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Vapor phase infiltration (VPI) has emerged as a promising tool for fabrication of novel hybrid materials. In the field of polymeric gas separation membranes, a beneficial impact on stability and membrane performance is known for several polymers with differing functional groups. This study for the first time investigates VPI of trimethylaluminum (TMA) into poly(1‐trimethylsilyl‐1‐propyne) (PTMSP), featuring a carbon–carbon double bond as functional group. Saturation of the precursor inside the polymer is already attained after 60 s infiltration time leading to significant densification of the material. Depth profiling proves accumulation of aluminum in the polymer itself, but a significantly increased accumulation is visible in the gradient layer between polymer and SiO2 substrate. A reaction pathway is proposed and supplemented by density‐functional theory (DFT) calculations. Infrared spectra derived from both experiments and simulation support the presented reaction pathway. In terms of permeance, a favorable impact on selectivity is observed for infiltration times up to 1 s. Longer infiltration times yield greatly reduced permeance values close or even below the detection limit of the measurement device. The present results of this study set a strong basis for the application of VPI on polymers for gas‐barrier and membrane applications in the future. [ABSTRACT FROM AUTHOR]

This feature article presents insights concerning the correlation of plasma‐enhanced chemical vapor deposition and plasma‐enhanced atomic layer deposition thin film structures with their barrier or membrane properties. While in principle similar precursor gases and processes can be applied, the adjustment of deposition parameters for different polymer substrates can lead to either an effective diffusion barrier or selective permeabilities. In both cases, the understanding of the film growth and the analysis of the pore size distribution and the pore surface chemistry is of utmost importance for the understanding of the related transport properties of small molecules. In this regard, the article presents both concepts of thin film engineering and analytical as well as theoretical approaches leading to a comprehensive description of the state of the art in this field. Perspectives of future relevant research in this area, exploiting the presented correlation of film structure and molecular transport properties, are presented. [ABSTRACT FROM AUTHOR]

This study tracks the physical aging behavior of coated and uncoated ultra‐thin poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) films on silicon wafers based on the refractive index using ellipsometry. The measured refractive index directly correlates with the free volume and hence the physical aging progression. Plasma‐enhanced chemical vapor deposition (PECVD) creates coatings with different thicknesses and oxidation degrees onto PTMSP films. Compared to uncoated PTMSP films, the PECVD‐coated films show a reduction of the refractive index increase of more than two orders of magnitude for less than 10 nm thin SiOx coatings. In contrast, SiOCH films show only a minor impact. The results reveal the superior physical aging behavior of PECVD‐coated films compared to untreated PTMSP films. [ABSTRACT FROM AUTHOR]