Manipulation of nanoscale phase separation and optical properties of P3HT/PMMA polymer blends for photoluminescent electron beam resist

A novel photoluminescence electron beam resist made from the blend of poly(3-hexylthiophene) (P3HT) and poly(methyl methacrylate) (PMMA) has been successfully developed in this study. In order to optimize the resolution of the electron beam resist, the variations of nanophase separated morphology produced by differing blending ratios were examined carefully. Concave P3HT-rich island-like domains were observed in the thin film of the resist. The size of concave island-like domains decreased from 350 to 100 nm when decreasing the blending ratio of P3HT/PMMA from 1:5 to 1:50 or lower, concurrently accompanied by significant changes in optical properties and morphological behaviors. The λ_max of the film absorption is blue-shifted from 520 to 470 nm, and its λ_max of photoluminescence (PL) is also shifted from 660 to 550 nm. The radiative lifetime is shorter while the luminescence efficiency is higher when the P3HT/PMMA ratio decreases. These results are attributed to the quantum confinement effect of single P3HT chain isolated in PMMA matrix, which effectively suppresses the energy transfer between the well-separated polymer chains of P3HT. The factors affecting the resolution of the P3HT/PMMA electron beam resists were systematically investigated, including blending ratios and molecular weight. The photoluminescence resist with the best resolution was fabricated by using a molecular weight of 13500 Da of P3HT and a blending ratio of 1:1000. Furthermore, high-resolution patterns can be obtained on both flat silicon wafers and rough substrates made from 20 nm Au nanoparticles self-assembled on APTMS (3-aminopropyltrimethoxysilane)-coated silicon wafers. Our newly developed electron beam resist provides a simple and convenient approach for the fabrication of nanoscale photoluminescent periodic arrays, which can underpin many optoelectronic applications awaiting future exploration.