# Influence of 𝐶⁢𝑢 on spin-polaron tunneling in the ferromagnetic state of 𝐿⁢𝑎_{2/3}⁢𝐶⁢𝑎_{1/3}⁢𝑀⁢𝑛_{1-𝑥}⁢𝐶⁢𝑢_𝑥⁢𝑂₃ from the resistivity data

## Abstract

Nearly a $`50\%`$ decrease of resistivity $`\rho (T,x)`$ (accompanied by a $`5\%`$ reduction of the peak temperature $`T_C(x)`$) due to just $`4\%`$ $`Cu`$ doping on the $`Mn`$ site of $`La_{2/3}Ca_{1/3}Mn_{1x}Cu_xO_3`$ is observed. Attributing the observed phenomenon to the substitution induced decrease of the polaron energy $`E_\sigma (x)`$ below $`T_C(x)`$, all data are found to be well fitted by the nonthermal coherent tunneling expression $`\rho (T,x)=\rho _0e^{\gamma M^2(T,x)}`$ assuming $`M(T,x)=M_R(x)+M_0(x)\mathrm{tanh}\left\{\sqrt{\left[T_C(x)/T\right]^21}\right\}`$ for the magnetization in the ferromagnetic state. The best fits through all the data points yield $`M_0(x)\sqrt{1x}M_0(0)`$, $`M_R(x)\sqrt{x}M_0(0)`$, and $`E_\sigma (x)E_\sigma (0)(1x)^4`$ for the $`Cu`$ induced modifications of the $`Mn`$ spins dominated zero-temperature spontaneous magnetization, the residual paramagnetic contribution, and spin-polaron tunneling energy, respectively, with $`E_\sigma (0)=0.12eV`$ and $`2R10\AA `$ for the spin-polaron’s size.

As is well known,  the ground state of the highly magnetoresistive conductor $`La_{2/3}Ca_{1/3}MnO_3`$ is ferromagnetic (FM) and the paramagnetic-ferromagnetic transition is accompanied by a sharp drop in resistivity below $`T_C`$. Such a correlation is considered as a basic element for the so-called magnetically induced electron localization scenario  in which the changes of observable resistivity at low temperatures are related to the corresponding changes of the local magnetization, and a coherent nonthermal tunneling charge carrier transport mechanism dominates other diffusion processes.

The effects of elemental substitution on the properties of $`La_{2/3}Ca_{1/3}MnO_3`$ have been widely studied in an attempt to further shed some light on the underlying transport mechanisms in this interesting material.  In particular, substitution of the rare-earth atoms (like $`Y`$ or $`Gd`$) on the $`La`$ site leads to the lowering of the ferromagnetic (and ”metal-insulator”) transition temperature $`T_C`$ due mostly to the cation size mismatch.  At the same time, the reduction of $`T_C`$ and a rather substantial drop of resistivity in the FM region due to $`Mn`$ ions replacement with metals (like $`Co`$ or $`Ni`$) are ascribed to a weakening of the Zener double-exchange interaction between two unlike ions.  In other words, similar to the effects of an applied magnetic field,  metal-ion doping was found  to decrease the polaron tunneling energy barrier (thus increasing the correlation length).

In this paper we present a comparative study of resistivity measurements on two manganite samples from the $`La_{2/3}Ca_{1/3}Mn_{1x}Cu_xO_3`$ family for $`x=0`$ and $`x=0.04`$ and for a wide temperature interval (from $`20K`$ to $`300K`$). As we shall see, this very small amount of impurity leads to a marked (factor of two) drop in resistivity value, hardly understandable along the conventional scattering theories. The data are in fact well fitted by a nonthermal spin tunneling expression for the resistivity assuming a magnetization $`M(T,x)`$ dependent charge carrier correlation length $`L(M)`$.

The samples examined in this study were prepared by the standard solid-state reaction from stoichiometric amounts of $`La_2O_3`$, $`CaCO_3`$, $`MnO_2`$, and $`CuO`$ powders. The necessary heat treatment was performed in air, in alumina crucibles at $`1300^{}C`$ for 2 days to preserve the right phase stoichiometry. Powder X-ray diffraction patterns are characteristic of perovskites. No appreciable changes in the diffraction patterns induced by $`Cu`$ doping have been observed (suggesting thus that no structural changes have occured after replacement of $`Mn`$ by $`Cu`$). Energy Dispersive X-ray microanalyses confirm the presence of copper on the manganese crystallographic sites.

