Design, synthesis, and engineering of advanced materials for block copolymer lithography

Block copolymers (BCPs) are an attractive alternative for patterning applications used to produce next-generation microelectronic devices. Advancements require the development of high interaction parameter χ BCPs that enable patterning at the sub-10 nm length scale. Several organosilicon BCPs were designed to both enhance χ and impart an inherent etch selectivity that facilitates pattern transfer processes. Increasing the BCP silicon content both increases χ and bolsters the etch resistance, providing a pathway to designing new high-χ materials. Unfortunately, the BCPs investigated are not amenable to thermal annealing because the organosilicon block preferentially segregates to an air/vacuum interface and drives orientation parallel to the surface. A series of spin-coatable, polarity-switching top coats (as well as other strategies) were developed to provide a “neutral” top interface and promote the perpendicular orientation of BCP domains. In addition, a methodology for evaluating the neutral condition, relying on thickness quantization and the corresponding wetting behavior (i.e. island/hole topography) of lamellae. The top coat strategy was demonstrated for several BCP systems, and perpendicular structures can successfully be etched on commercial tools and be transferred into underlying substrates. The interaction parameter χ was evaluated using two methods to compare the performance of several BCPs: the order-disorder transition (ODT) of symmetric diblock copolymers, and the absolute scattering profile of a disordered BCP melt. Both methods, while severely limited for quantitative comparison, indicate trends towards higher χ with additional appended polar and organosilicon functional groups. Furthermore, the pattern fidelity is shown to be a function of the overall BCP segregation strength. The free energy of confined lamella was modeled algebraically to produce response surface plots capable of identifying process conditions favorable for perpendicular orientation. Thickness independent perpendicular orientation is only favorable using two neutral interfaces. Incommensurate film thicknesses are the most favorable, with commensurability conditions dependent on the wetting behavior at each interface. The modeling was supplemented with an extensive body of thin film experimental work that qualitatively agrees well with the above conclusions.