Sol-Gel synthesis offers relatively inexpensive scale processing of mixed oxide materials with a good control over the stoichiometry and morphology which helps to tailor the required materials on atomic scale to suit specific applications. Nanophasic polycrystalline samples of La0.7Pb0.3MnO3 (LPMO) manganites having perovskite type structure synthesized by novel Sol-Gel technique using acetate precursor route were sintered at various temperatures in the range 950-1150 degrees C for studying the effect of grain size modifications on their structural, transport and magnetotransport properties. X-ray diffraction (XRD) studies show that the samples exhibit rhombohedral structure crystallizing in space group R-3C. Microstructural investigations using Scanning Electronic Microscopy (SEM), Atomic Force Microscopy (AFM) and Lateral Force Microscopy (LFM) measurements reveal the observation of secondary grain growth behavior starting in the sample sintered at 1000 degrees C. The d.c. four probe resistivity measurements with and without applied magnetic field in the temperature range of 2-380 K, show the effect of secondary grain growth on the magnetoresistance (MR) behavior of LPMO manganites. The microstructural studies show the atomic scale engineering at nanoscale which is reflected in the improvement of surface to volume ratio (D(-1)) which in turn modifies the physical properties of samples under investigation. All the samples exhibit resistivity minima at approximately 30 K which can be explained in terms of e-e interaction at 0 Tesla field. There is a correlation between the parameters derived from e-e scattering model and the secondary grain growth present in the samples. The results of the microstructural and MR measurements on the nanostructured LPMO manganites have been discussed in detail.

Structural, magnetic and transport studies have been carried out on (La0.7−2xEux)(Ca0.3Srx)MnO3 (0.05⩽x⩽0.25) compounds forming in a distorted orthorhombic structure (space group Pnma, No. 62). The Eu and Sr substitutions avoid any average A-site cation size disparity throughout the series. However, increasing both the cation size mismatch at the A-site and carrier concentration induces interesting changes in structural, transport and magnetic properties. Both insulator–metal transition temperature (Tp) and Curie temperature (TC) decrease with increasing x. The resistivity of all the samples in the semiconducting regime fits to the Variable Range Hopping (VRH) of Mott type model. Carrier localization length, L, obtained from VRH plots, decreases from 4.6 Å for x=0.05 to 3.9 Å for the x=0.20 sample. In the metallic region, the n term in the resistivity fits to the Zener-Double exchange polynomial law (ρ=ρ0+ρ2T2+ρnTn) increases from n=5.5 for x=0.05 to n=7.5 for x=0.15. From magnetic susceptiblity measurements, it is observed that there is an increase in the deviation in susceptibility from Curie–Weiss behavior with increasing size disorder and Mn4+ ion concentration. Further, complex magnetic behavior appears in paramagnetic and ferromagnetic regimes for half-doped sample indicative of phase separation. A disparity between Tp and TC is also observed and is as a result of phase segregation. At low temperatures, a large CMR effect occurs with a decrease in Tp.

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Electrical, magnetotransport, and magnetization measurements have been carried out on half-doped (La0.5−xTbx)(Ca0.38−ySr0.12+y)MnO3 (0.025⩽x⩽0.125; y=0.8x) compounds. The increase in Tb3+ and Sr2+ contents keeps the average A-site ionic radius constant at ∼1.215 Å but introduces increasing size disorder. The insulator-metal transition temperature (Tp) falls from 191 to 107 K and the Curie temperature (TC) falls from 230 to 106 K as x increases from 0.025 to 0.125. Interestingly, with increasing size disorder, the disparity between TC and Tp disappears and magnetoresistance increases around Tp but decreases at low temperatures. This is discussed in the light of phase segregation.

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