Off-Stoichiometry Improves Photostructuring of Thiol-Enes Through Diffusion-Induced Monomer Depletion

• Thiol-enes are a group of alternating copolymers with highly ordered networks used in a wide range of applications. Here, “click” chemistry photostructuring in off-stoichiometric thiol-enes is shown to induce microscale polymeric compositional gradients due to species diffusion between non-illuminated and illuminated regions, creating two narrow zones with distinct composition on either side of the photomask feature boundary: a densely cross-linked zone in the illuminated region and a zone with an unpolymerized highly off-stoichiometric monomer composition in the non-illuminated region. By the use of confocal Raman microscopy, it is here explained how species diffusion causes such intricate compositional gradients in the polymer, and how off-stoichiometry results in improved image transfer accuracy in thiol-ene photostructuring. Furthermore, increasing the functional group off-stoichiometry and decreasing photomask feature size is shown to amplify the induced gradients, which potentially leads to a new methodology for microstructuring.

Subject headings

TEKNIK OCH TEKNOLOGIER  -- Nanoteknik (hsv//swe)

ENGINEERING AND TECHNOLOGY  -- Nano-technology (hsv//eng)

TEKNIK OCH TEKNOLOGIER  -- Materialteknik -- Textil-, gummi- och polymermaterial (hsv//swe)

ENGINEERING AND TECHNOLOGY  -- Materials Engineering -- Textile, Rubber and Polymeric Materials (hsv//eng)

Keyword

thiol-ene

oste

OSTEmer

polymer

photopatterning

photolithography

monomer diffusion

click chemistry

Raman confocal microscopy

microfluidics

Electrical Engineering

Elektro- och systemteknik

Teknisk materialvetenskap

Materials Science and Engineering

Publication and Content Type

ref (subject category)

art (subject category)