New Insights into Spin Coating of Polymer Thin Films in Both Wetting and Nonwetting Regimes

Spin coating is a common method for fabricating polymer thin films on flat substrates. The well-established Meyerhofer relationship between film thickness (h) and spin rate (ω), h ∝ ω^-1/2, enables the preparation of thin films with desired thickness by adjusting the spin rate and other experimental parameters. The 1/2 exponent has been verified by previous studies involving organic thin films prepared on silicon wafers. In this study, 88% and >99% hydrolyzed poly(vinyl alcohol) (PVOH) polymers were adsorbed and spin-coated from an aqueous solution onto four different substrates. The substrates were prepared by covalently attaching poly(dimethylsiloxane) (PDMS) of different molecular weights onto silicon wafers (SiO₂). Atomic force microscopy images indicate that the PVOH films transitioned from stable on SiO₂, to metastable, and then to unstable as PDMS molecular weight was increased. Notably, none of the polymer-substrate systems studied here exhibited the thickness-spin rate profile predicted by the Meyerhofer model. Based on the experimental results, a more general adsorption-deposition model is proposed that decouples the total spin-coated thickness into two components─the adsorbed thickness (h₁) and the spin-deposited thickness (h₂). The former accounts for polymer-substrate interactions, and the latter depends on polymer concentration and spin rate. In unstable systems, the exponents were found to be ∼0 because slip takes place at the solution-substrate interface during spin and the spin-deposited thickness is 0. In metastable and stable systems, a universal relationship between spin-deposited thickness and spin rate emerged, independent of the substrate type and polymer concentration for each polymer examined. Our findings indicate the importance of film stability and polymer-substrate interactions in the application of spin coating.