Solvent-induced morphological diversification in poly(l-lactide-b-ɛ-caprolactone) block copolymer thin films

Biodegradable block copolymer of poly(l-lactide-b-ɛ-caprolactone) (P(LA-b-CL)) was dissolved in various solvents with different solubility as well as volatility, and spin-cast on a highly oriented pyrolytic graphite (HOPG) to prepare thin films. The surface morphologies were observed by using atomic force microscopy (AFM) in a dynamic force (tapping) mode. Particle like morphology was found in the thin films prepared form the dichloromethane and acetone. Higher volatility of dichloromethane and acetone resulted in the reflection of the particle like objects in the solution to HOPG substrate. In contrast, the P(LA-b-CL)s in toluene and 1,4-dioxane exhibited different morphologies compared to those in dichloromethane and acetone. Lower volatility of toluene and 1,4-dioxane assisted the epitaxial crystallization of PCL component along the HOPG lattice, that was revealed by enzymatic degradation of PLLA component by proteinase K. Thus, adjusting the solubility and solvent volatility for the film formation provided morphological divergence of the P(LA-b-CL) block copolymer, and this technique would be applicable for the surface patterning of biodegradable polymers.