Chemical Modification Mechanisms in Hybrid Hafnium Oxo-methacrylate Nanocluster Photoresists for Extreme Ultraviolet Patterning

The potential implementation of extreme ultraviolet (EUV) lithography into next generation device processing is bringing urgency to identify resist materials that optimize EUV lithographic performance. Inorganic/organic hybrid nanoparticles or clusters constitute a promising new class of materials, with high EUV sensitivity from the core and tunable chemistry through the coordinating ligands. Development of a thorough mechanistic understanding of the solubility switching reactions in these materials is an essential first step toward their implementation in patterning applications but remains challenging due to the complexity of their structures, limitations in EUV sources, and lack of rigorous in situ characterization. Here, we report a mechanistic investigation of the solubility switching reactions in hybrid clusters comprising a small HfOx core capped with a methacrylic acid ligand shell (HfMAA). We show that EUV-induced reactions can be studied by performing in situ infrared (IR) spectroscopy of electron-irradiated films using a variable energy electron gun. Combining additional ex situ metrology, we track the chemical evolution of the material at each stage of a typical resist processing sequence. For instance, we find that a cross-linking reaction initiated by decarboxylation of the methacrylate ligands under electron irradiation constitutes the main solubility switching mechanism, although there are also chemical changes imparted by a typical post application bake (PAB) step alone. Lastly, synchrotron-based IR microspectroscopy measurements of EUV-irradiated HfMAA films enable a comparison of reactions induced by EUV vs electron beam irradiation of the same resist material, yielding important insight into the use of electron beam irradiation as an experimental model for EUV exposure.