Enhancement of Low-field Magnetoresistance in Self-Assembled Epitaxial La0.67Ca0.33MnO3:NiO and La0.67Ca0.33MnO3:Co3O4 Composite Films via Polymer-Assisted Deposition

Polymer-assisted deposition method has been used to fabricate self-assembled epitaxial La0.67Ca0.33MnO3:NiO and La0.67Ca0.33MnO3:Co3O4 films on LaAlO3 substrates. Compared to pulsed-laser deposition method, polymer-assisted deposition provides a simpler and lower-cost approach to self-assembled composite films with enhanced low-field magnetoresistance effect. After the addition of NiO or Co3O4, triangular NiO and tetrahedral Co3O4 nanoparticles remain on the surface of La0.67Ca0.33MnO3 films. This results in a dramatic increase in resistivity of the films from 0.0061 Ω•cm to 0.59 Ω•cm and 1.07 Ω•cm, and a decrease in metal-insulator transition temperature from 270 K to 180 K and 172 K by the addition of 10%-NiO and 10%-Co3O4, respectively. Accordingly, the maximum absolute magnetoresistance value is improved from −44.6% to −59.1% and −52.7% by the addition of 10%-NiO and 10%-Co3O4, respectively. The enhanced low-field magnetoresistance property is ascribed to the introduced insulating phase at the grain boundaries. The magnetism is found to be more suppressed for the La0.67Ca0.33MnO3:Co3O4 composite films than the La0.67Ca0.33MnO3:NiO films, which can be attributed to the antiferromagnetic properties of the Co3O4 phase. The solution-processed composite films show enhanced low-field magnetoresistance effect which are crucial in practical applications. We expect our polymer-assisted deposited films paving the pathway in the field of hole-doped perovskites with their intrinsic colossal magnetoresistance.