Effect of the Density of Reactive Sites in P(S-r-MMA) Film During Al2O3 Growth by Sequential Infiltration Synthesis

TL;DR

This study explores how the density of reactive sites in P(S-r-MMA) films influences alumina growth via sequential infiltration synthesis, revealing linear dependence on MMA content and insights into process kinetics.

Contribution

It provides new understanding of infiltration synthesis mechanisms and demonstrates how reactive site density affects alumina growth in copolymer films.

Findings

Alumina growth linearly depends on MMA content.

Low MMA concentration suffices for volumetric alumina growth.

MMA fraction influences TMA diffusivity and process kinetics.

Abstract

Sequential infiltration synthesis (SIS) consists in a controlled sequence of metal organic precursors and co-reactant vapor exposure cycles of polymer films. Two aspects characterize a SIS process: precursor molecule diffusion within the polymer matrix and precursor molecule entrapment into polymer films via chemical reaction. In this paper, we investigated SIS process for the alumina synthesis using trimethylaluminum (TMA) and H2O in thin films of poly(styrene-random-methyl methacrylate) (P(S-r-MMA)) with variable MMA content. The amount of alumina grown in the P(S-r-MMA) films linearly depends on MMA content. A relatively low concentration of MMA in the copolymer matrix is enough to guarantee the volumetric growth of alumina in the polymer film. In pure polystyrene, metal oxide seeds grow in the sub-surface region of the film. In-situ dynamic spectroscopic ellipsometry (SE) analyses provide quantitative information about TMA diffusivity in pristine P(S-r-MMA) matrices as a function of MMA fraction, allowing further insight into the process kinetics as a function of the density of reactive sites in the polymer film. This work improves the understanding of infiltration synthesis mechanism and provides a practical approach to potentially expand the library of polymers that can be effectively infiltrated by introducing reactive sites in the polymer chain.