# Suppression of superconductivity in high-𝑇_𝑐 cuprates due to nonmagnetic impurities: Implications for the order parameter symmetry

\[

## Abstract

We studied the effects of nonmagnetic impurities on high-temperature superconductors by solving the Bogoliubov-de Gennes equations on a two-dimensional lattice via exact diagonalization technique in a fully self-consistent way. We found that $`s`$-wave order parameter is almost unaffected by impurities at low concentrations while $`d_{x^2y^2}`$-wave order parameter exhibits a strong linear decrease with impurity concentration. We evaluated the critical impurity concentration $`n_i^c`$ at which superconductivity ceases to be 0.1 which is in good agreement with experimental values. We also investigated how the orthorhombic nature of the crystal structure affects the suppression of superconductivity and found that anisotropy induces an additional $`s`$-wave component. Our results support $`d_{x^2y^2}`$-wave symmetry for tetragonal and $`s+d_{x^2y^2}`$-wave symmetry for orthorhombic structure.

\]

Symmetry of the order parameter (OP) in high-$`T_c`$ cuprates is important both for understanding the mechanism of superconductivity and also for technological applications. For example, $`d`$-wave symmetric OP effectively refutes phonon mechanism and for a device made of a $`d`$-wave superconductor having no gap in energy spectrum, no refinement would get rid of the dissipation at low frequencies, even at low temperatures. 3d metal (Zn, Ni, Al, Ga, Fe, …) atom substitution for Cu atoms in high-$`T_c`$ cuprates may identify symmetry of the OP . It is a well known fact that for conventional superconductors having isotropic order parameter, nonmagnetic impurities with small concentrations have no effect on critical temperature while magnetic impurities act as strong pair breakers, and as a result of this superconductivity is suppressed very rapidly . On the other hand, nonmagnetic impurities are very effective in anisotropic superconductors. For a pure superconductor, anisotropy leads to increase in $`T_c`$  and the critical temperature suppression rate with increasing impurity concentration is proportional to the strength of anisotropy. Unlike the conventional superconductors, in hole-doped  high-$`T_c`$ cuprates both magnetic (Ni) and nonmagnetic (Zn) impurities suppress $`T_c`$ very effectively.

Dependence of the superconducting properties (critical temperature, order parameter, density of states, …) on impurity or point defect concentration is a subject of ongoing research. So far, most of the experiments have been performed to investigate effects of Zn and Ni substitution in YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7-δ</sub> compounds. Alternatively, disorder can also be introduced by creating defects with ion irradiation , but in this case affected region is often uncontrollable.

In spite of the complexity of the high-$`T_c`$ cuprates (boundaries, defects, …), insufficient control of the actual impurity or point defect concentration, solubility, and homogeneity of the distribution of the dopants which may lead to contradictory data, we can summarize some of the experimental results as follows:

* For YBa<sub>2</sub>(Cu<sub>1-x</sub>Zn<sub>x</sub>)<sub>3</sub>O<sub>7-δ</sub> compounds, at small concentrations, $`x<0.04`$, Zn ions occupy preferably Cu-sites in the CuO<sub>2</sub> planes, however for $`x>0.04`$ the substituent starts to occupy Cu-sites in the chain . Since this compound has two planes and one chain in a unit cell, for $`x<0.04`$ the actual (effective) impurity concentration $`n_i`$, i. e. the number of impurities per unit cell per CuO<sub>2</sub> plane, becomes $`3x/2`$.
* The critical temperature decreases linearly with increasing impurity concentration in substitution  (for $`x>0.04`$ the drop rate decreases due to partial occupancy of Zn at chain sites) and point defect concentration irradiation experiments.
* Due to orthorhombicity of YBCO material, CuO<sub>2</sub> planes exhibit an anisotropic behavior and admixture of $`d`$\- and $`s`$-wave is possible.
* Zn substitution does not alter the carrier concentration in CuO<sub>2</sub> planes .

On the theoretical side, the existing pair-breaking models overestimate the suppression of critical temperature and predict an increasing slope with increasing impurity concentration which contradicts the observed linear dependence of $`T_c`$ on $`n_i`$. The effects of neither magnetic (Ni) nor nonmagnetic (Zn) impurities on the superconducting properties of the cuprates have been explained clearly. Main reason for the discrepancy between theory and experiments is that the conventional Abrikosov-Gor’kov (AG) -type pair-breaking models ignore position dependence of the order parameter near impurity sites. Recently, Franz and his coworkers , and Zhitomirsky and Walker  argued that spatial variation of the order parameter must be taken into account for short coherence length superconductors.

In the present paper, we investigate effects of nonmagnetic impurities on high-$`T_c`$ cuprates for both tetragonal and orthorhombic phases by solving the Bogoliubov-de Gennes (BdG) equations  in a fully self-consistent way. In particular, we address possibility of extracting OP symmetry by examining effects of nonmagnetic impurities. Our results support $`d_{x^2y^2}`$-wave pairing symmetry for tetragonal and $`s+d_{x^2y^2}`$-wave for orthorhombic structure. Possibility of admixture of $`s`$\- and $`d`$-wave symmetries have already been proposed in various experimental and theoretical works.