The electrical resistivity $`\rho (T,x)`$ was measured using the conventional four-probe method. To avoid Joule and Peltier effects, a dc current $`I=1mA`$ was injected (as a one second pulse) successively on both sides of the sample. The voltage drop $`V`$ across the sample was measured with high accuracy by a $`KT256`$ nanovoltmeter. Fig.1 presents the temperature dependence of the resistivity $`\rho (T,x)`$ for two $`La_{2/3}Ca_{1/3}Mn_{1x}Cu_xO_3`$ samples, with $`x=0`$ and $`x=0.04`$, respectively. Notice a rather sharp (nearly a $`50\%`$) drop of resistivity (both near the peak and on its low temperature side) for the doped sample along with a small reduction of the transition (peak) temperature $`T_C(x)`$ reaching $`T_C(0)=265K`$ and $`T_C(0.04)=250K`$, respectively.

Since no tangible structural changes have been observed upon copper doping, the Jahn-Teller mechanism can be safely ruled out and the most reasonable cause for the resistivity drop in the doped material is the reduction of the spin-polaron tunneling energy $`E_\sigma `$ which within the localization scenario  is tantamount to an increase of the charge carrier correlation length $`L=\sqrt{2\mathrm{}^2/mE_\sigma }`$ (here $`m`$ is an effective polaron mass). In the FM region (below $`T_C(x)`$), the tunneling based resistivity reads  $`\rho [M(T,x)]=\rho _se^{2R/L(M)}`$ where $`\rho _s^1=e^2R^2\nu _{ph}N_m`$ with $`R`$ being the tunneling distance (and $`2R`$ being a size of a small spin polaron), $`\nu _{ph}`$ the phonon frequency, and $`N_m`$ the density of available states. In turn, the correlation length $`L(M)`$ depends on the temperature and concentration of copper $`x`$ through the corresponding dependencies of the magnetization $`M(T,x)`$. Assuming, along the main lines of conventional mean-field approximation schemes  that $`L(M)=L_0/(1M^2/M_L^2)`$ (with $`M_L`$ being a fraction of the saturated magnetization $`M(0)`$), we arrive at the following expression for the tunneling dominated resistivity

$$\rho (T,x)=\rho _0e^{\gamma M^2(T,x)},$$
(1)   
with $`\rho _0=\rho _se^{2R/L_0}`$ and $`\gamma =2R/L_0M_L^2`$.

To account for the observed behavior of the resistivity, we identify $`T_C`$ with the doping-dependent Curie temperature $`T_C(x)`$, and consider that the temperature and $`x`$ dependence of the magnetization is the sum of a classical Curie-Weiss contribution and a residual term, namely

