Solvent annealing and thickness control for the orientation of silicon-containing block copolymers for nanolithographic applications

Block copolymers are an ideal solution for a wide variety of nanolithographic opportunities due to their tendency to self-assemble on nanoscopic length scales. High etch selectivity and thin-film orientation are crucial to the success of this technology. Most conventional block copolymers have poor etch selectivity; however, incorporating silicon into one block produces the desired etch selectivity. A positive side effect of the silicon addition is that the χ value (a block-to-block interaction parameter) of the block copolymer increases. This decreases the critical dimension of potential features. Unfortunately, one negative side effect is the increase in the surface energy difference between the blocks. Incorporating silicon decreases the surface energy of that block. Typically, annealing is used to induce the chain mobility that is required for the block copolymer to reach its minimum thermodynamic energy state. Thermal annealing is the easiest annealing technique; however, if the glass transition temperature (Tg) of one block is above the thermal decomposition temperature of the other block, the latter will degrade before the former can reorient. In addition, annealing silicon-containing block copolymers usually results in a wetting layer and parallel orientation since the lower surface energy block favors the air interface, minimizing the free energy. Solvent annealing replaces the air interface with a solvent, thereby changing the surface energy. The solvent plasticizes the block copolymer, effectively decreasing the Tgs of both blocks. Another benefit is the ability to reversibly alter the orientation by changing the solvent or solvent concentration. The challenge with solvent annealing is that it depends on a number of parameters including: solvent selection, annealing time, and vapor concentration, which generate a very large variable space that must be searched to find optimum screening conditions.