samples are of good quality, with sharp x-ray diffraction peaks. The XRD pattern for MgCNi3 is shown in Fig. 1 as an example. The lattice parameter for the un-substituted MgCNi3 was found to be 3.810 ($`\pm `$ 0.0004)$`\AA `$ which is in agreement with the values reported in the literature. No significant change in lattice parameter was noticed upon partial substitution of Ni with Fe or Co. This observation is consistent with the very small variation of the lattice parameter, a(x=0) = 3.806 $`\AA `$, a(x=3) = 3.802 $`\AA `$, seen in the study of MgCNi3-xCox by Ren et. al.Ren2001 .

The variation of resistance R with temperature T of the pristine MgCNi3 is shown in Fig. 2. It can be seen that the shape of the R(T) curve presented here is very similar those reported by He et. al.He2001  and Li et. al.Li2001a . The residual resistivity ratio of this sample ($`R(300K)/R(10K)`$) is 2.2 similar to that obtained by He et. al.He2001 . However, the magnitude of the resistivity obtained in this study is approximately 30 times more than that of He et. al.He2001  and 10 times that of Li et. alLi2001a . This discrepancy can be understood in terms of the possible differences in the microstructure that can be expected from the fact that unlike in the study of He et. al.He2001 , our samples were not subjected to high pressure sintering. Fig. 3 shows an SEM pattern of one of the MgCNi3 samples. The fractal character of the sample, which is quite evident from this photograph, entails a much longer and corrugated path (as compared to the bulk) for the electrons. This makes the usual procedure of multiplying the resistance by the (external) Area/Length of the sample to get the resistivity $`\rho `$ erroneousbadmetal . Since the actual path length of the electrons in such a poorly connected medium is longer than that in the bulk, the apparent resistance will be larger than what is expected from a scaling based merely on the external geometrybadmetal . Hence there is a need for a geometric renormalisation while converting resistance into resistivity in sintered samples. Our sample is more loosely packed (compared to that of He et. al.He2001 ) and hence the larger apparent resistivity of our sample. A superconducting transition with an onset (mid) Tc of 8.13 K (7.69 K) is observed (90-10% of the transition width $`\mathrm{\Delta }`$Tc = 0.34K). The ac susceptibility measurement (7) shows a lower Tc (onset Tc = 7.35 K) consistent with the values reported in literature He2001 .

### III.1 Analysis of Normal state Resistance

Assuming compliance with Matheissen’s rule, we have tried to fit the normal state resistance of MgCNi3 with the expression for a conventional metal,

$$R(T)=A+BT^2+C\left(\frac{T}{\mathrm{\Theta }}\right)^5_0^{\left(\frac{\mathrm{\Theta }}{T}\right)}𝑑x\frac{x^5}{\left[(e^x1)(1e^x)\right]}$$
(1)
In Eq. 1, the constant $`A`$ represents the contribution to resistance from electron-impurity scattering, T2 term accounts for the contribution to resistance from electron-electron scattering and also from spin fluctuations, and last term is the Bloch-Gruneisen integral which represents the electron-phonon scattering. The coefficient $`B`$ obtained using the fit turns out to be negative and also the fitted value of the Debye temperature ( $`\mathrm{\Theta }`$ $``$ 110K) is too low. If we substitute this value of $`\mathrm{\Theta }`$ and the reported value of the electron phonon coupling constant ($`\lambda `$ = 0.77) in the McMillan’s formula for Tc given by

$$T_c=\left(\frac{\mathrm{\Theta }_D}{1.45}\right)\mathrm{exp}\left(\frac{1.04(1+\lambda )}{\lambda \mu ^{}(1+0.62\lambda )}\right),$$
(2)
we get the superconducting transition temperature Tc $``$ 4 K, much less than the experimental value (we have taken $`\mu ^{}`$ to be 0.1).

