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Electron-Beam-Induced Oligomerization of Perylene at the Surface of Perylene Single Crystals.

Created on 04 Sep 2026

Authors

Ken Morita, Hiromi Okamoto, Kohei Imura

Published in

The journal of physical chemistry letters. Volume 17. Issue 35. Pages 10021-10027. Sep 03, 2026.

Abstract

Electron-beam (e-beam) irradiation provides a powerful strategy for inducing chemical reactions with high spatial selectivity. Herein, we demonstrate space-selective oligomerization of perylene molecules in single crystals under a low-vacuum scanning electron microscope. Mass spectrometry analysis of the reaction products reveals formation of perylene oligomers ranging from dimers to tetramers. Meanwhile, optical spectroscopy analysis of the products shows a redshift compared with that of the monomer, and a broad extinction band emerges beyond 800 nm after irradiation. The products also exhibit an intense near-infrared photoluminescence band centered at 720 nm upon 633 nm excitation. Raman spectroscopy combined with non-negative independent component analysis enables decomposition of the Raman bands into those arising from various reaction products. Using density functional theory calculations, one of the major oligomers is consistent with a perylene dimer with extended π-conjugation, called quaterrylene. Raster scanning of e-beam irradiation allows creation of dotted and textured patterns with a nanometer-scale (≈340 nm) resolution, yielding spatially controlled photoluminescent microstructures. This approach establishes a simple and versatile route for spatially resolved synthesis of π-extended PAHs and opens new possibilities for patterned organic emitters in microscale optoelectronic devices.

PMID:
42691361
Bibliographic data and abstract were imported from PubMed on 04 Sep 2026.

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