Suppressed Surface Reorganization in a High-Density Poly(methyl methacrylate) Brush

A high-density poly(methyl methacrylate) (PMMA) brush (σ = 0.77 chain/nm²) with a lower molecular weight distribution was prepared onto a silicon wafer by surface-initiated atom transfer radical polymerization. The surface of the PMMA brush chains was characterized upon the process of the environmental change, from air to water, using contact angle measurements in conjunction with sum-frequency generation spectroscopy. The surface structure and properties altered less with the changing environment from air to water for the PMMA brush than for a spin-coated film; that is, the extent of surface reorganization could be suppressed by grafting densely-packed chains onto a substrate. Also, the water penetration into the brush surface was inhibited because of the densely packed chain structure.