This and the reported Li2001a  temperature variation of the Hall constant are consistent with a two band model of conduction involving $`\mathrm{`}`$light’ electrons coupled to low frequency phonons and $`\mathrm{`}`$heavy’ holes coupled to high frequency phononsvalsa . As mentioned in the Introduction, band structure calculations show that two bands cross the Fermi level (see Fig. 4) one almost full and the other nearly empty. There are equal number of electron-like and hole-like charge carriersnumberexplanation  in this compound and the effective mass of the hole-like carrier is almost ten times that of the electron-like carrier. Therefore the normal state electrical conduction will be mainly due to electrons and hence we can expect the Hall constant to be negative. However, both the electrons and holes will be contributing to the conductivity $`\sigma (T)`$ and hence it will be the sum of the conductivities $`\sigma _e(T)`$ and $`\sigma _h(T)`$ due to the electrons and holes, respectively. Therefore the effective resistivity $`\rho (T)`$ can be written as

$$\rho (T)=A_0+\frac{\rho _e(T)\rho _h(T)}{\rho _e(T)+\rho _h(T))}$$
(3)
where $`\rho _e(T)`$ = $`1/\sigma _e(T)`$ and $`\rho _h(T)`$ = $`1/\sigma _h(T)`$ , and $`A_0`$ is a constant added to take care of the effect of defects in the sample. In Eq.3 $`\rho _e(T)`$ and $`\rho _h(T)`$ have separate temperature dependences,

$$\rho _{e,h}=A_{e,h}+B_{e,h}T^2+C\left(\frac{T}{\mathrm{\Theta }_{e,h}}\right)^5_0^{\left(\frac{\mathrm{\Theta }_{e,h}}{T}\right)}𝑑x\frac{x^5}{\left[(e^x1)(1e^x)\right]}$$
(4)
With $`B_e`$ and $`B_h`$ both positive, it is possible to obtain an effective resistivity such that a fit with Eq. 1 would give a negative $`B`$.

The continuous line in Fig. 2 is a fitfitexplanation  of the normal state resistance, R(T) using the two band model for conduction given by Eq. 3. It can be seen from the figure that the fit is very good (better than 0.15%). $`\mathrm{\Theta }_e`$ obtained from the fit is seen to be smaller than $`\mathrm{\Theta }_h`$. That is, the electron-like carriers are coupled to low frequency phonons as compared to hole-like carriers which are coupled to higher frequency phonons. Assuming the value of the hole-phonon coupling constant $`\lambda `$ to be the same as that obtained from the specific heat measurementHe2001 , we get a Tc comparable to the experimental value. Thus we can infer that superconductivity in MgCNi3 is due to hole-like carriers. Since $`\rho _e(T)`$ is much less than $`\rho _h(T)`$, the effective resistivity $`\rho (T)`$ will be close to $`\rho _e(T)`$ and hence the value of $`\mathrm{\Theta }`$ that one gets with a fit of $`\rho (T)`$ to Eq. 1 will be close to $`\mathrm{\Theta }_e`$.

The reported variation of the Hall constant $`R_H(T)`$ can also be qualitatively explained in the two band model. The Hall constant $`R_H(T)`$ is the weighted sum of the Hall constants $`R_{He}`$ and $`R_{Hh}`$ due to the electrons and holes, respectively, and it is given by,

$$R_H=\frac{\left(R_{He}\sigma _e^2+R_{Hh}\sigma _h^2\right)}{\left(\sigma _e+\sigma _h\right)^2}=R_{He}\frac{\left[1\left(\frac{\rho _e}{\rho _h}\right)\right]}{\left[1+\left(\frac{\rho _e}{\rho _h}\right)\right]},$$
(5)
Since the number of electrons is equal to the number of holes $`R_{Hh}`$ = -$`R_{He}`$ and hence $`R_H`$ $`<`$ 0. If $`\frac{d}{dT}\left(\frac{\rho _e}{\rho _h}\right)`$ $`>`$ 0, then the magnitude of $`R_H`$ also will decrease with temperature thus explaining the reported Hall effect behaviour. We thus see that a consistent interpretation of the temperature dependence of both the normal state resistivity and the Hall constant can be achieved by invoking a two band model of conduction. It remains to be seen whether the same physical picture can provide a satisfactory interpretation of the anomalies seen in the thermopower and NMR relaxation rate.

