Fate of bis-(4-tert-butyl phenyl)-iodonium under photolithography relevant irradiation and the environmental risk properties of the formed photoproducts.

Aryl-iodonium salts are utilized as photoacid generators (PAGs) in semiconductor photolithography and other photo-initiated manufacturing processes. Despite their utilization and suspected toxicity, the fate of these compounds within the perimeter of semiconductor fabrication plants is inadequately understood; the identification of photolithography products is still needed for a comprehensive environmental impact assessment. This study investigated the photolytic transformation of a representative iodonium PAG cation, bis-(4-tert-butyl phenyl)-iodonium, under conditions simulating industrial photolithography. Under 254-nm irradiation, bis-(4-tert-butyl phenyl)-iodonium reacted rapidly with a photolytic half-life of 39.2 s; different counter ions or solvents did not impact the degradation kinetics. At a semiconductor photolithography-relevant UV dosage of 25 mJ cm-2, 33% of bis-(4-tert-butyl phenyl)-iodonium was estimated to be transformed. Six aromatic/hydrophobic photoproducts were identified utilizing a combination of HPLC-DAD and GC-MS. Selected photoproducts such as tert-butyl benzene and tert-butyl iodobenzene had remarkably higher acute microbial toxicity toward bacterium Aliivibrio fischeri compared to bis-(4-tert-butyl phenyl)-iodonium. Octanol-water partition coefficients estimated using the Estimation Programs Interface Suite™ indicated that the photoproducts were substantially more hydrophobic than the parent compound. The results fill a critical data gap hindering the environmental impact assessment of iodonium PAGs and provide clues on potential management strategies for both iodonium compounds and their photoproducts.

Bioconcentration potential and microbial toxicity of onium cations in photoacid generators.

Despite the widespread utilization of onium salts as photoacid generators (PAGs) in semiconductor photolithography, their environmental, health, and safety (EHS) properties remain poorly understood. The present work reports the bioconcentration potential of five representative onium species (four sulfonium and one iodonium compound) by determining the octanol-water partition coefficient (POW) and lipid membrane affinity coefficient (KMA); microbial toxicity was evaluated using the bioluminescent bacterium Aliivibrio fischeri (Microtox bioassay). Four of the oniums exhibited varying degrees of hydrophobic (lipophilic) partitioning (log POW: 0.08-4.12; KMA: 1.70-5.62). A strong positive linear correlation was observed between log POW and KMA (KMA = log POW + 1.76, R2 = 0.99). The bioconcentration factors (log BCF) estimated from POW and KMA for the four oniums ranged from 0.13 to 3.67 L kg-1. Bis-(4-tert-butyl phenyl)-iodonium and triphenylsulfonium had 50% inhibitory concentrations (IC50) of 4.8 and 84.6 µM, whereas the IC50 values of the other three oniums were not determined because these values were higher than their aqueous solubility. Given the increased regulatory scrutiny regarding the use and potential health impacts from onium PAGs, this study fulfills critical knowledge gaps concerning the EHS properties of PAG oniums, enabling more comprehensive evaluation of their environmental impacts and potential risk management strategies.