Fabrication and characterization of block copolymer micelle multilayer films prepared using dip-, spin- and spray-assisted layer-by-layer assembly deposition

We demonstrated mechanistic insight into all block copolymer micelle (BCM) multilayer films prepared using three methods: dip-, spin- and spray-assisted layer-by-layer (LbL) methods. The resultant films showed specific film growth mechanisms such as linear and non-linear growth, and distinct surface morphologies with tunable porosities were demonstrated via the respective assembly methods, despite an identical polymer composition and concentration. In particular, the porosity, as measured by ellipsometry, was readily controlled from 2.6% to 55.9% by manipulating the LbL deposition methods and thickness. AFM and SEM data indicate the fundamental morphological evolution of 0-dimensional nano-objects and control of the surface roughness by means of the various deposition methods. Therefore, the systematic study of the three LbL methods shown herein provides deep insight into the control of the structures of multilayer films according to the characteristics of nano-objects and assembly methods.