We have also tried to study the effect of the proximity of the peak in the density of states (van Hove singularity) close to the Fermi level on the resistivity. It is seenvalsa  that the chemical potential increases with temperature. As a result of this, some of the electrons from the almost filled band go to the almost empty band ($`n_b(T)`$ increases at the expense of $`n_a(T)`$numberexplanation ). Thus the numbers of both the electron-like and hole-like carriers increase with temperature. As can be seen from Fig. 5, carrier concentration increases by approximately 4% when the temperature is raised from 0K to 300K. This is one of reasons why the resistivity is not linear in temperature even in the high temperature regime.

### III.2 Effect of Fe and Co substitution

Figs. 6 and 7 represent the superconducting transitions traced by the resistance and susceptibility measurements respectively for the Co substituted compounds. The transition temperature decreases monotonically with increase in Co concentration, similar to the results now available in literature Ren2001 ; Hayward2001 . The variation of the mid point Tcwith respect to x, the Co concentration, is shown as an inset of Fig. 6. The decease in the diamagnetic signal (and hence the superconducting volume fraction) can also be seen in Fig. 7, which again is consistent with the results reported in the literatureHayward2001 . Fe substitution, on the other hand, leads to an increase Tc followed by a decrease. The superconducting transitions traced for the Fe substituted compounds are shown in Figs. 8 and 9. The maximum Tc is obtained when the Fe concentration is 0.05. The onset of the superconducting transition occurs at 9K for this sample in our resistivity scan. Increasing Fe concentration beyond 0.05 is found to suppress Tc. The inset of Fig. 8 represents the mid point Tc as a function of Fe concentration.

An increase in Tc was expected for Fe substitution till x=0.25 and for Co substitution till x=0.5, on the basis of a simple minded interpretation of the results of the band structure calculations. However, we observed a monotonic decrease in Tc for Co substitution and an increase followed by a decrease for Fe substitution. These results are clearly at variance with what is expected from the band structure calculations. The observed variation in Tc can be explained in terms of an increase in Tc due to increase in the density of states and a decrease due to spin fluctuations: As mentioned in the Introduction, NMR measurementsSinger2001  have shown existence of ferromagnetic spin fluctuations in MgCNi3. Also, magnetic susceptibility measurements have demonstrated that Co doping enhances spin fluctuations in MgCNi3Hayward2001 . If we assume the pairing in MgCNi3 is of the s-wave type, then it will be suppressed by coupling of electrons (more precisely, the holes) with spin fluctuations. Since we get an increase in Tc for small concentrations of Fe, we believe that the spin fluctuation effect will be relatively less for Fe substituted compounds as compared to that of Co substituted ones. This is to be verified experimentally.

### III.3 Effect of Pressure

Figure 10 shows the variation of the total energy as a function of $`V/V_0`$ ($`V_0`$ is the equilibrium volume) obtained from our band structure calculationsvalsa . The clear change in slope at $`V/V_0`$ $``$ 0.985 is suggestive of a possible lattice instability. The calculated (using TB-LMTO) bulk moduli of MgCNi3 and fcc Ni are 210 and 250 GPa, respectively. The measured bulk modulus of fcc Ni, on the other hand, is 180 GPa. Thus the LDA calculation over estimates the bulk modulus. We correct for this discrepancy by scaling the calculated bulk modulus by a factor 180/250 (the ratio of the measured and calculated bulk moduli of fcc Ni) and thus estimate the bulk modulus of MgCNi3 to be 151 GPa. With this value of the bulk modulus, we expect the lattice instability to occur at a pressure $``$ 2GPa. It is known that there is no structural or magnetic phase transitions in MgCNi3 as the temperature is varied, at ambient pressureHuang2001 . But, there is no investigation of the structure of MgCNi3 at high pressure. It would be of interest to do high pressure x-ray diffraction on MgCNi3 to see if the predicted lattice instability indeed occurs or not. Here we report the results of resistivity measurement up to a pressure $``$ 7 GPa.

