Advanced photoresist technologies by intricate molecular brush architectures: Diblock brush terpolymer‐based positive‐tone photoresist materials

Abstract

The reported diblock brush terpolymer displays the fundamental advantages of high macromolecular and regiochemical control in simultaneous top‐down/bottom‐up construction of advanced positive‐tone photoresist materials. By selective partition the substrate adhesion, surface‐active migration, and chemically‐reactive deblocking functional compositions into the cylindrical polymer brush architectures, large‐areas of vertical alignment of the polymers within thin films are realized. The bottom‐up premeditated system enables effective top‐down lithography to produce near‐molecular pixel resolution (2–3 molecules) at low operation dosage.

Synthesis and Applications of Compartmentalised Molecular Polymer Brushes

“…Wooley and co-workers have demonstrated the versatility of norbornyl-bearing trithiocarbonate chain-transfer agents by the synthesis of polystyrene (PS), [16] poly(tert-butyl acrylate) (PtBA), [16] poly(hydroxystyrene), [17] poly(lactic acid) (PLA) [18] and fluorinated polymers [17,19] with excellent control over the dispersity.S equential ROMP of these macromonomers using am odified second generation Grubbs catalyst then yielded compartmentalised molecular brushes of various morphologies,including a" dumbbell"-like architecture. [18] Atom-transfer radical polymerisation (ATRP) and ringopening polymerisation (ROP) may also be used for the construction of norbornyl macromonomers without initiating ROMP.C onjugation of ah ydroxy functionality onto the norbornyl unit allows for ROPofcyclic monomers,including ThØophile Pelras (left) graduated from the UniversitØ de Haute-Alsacei n Mulhouse, France.…”

Synthese und Anwendung von kompartimentierten molekularen Polymerbürsten

“…Wooley und Mitarbeiter demonstrierten die Vielseitigkeit von Norbornyl‐tragenden Trithiocarbonaten als Kettentransferagentien bei der Synthese von Polystyrol (PS), Poly( tert ‐butylacrylat) (PtBA), Polyhydroxystyrol, Polylactid (PLA) und fluorierten Polymeren mit exzellenter Kontrolle über die Dispersität . Sequenzielle ROMP solcher Makromonomere unter der Verwendung von Grubbs‐Katalysatoren der zweiten Generation lieferte eine Kompartimentierung von Molekularbürsten mit verschiedenen Morphologien, unter anderem auch hantelförmige Architekturen.…”

“…Die oben genannten Weiterentwicklungen bei Synthesemethoden, die hauptsächlich durch die revolutionären Fortschritte im Bereich der kontrollierten Polymerisationsarten möglich wurden, haben das Forschungsinteresse an Molekularbürsten seit deren erster Beschreibung in den 1980er Jahren hin zur Herstellung hochfunktionaler Architekturen vorangetrieben. Molekulare Copolymerbürsten wurden vielfältig für die Nanofabrikation, in der Zellbildgebung und sogar bei der Nachahmung komplexer biologischer Funktionen, z. B. als größen‐ oder ladungsselektive molekulare Transporter, angewendet .…”

Syntheses of triblock bottlebrush polymers through sequential ROMPs: Expanding the functionalities of molecular brushes

“…During the past decade, functional bottlebrush polymers, or molecular brushes, have attracted increasing attention, due to their unique physiochemical properties and supramolecular assembly behaviors, as well as demonstrated applications in lithography, nanomedicine, and photonics . Three approaches, namely “grafting through,” “grafting onto,” and “grafting from,” have been developed to achieve well‐defined bottlebrush polymers. While each synthetic tactic holds its own advantages, it has been recognized that the “grafting‐through” strategy can provide greater feasibility on ensuring quantitative grafting efficiency and on tuning the chemical compositions, the functions, and the relative concentric and lengthwise dimensions, throughout the entire macromolecular framework.…”