$$M(T,x)=M_R(x)+M_0(x)\mathrm{tanh}\left\{\sqrt{\left[T_C(x)/T\right]^21}\right\}.$$
(2)   
Specifically, $`M_R(x)`$ is interpreted as a $`Cu`$ induced paramagnetic contribution while $`M_0(x)`$ accounts for the deviation of the ferromagnetically aligned $`Mn`$ magnetic moments of the undoped material in the presence of copper atoms. In fact, save for the $`M_R(x)`$ term, Eq.(2) is an analytical (approximate) solution of the well-known Curie-Weiss mean-field equation on spontaneous magnetization, viz. $`M(T,x)/M(0,x)=\mathrm{tanh}\left\{\left[M(T,x)/M(0,x)\right](T_C(x)/T)\right\}`$. To exclude any extrinsic effects (like grain boundary scattering), we consider the normalized resistivity $`\mathrm{\Delta }\rho (T,x)/\mathrm{\Delta }\rho (0,x)`$ with $`\mathrm{\Delta }\rho (T,x)=\rho (T,x)\rho (T_C(x),x)`$ and $`\rho (0,x)`$ being the resistivity taken at the lowest available temperature. Fig.2 depicts the above-defined normalized resistivity versus the reduced temperature $`T/T_C(x)`$ for the two samples. First of all, notice that the $`x=0`$ and $`x=0.04`$ data merge both at low temperatures and above $`T_C(x)`$, while starting from $`T_C(x)`$ and below the $`Cu`$-doped (squares) and $`Cu`$-free (circles) samples follow different routes. On the other hand, approaching $`T_C(x)`$ from low temperatures, a (most likely) fluctuation driven  crossover from undoped to doped transport mechanism is clearly seen near $`T/T_C(x)0.9`$. The solid lines are the best fits through all the data points according to Eqs.(1) and (2), yielding $`M_0(0)/M_L=1.41\sqrt{L_0/2R}`$, $`M_R(0)=0`$, $`M_0(0.04)=0.98M_0(0)`$, and $`M_R(0.04)=0.06M_0(0)`$ for the model parameters. Recalling that in our present study the copper content is $`x=0.04`$, the above estimates can be cast into the following explicit $`x`$ dependencies of the residual $`M_R(x)\sqrt{x}M_0(0)`$ and spontaneous $`M_0(x)\sqrt{1x}M_0(0)`$ magnetizations, giving rise to an exponential (rather than power) $`x`$ dependence of the observed resistivity $`\rho (T,x)`$ (see Eqs.(1) and (2)). Furthermore, assuming (as usual ) $`2R/L_01`$ for the (undoped) tunneling distance to correlation length ratio and using the found value of the residual resistivity $`\rho (T_C(0),0)=\rho _03.5m\mathrm{\Omega }m`$, the density of states  $`N_m9\times 10^{26}m^3eV^1`$ and the phonon frequency  $`\nu _{ph}2\times 10^{13}s^1`$ (estimated from Raman shift for optical $`MnO`$ modes), we obtain $`R5\AA `$ for an estimate of the tunneling distance (corresponding to $`2R10\AA `$ for a spin-polaron’s size) which in turn results in $`L_010\AA `$ (using a free electron approximation for a polaron’s mass $`m`$) and $`E_\sigma (0)0.12eV`$ for a zero-temperature copper-free carrier charge correlation length and the spin-polaron tunneling energy, respectively, both in good agreement with reported  estimates of these parameters in other systems. Based on the above estimates, we can roughly estimate the copper induced variation of the correlation length $`L(x)`$ and the corresponding spin polaron tunneling energy $`E_\sigma (x)`$. Indeed, according to the earlier introduced definitions, $`L[M(T_C(x))]=L_0/(1M_R^2(x)/M_L^2)L_0/(12x)`$ and $`E_\sigma (x)L^2(x)`$ which lead to $`L(x)L(0)/(1x)^2`$ and $`E_\sigma (x)E_\sigma (0)(1x)^4`$ for small enough $`x`$. These explicit $`x`$ dependencies (along with the composition variation of the transition temperature $`T_C(x)T_C(0)(1x)`$) remarkably correlate with the $`Co`$ induced changes in $`La_{2/3}Ca_{1/3}Mn_{1x}Co_xO_3`$ recently observed by Rubinstein et al. 

Interestingly, the above-obtained estimates agree very well with the observed peak (at $`T_C(x)`$) and residual (at $`T0`$) resistivities defined through the model parameters as follows (see Eqs.(1) and (2))

$$\rho (T_C(x),x)=\rho _0e^{\gamma M_R^2(x)},$$
(3)   
and

$$\rho (0,x)=\rho _0e^{\gamma M^2(0,x)},$$
(4)   
with $`\rho _0`$, $`M_R(x)`$, and $`M(0,x)`$ defined earlier. This provides thus an elegant self-consistency check for the employed interpretation.

In summary, a rather substantial drop in resistivity $`\rho (T,x)`$ of $`La_{2/3}Ca_{1/3}Mn_{1x}Cu_xO_3`$ sample upon just $`4\%`$ $`Cu`$ doping is reported. Along with lowering the Curie point $`T_C(x)`$, the copper substitution is argued to add a small paramagnetic contribution $`M_R(x)`$ to the $`Mn`$ spins dominated spontaneous magnetization $`M`$ of the undoped material leading to a small decrease of the spin-polaron tunneling energy $`E_\sigma (x)`$. However, due to the tunneling dominated carrier transport process, this small amount of impurity is sufficient for the drastical changes in resistivity absolute value across the whole temperature range. The temperature and $`x`$ dependencies of the observed resistivity was found to be rather well fitted by a nonthermal coherent tunneling of spin polarons with a heuristic expression for the magnetization $`M(T,x)`$ in the ferromagnetic state (as an approximate analytic solution of the mean-field Curie-Weiss equation), resulting in the exponential (rather than linear) doping dependence of $`\rho (T,x)`$.

###### Acknowledgements.

Part of this work has been financially supported by the Action de Recherche Concertées (ARC) 94-99/174. S.S. thanks FNRS (Brussels) for some financial support.