The superconducting transitions and the temperature dependence of resistivity of MgCNi3 traced for different external pressures are shown in Fig. 11. Tc is found to decrease with increasing pressure up to $``$ 1.7 GPa and it increases beyond this pressure. Fig. 12 (a) depicts the variation of the onset Tc with respect to the applied pressure. The normal state resistance also shows a similar trend as can be inferred from Fig. 12 (b) where the variation of the resistance at 10 K is plotted as a function of the applied pressure. Thus the variation of Tc with pressure is consistent with the behaviour expected of a superconductor with the conventional electron(hole)-phonon mechanism- larger the normal state resistivity, higher the Tc. Band structure calculations show a monotonic decrease in $`N(E_F)`$ with pressure. This would imply a monotonic decrease in the electron-phonon coupling constant $`\lambda `$, if there is no phonon softening. Fit of the resistance to Eq.1 showed an increase in $`\mathrm{\Theta }`$ with pressure upto 2GPa and a decrease there-after. This implies a lattice softening commencing at 2GPa. If we assume the usual scaling ($`\lambda `$ $``$ $`N(E_F)/\mathrm{\Theta }^2`$) of the electron(hole)-phonon coupling constant with the density of states and the Debye temperature $`\mathrm{\Theta }`$, and calculate Tc using McMillan’s formula, we find a variation of Tc with pressure that qualitatively matches with the experimental observation. It is not yet clear whether the decrease in $`\theta `$ with pressure beyond 2GPa is due to a softening of a particular phonon mode or due to a structural phase transition. Another mechanism that contributes to the increase in Tc would be the suppression of spin fluctuations by pressure, thereby enhancing pairing.

Before concluding, we would like to touch upon the role of carbon, in relation to superconductivity, in this compound. It is knownAmos2002  that this compound can form with variable C stoichiometry. However, superconductivity is absentHe2001 ; Amos2002  when the C content is less than $``$ 0.9. We have performed band structure calculation (using TB-LMTO) of MgC0.875Ni3 by constructing an appropriate supercellvalsa . The density of states at the Fermi level thus calculated is almost the same as that of MgCNi3. Furthermore, MgC0.875Ni3 is non-magnetic as per this spin-polarised calculation. Thus the absence of superconductivity in MgCNi3 below a C concentration $``$ 0.9 is also surprising. We have, however, found a factor of two reduction in the height of the peak in DOS close to the Fermi level. This would support the proposalRosner2002  of a possible connection between the van Hove singularity and superconductivity in MgCNi3.

## IV Conclusions

To conclude, we have synthesised MgCNi3 and analyzed its superconducting and normal state properties. We have also studied the effect of hole doping at the Ni site and the effect of application of pressure on MgCNi3. It is found that a two band model for conduction provides a framework for consistently explaining the observed temperature dependence of the normal state resistance and the Hall constant. Co substitution quenches superconductivity, whereas Fe substitution causes an increase in Tc followed by a decrease. This may be understood in terms of a competition between increase in Tc due to increase in the density of states at the Fermi level and a decrease due to spin fluctuations. We speculate that spin fluctuations in Fe substituted samples are weaker than in the Co substituted samples. In fact, it is knownHayward2001  that there is an enhancement of spin fluctuations by Co substitution in MgCNi3. The observed nonmonotonic variation of Tc with pressure may also be pointing out the importance of spin fluctuations vis-a-vis superconductivity in MgCNi3. The decrease in Tc for small applied pressures can be understood in terms of the decrease in the density of states at the Fermi level. The subsequent increase in Tc with pressure is suggestive of a lattice softening or a structural phase transition, consistent with the total energy calculations. More experimental and theoretical efforts are needed to understand these issues better.

###### Acknowledgements.

The authors acknowledge Mrs. M. Radhika, Materials Development Division, IGCAR for providing the SEM micrographs of the MgCNi3 samples.