Magnetic nanoparticle-containing soft–hard diblock copolymer films with high order

For sensor applications, superparamagnetic anisotropy is an indispensable property, which is typically achieved by employing an external field to guide the arrangement of magnetic nanoparticles (NPs). In the present investigation, the diblock copolymer polystyrene-block-poly(N-isopropylacrylamide) (PS-b-PNIPAM) is printed as a template to localize magnetic iron oxide NPs without any external field. Via microphase separation, cylindrical nanostructures of PS in a PNIPAM matrix are obtained, aligned perpendicular to the substrate. Since the magnetite NPs (Fe$_3$O$_4$) are functionalized with hydrophobic organic chains showing affinity to the PS blocks, they can selectively aggregate inside the PS cylinders. Moreover, solvent vapor annealing allows the achievement of nanostructures inside the hybrid system with a very high order, even at a high NP loading. Therefore, NPs can accumulate within PS domains to form perpendicularly aligned aggregates with high periodicity. The magnetic properties of the hybrid films are determined at various temperatures in two orthogonal directions (with PS cylinders vertical and parallel to the applied magnetic field). All hybrid films show superparamagnetism and a remarkable magnetic anisotropy is achieved at certain NP concentrations. This investigation shows a facile route to prepare superparamagnetic films with magnetic anisotropy and offers a novel possibility to future magnetic sensor fabrication