Mechanistic Advantages of Organotin Molecular EUV Photoresists

Extreme ultraviolet (EUV)-induced radiation exposure chemistry in organotin–oxo systems, represented by the archetypal [(R–Sn)12O14(OH)6]­(A)2 cage, has been investigated with density functional theory. Upholding existing experimental evidence of Sn–C cleavage-dominant chemistry, computations have revealed that either electron attachment or ionization can single-handedly trigger tin–carbon bond cleavage, partially explaining the current EUV sensitivity advantage of metal oxide systems. We have revealed that tin atoms at different parts of the molecule react differently to ionization and electron attachment and have identified such selectivity as a result of local coordination chemistry instead of the macro geometry of the molecule. An ionization–deprotonation pathway has also been identified to explain the observed evolution of an anion conjugate acid upon exposure and anion mass dependence in resist sensitivity