The BdG equations on two-dimensional lattice have the following form

$$\underset{j}{}\left(\begin{array}{cc}H_{ij}& \mathrm{\Delta }_{ij}\\ \mathrm{\Delta }_{ij}^{}& H_{ij}^{}\end{array}\right)\left(\begin{array}{c}u_n(j)\\ v_n(j)\end{array}\right)=E_n\left(\begin{array}{c}u_n(i)\\ v_n(i)\end{array}\right),$$
(1)   
where $`u_n(i)`$ and $`v_n(i)`$ are quasiparticle amplitudes at site $`i`$ with eigenvalue $`E_n`$, and $`\mathrm{\Delta }_{ij}`$ is the pairing potential. The normal-state part of the Hamiltonian can be written as

$`H_{ij}`$ $`=`$ $`(t_{ij}+U_{ij}n_{ij}/2)(1\delta _{ij})`$ (3)   
$`+(V_i^{\mathrm{imp}}\mu +U_{ii}n_{ii}/2)\delta _{ij},`$   
where $`t_{ij}`$ is the hopping amplitude, $`\mu `$ is the chemical potential, $`U_{ij}n_{ij}/2`$ and $`U_{ii}n_{ii}/2`$ are the Hartree-Fock potentials with on-site interaction $`U_{ii}`$ and off-site interaction $`U_{ij}`$, respectively. Finally $`V_i^{\mathrm{imp}}`$ is the impurity potential. The pairing potentials are defined by

$$\mathrm{\Delta }_{ij}=U_{ij}F_{ij}.$$
(4)   
The charge density $`n_{ij}`$ in the Hartree-Fock potentials and the anomalous density $`F_{ij}`$ in the pairing potential are determined from

$$n_{ij}=\underset{\sigma }{}\mathrm{\Psi }_\sigma ^{}(i)\mathrm{\Psi }_\sigma (j),$$
(5)   
$$F_{ij}=\mathrm{\Psi }_{}(i)\mathrm{\Psi }_{}(j),$$
(6)   
where $`\sigma `$ is spin index, and $`\mathrm{\Psi }_\sigma ^{}(i)`$ and $`\mathrm{\Psi }_\sigma (i)`$ are related to the quasiparticle creation ($`\gamma _{n\sigma }^{}`$) and annihilation ($`\gamma _{n\sigma }`$) operators

$$\left[\begin{array}{c}\mathrm{\Psi }_{}(i)\\ \mathrm{\Psi }_{}^{}(i)\end{array}\right]=\underset{n}{}\left[\gamma _n\left(\begin{array}{c}u_n(i)\\ v_n(i)\end{array}\right)+\gamma _n\left(\begin{array}{c}v_n^{}(i)\\ u_n^{}(i)\end{array}\right)\right],$$
(7)   
where $`\gamma `$ and $`\gamma ^{}`$ satisfy the Fermi commutation relations. The self-consistency conditions can be written in terms of $`u_n`$, $`v_n`$, and $`E_n`$

$`n_{ij}=2{\displaystyle \underset{n}{}}u_n^{}(i)v_n(j)f(E_n)`$ (8)   
$`+v_n(i)v_n^{}(j)[1f(E_n)],`$ (9)   
$`F_{ij}={\displaystyle \underset{n}{}}u_n(i)v_n^{}(j)[1f(E_n)]`$ (10)   
$`v_n^{}(i)u_n(j)f(E_n),`$ (11)   
where $`f(E_n)=1/[\mathrm{exp}(E_n/k_BT)1]`$ is the Fermi distribution function.

We solve the BdG equations on a 20x20 square lattice (hence, we diagonalize a 1600x1600 matrix) with periodic boundary conditions by exact diagonalization technique using IMSL subroutines. After choosing a suitable initial guess for OP, we solve Eq. (1). Next, we calculate the new charge density $`n_{ij}`$ and anomalous density $`F_{ij}`$ via Eqs. (9) and (11) and iterate this procedure until a reasonable convergence is achieved. The BdG equations are solved self-consistently. Self-consistency conditions \[Eqs. (9) and (11)\] lead to 10 separate equations. The first five \[obtained from Eq. (9)\] renormalize on-site energies and hopping matrix elements while the last five \[obtained from Eq. (11)\] affect the on-site and nearest-neighbor interaction terms. Although, the first five of these self-consistency conditions can be neglected for conventional superconductors where $`U/t1`$, for strong interaction case we should keep them, since they play important role especially in the presence of impurities. The impurity potential $`V_i^{\mathrm{imp}}`$ is treated in the unitary limit, i.e. $`V_i^{\mathrm{imp}}t`$, and taken nonzero for randomly chosen lattice sites.

