Lithographic Performance of Aryl Epoxy Thermoset Resins as Negative Tone Photoresist for Microlithography.

Photoresists (or photo-resins) are the main and most important raw material used for lithography techniques such as deep X-ray (DXRL), ultraviolet (UVL), deep-UV (DUVL), and extreme UV (EUVL). In previous work, we showed how complicated could be the synthesis of the resins used to produce photoresist. In this study, we follow up on the strategy of tuning deep and macro levels of properties to formulate photo-resins. They were developed from a primary basis, using epoxy resins, a solvent, and a photoinitiator in several concentrations. The formulations were evaluated initially by the UVL technique, using a squared pattern of 2.3 mm. The most suitable compositions were then studied in a pattern structure varying from 50 down to 1 µm width, applying UVL and DUVL. The patterned structures were compared with the chemical composition of the photo-resins. Considering the deep level of properties, polydispersion, and epoxidation degree were evaluated. Regarding the macro level of properties, the concentration of photoinitiator was studied. Promising results have been achieved with the control of the deep and macro levels methodology. By means of UV lithography, it was possible to note, for a large feature size above 2.0 mm, the formulations presented good quality structures with a broad range of epoxidation degrees and photoinitiator concentrations, respectively from 3 to 100% (mol·mol) and from 10 to 40% (mol·mol). For structures smaller than 50 µm width, the composition of the photo-resins may be restricted to a narrow range of values regarding the formulation. The results indicate that the polydispersion of the oligomers might be a significant property to control. There is a tendency to better outcome with a low polydispersity (resins P1 and P2). Regarding UV and deep-UV irradiation, the best results were achieved with UV. Nevertheless, for DUV, the sensitivity seems to be more intense, leading to well-defined structures with over-exposure effects.