Enhancing the surface properties and functionalization of polymethyl methacrylate with atomic layer-deposited titanium(IV) oxide

Polymethyl methacrylate (PMMA) is a widely used polymer in applications such as engineering structural plastics, energy storage materials, and biomaterials. However, its poor surface properties lead to fracture and deformation. Functionalization of the PMMA surface can make it more resistant to aggressive environments and prevent it from biodegradation, discoloration, and increased surface roughness. Here, atomic layer deposition (ALD) was used to deposit TiO2 thin films from tetrakis(dimethylamido)titanium (TDMAT) and ozone on PMMA substrates to improve its surface properties without the need for plasma assistance or another interlayer. Spectroscopic ellipsometry was used for the first time to measure the metal oxide film thickness on thick PMMA substrates. Two different growth regimes were observed, one for initial and the other for later ALD cycles. Initially, the growth rate on PMMA was 1.39 A/cycle, which is ~ 3.5 times higher than that on stand-alone silicon (0.4 A/cycle); this is attributed to cyclic chemical vapor deposition of TDMAT and moisture within PMMA concomitant with TiO2 ALD from TDMAT and ozone. However, after the formation of ~ 30-nm-thick film on PMMA, the TiO2 growth rate became similar to that on silicon. Moreover, our results revealed that the presence of PMMA in the deposition reactor affects the TiO2 growth rate on silicon substrates as well. These findings are discussed and corroborated with residual gas analyzer and X-ray absorption near-edge structure data. The thermal stability of the PMMA samples was examined by thermogravimetric analysis. Chemical composition and surface roughness of coated PMMA were studied by X-ray photoelectron spectroscopy and optical profilometry, respectively. The TiO2 coating increased wettability by ~ 70% and surface hardness by 60%.