We first solve the BdG equations for tetragonal case $`t_x=t_y=t`$ where $`t_x`$ and $`t_y`$ are nearest-neighbor hopping amplitudes along $`x`$ and $`y`$ directions, respectively. For $`s`$-wave OP symmetry we assume that on-site (attractive) interaction is $`U_{ii}=1.7t`$ and there is no nearest-neighbor interaction. In the case of $`d`$-wave OP symmetry on-site (repulsive) interaction is $`U_{ii}=1.4t`$ and nearest-neighbor (attractive) interaction is $`U_{ij}=1.4t`$. With this choice of parameters we fix chemical potential $`\mu `$ so that band filling factor $`n0.8`$ and zero temperature coherence length $`\xi _04a`$. These values are in good agreement with the commonly accepted experimental values.

Figure 1 shows that, at low impurity concentrations $`s`$-wave OP symmetry is almost unaffected by the impurities or point defects. Although we use several on-site interaction values by keeping the band filling factor and zero temperature coherence length constant, we don’t get any qualitative change. This result is consistent with Anderson theorem and AG theory. However, experimental data for high-$`T_c`$ cuprates exhibit a much stronger suppression of superconductivity with increasing disorder.

On the other hand, our $`d`$-wave calculations give results similar to the behavior observed in experiments. For $`d`$-wave symmetry we find that on-site pairing potential is negligibly small. In Fig. 1, $`\mathrm{\Delta }_d`$ is amplitude of the nearest-neighbor pairing potential. We obtain a linear decrease in the mean OP, which is assumed to be proportional to the critical temperature $`T_c`$ , and the slope of the straight line is in good agreement with the experimental data summarized in Table I. The critical impurity or point defect concentration $`n_i^c`$ at which superconductivity ceases is also near to experimental value $`0.1`$. In comparing our results with experimental data we should keep the following point in our mind. For $`x<0.04`$, substitutional impurities go to preferentially CuO<sub>2</sub> planes and hence the actual concentration is $`3x/2`$. However for higher concentrations some of the Zn atoms occupy the chain sites, and in this case we can not relate the in plane concentration to the actual one. Therefore, we used the initial points, i. e. $`x<0.04`$, to evaluate the initial drop in Table I. To obtain the experimental value for critical impurity concentration $`n_i^c`$, we extrapolated the linear parts of the experimental curves to intersect the impurity concentration axes.

Similar equations have already been solved by Xiang and Wheatley, however our additional self-consistency conditions and choice of parameters lead to a correct prediction for the critical impurity concentration. It is important to note that we can not have a self-consistent solution of the OP for extended $`s`$-wave by using any physical values for the above model parameters. This fact was pointed out by Wang and MacDonald, and they found that extended $`s`$-wave component is smaller than $`d`$-wave component by about two orders of magnitude.

When we introduce an orthorhombic distortion by taking $`t_y=1.5t_x`$, as suggested by experimental data, we observe that an $`s`$-wave component (of approximately ten percent of $`d`$-wave components) is induced. Figures 2 and 3 show the variation of $`\mathrm{\Delta }_{dx}`$ and $`\mathrm{\Delta }_{dy}`$ components, respectively. In the absence of disorder, $`\mathrm{\Delta }_{dy}/\mathrm{\Delta }_{dx}1.5`$ with $`\mathrm{\Delta }_{dx}=0.082t`$. With increasing disorder, the larger one, i.e. $`\mathrm{\Delta }_{dy}`$, is suppressed faster. When we reach the critical impurity concentration both components vanish simultaneously. Moreover, $`d`$-wave components of the OP decrease linearly with $`n_i`$ and vanish at $`n_i0.1`$ as in the case of pure $`d`$-wave symmetry. Here $`\mathrm{}`$ denotes averaging over 20 different impurity configurations.

As can be seen from Fig.4, $`s`$-wave component also decreases with $`n_i`$, however while $`d`$-wave components exhibit a linear dependence on impurity concentration s-wave component shows a downward curvature similar to prediction of the AG theory.

In conclusion, we investigated the effects of nonmagnetic impurities and point defects within a BCS mean-field framework by means of BdG equations. For tetragonal structure, we found out that the observed suppression of superconductivity, when impurities are substituted or point defects are introduced, can be explained only if the OP is $`d_{x^2y^2}`$-wave symmetric. In case of $`s`$-wave symmetry, superconductivity is almost unaffected by disorder. When a slight anisotropy is introduced by distorting copper oxide planes from a square to rectangular lattice we observed that a small amount of $`s`$-wave contribution is induced. For both tetragonal and orthorhombic structures we evaluate the critical concentration at which superconductivity ceases to be very near to experimental value $`0.1`$.

Acknowledgments:

This work was supported by the Scientific and Technical Research Council of Turkey (TUBITAK) under grant No. TBAG 1736.