Solids
Effect of hyperstoichiometric manganese on the structure and transport, magnetic, and magnetoresistance properties of manganite-lanthanum (La$_{0.7}$Ca$_{0.3}$)$_{1-x}$Mn$_{1+x}$O$_3$ perovskites
V. P. Pashchenkoa,
A. V. Pashchenkoa,
V. K. Prokopenkoa,
Yu. F. Revenkoa,
A. A. Shemyakov,
A. G. Silchevab a Galkin Donetsk Institute for Physics and Engineering, Donetsk
b Lugansk Taras Shevchenko National University
Abstract:
Ceramic ($\mathrm{La}_{0.7}\mathrm{Ca}_{0.3})_{1-x}\mathrm{Mn}_{1+x}\mathrm{O}_3$ samples are studied by X-ray diffraction, resistive, magnetic,
$\mathrm{NMR}^{55}\mathrm{Mn}$, and magnetoresistance methods. The concentration changes of lattice parameter a of the cubic perovskite structure and its average ionic radius are in good agreement if the concentrations of anion and cation vacancies and nanostructured clusters with
$\mathrm{Mn}^{2+}$ in the A positions increase with
$x$. Phase transition temperatures
$T_{ms}$ and
$T_c$ weakly depend on
$x$, and the electrical resistivity and the activation energy decrease substantially with increasing
$x$ due to a change in the imperfection of the perovskite structure. An analysis of the broad asymmetric
$\mathrm{NMR}^{55}\mathrm{Mn}$ spectra of the samples indicate a high-frequency
$\mathrm{Mn}^{3+}\leftrightarrow\mathrm{Mn}^{4+}$ electron superexchange and nonuniform magnetic and valence states of these ions because of a nonuniform distribution of ions and defects, which decrease the amplitude resonance frequency with increasing
$x$. The magnetoresistive (MR) effect near phase-transition temperatures
$T_{ms}$ and
$T_c$ increases substantially with
$x$ and is caused by the effect of a magnetic field on the scattering of charge carriers by intracrystallite nanostructured heterogeneities of an imperfect perovskite structure. The second MR effect is located in the low-temperature range, is related to tunneling through mesostructural crystallite boundaries, and decreases weakly with increasing
$x$. A correlation is found between the hyperstoichiometric manganese content, the imperfection of the perovskite structure, and the magnitude of the MR effect.
Received: 01.11.2011
Accepted: 12.03.2012