The work in this thesis covers the design, growth and characterisation of neutron multilayers. The achieved reflectivity performance of a neutron multilayer depends on the achieved optical contrast between the layers as well as the achieved interface width between the layers. Because the reflectivity of a neutron multilayer depends exponentially on the square of the interface width, even a modest improvement can substantially increase the achieved reflectivity performance. It is for this reason that a large part of this work has been focused on growing smoother and more abrupt interfaces in neutron multilayers. As multilayers are such an integral component of most neutron optical instruments, any improvement in terms of reflectivity performance has broad implications for all conducted neutron scattering experiments. The conventional material system of choice for neutron optical components is Ni/Ti, owing to the high contrast in scattering length density (SLD). The reflected intensity of such components is largely dependent on the interface width, primarily caused by the formation of nanocrystallites, interdiffusion, and/or intermixing. Apart from hampering the reflectivity performance, the finite interface width between the layers also limits the minimum usable layer thickness in the mirror stack. In this work, Ni/Ti based multilayers are grown using ion-assisted magnetron sputtering. By co-depositing B 4 C in the multilayer stack, the formation of nanocrystallites as well as intermetallics between the interfaces were succesfully prevented. The co-deposition of B 4 C has been combined with a modulated ion assistance scheme, where an initial buffer layer is grown at a low ion energy creating abrupt interfaces, while the remainder of the layer is grown at a higher ion energy, smoothening the interfaces. X-ray reflectivity (XRR) measurements show significant improvements in terms of reflectivity when the multilayers are co-deposited with B 4 C . This has further been investigated using low neutron-absorbing isotope-enriched 11 B 4 C . The deposited 11 B 4 C containing multilayers have been characterized using neutron reflectometry, X-ray reflectivity, transmission electron microscopy (TEM), elastic recoil detection analysis (ERDA), X-ray photoelectron spectroscopy (XPS) and grazing incidence small angle scattering (GISAXS). Structural characteristics in the growth direction of the multilayer such as interface width and thickness variations have been determined by combined fits on X-ray and neutron reflectivity measurements, while the interface morphology has been investigated using GISAXS. The coupled fits to specular X-ray and neutron reflectivity measurements suggest a significant improvement in interface width for the samples that have been co-deposited with 11 B 4 C using a modulated on assistance scheme during deposition, where an interface width of 2.7 Å has been i Abstract achieved in a 11 B 4 C containing multilayer. The GISAXS measurements show that the co-deposition of 11 B 4 C leads to mounded interfaces ...