Efficient Self‐Contained Photoacid Generator System Based on Photochromic Terarylenes. Issue 45 (28th September 2016)

• Record Type: Journal Article
• Authors: Li, Ruiji; Nakashima, Takuya; Kanazawa, Rui; Galangau, Olivier; Kawai, Tsuyoshi
• Is Part Of: Chemistry. Volume 22:Issue 45(2016)
• Page Start: 16250
• Page End: 16257
• Publication Date: 2016-09-28
• Subjects: photoacid generator -- photochemistry -- photochromism -- photolithography -- terarylene; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201603768
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A series of highly sensitive neutral photoacid generators (PAGs) based on photochromic terarylenes was prepared. Like the example presented herein, these compounds show a subsequent thermal elimination of a Brønsted acid after a light‐triggered 6π‐electrocyclization, concomitant with the hexatriene aromatization. A novel type of molecular systems was developed, in which one thiazolyl moiety was replaced by a thienyl group. Depending on the solvents and on the nature of the acid source, the quantum yield (QY) for acid generation could reach up to 0.6. Comparative studies on the acid source clearly showed that aromatic leaving groups tend to extinguish the molecular system photoefficiency. A second type was also prepared, in which the nature of the hetero‐aromatic rings were identical to our previous example, but their sequence was modified. Therefore, a second level of improvement was achieved in nonpolar solvents, pushing the QY value up to 0.7. Finally, we demonstrated the mesylic acid‐releasing PAG as a photocatalyst in a chemically amplified positive resist system. Abstract : Let there be acid : An elimination reaction of an acid molecule was combined as a subsequent reaction of a photochromic 6π‐electrocyclization reaction of terarylenes, which was applied in a chemically amplified resist system (see figure).