Tightly bound ligands for hafnium nanoparticle EUV resists

Relative ligand binding energies were determined for a series of common ligand types with hafnium oxide nanoparticles, and from these results a series of novel strong binding ligands were developed. The relative equilibrium concentrations of two competing ligands bound to the nanoparticles were measured using nuclear magnetic resonance spectroscopy (NMR). For each ligand type, equilibrium constants and relative binding energies were then calculated and compared. Methane sulfonic acid was found to have the strongest binding energy, 2.0 Kcal/mol stronger than acetic acid. A group of three sulfonate ligands capable of freeradical crosslinking were made, along with three sulfonate ligands capable of creating aqueous developable nanoparticles. One of these ligands resulted in insoluble nanoparticles, however, the other two ligands resulted in nanoparticles that coated well on a silicon substrate and had dissolution rates greater than 100 nm per second.

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