Block copolymer self-assembly has been used as nanopatterning towards applications of lithography for decades. For the purpose of smaller, faster and cheaper transistor developments, block copolymers with high Flory-Huggins parameter and better etching contrast need to be further developed. PDMS based block copolymers are of the most interest among all candidates. I synthesized a library of well defined PDMS-b-PMMA, PDMS-b-PS and PDMS-b-PEO through "click" chemistry. The Flory-Huggins interaction parameters of these block copolymers are characterized much higher than conventional block copolymers as expected. Therefore, sub-10 nm domain periods are achieved by these materials in bulk. Significantly, long range ordered nanoline and nanodot patterns have been produced by PDMS-b-PMMA. Furthermore, a small molecule (L)-tartaric acid used as a hydrogen bonding donor was proved to efficiently suppress the crystallinity of PEO and significantly enhance the self-assembly behavior. Finally, the triazole moiety in the middle of the block copolymer which synthesized by "click" chemistry was functionalized to produce an ionic junction block copolymer. The electrostatic interactions before the opposite charges act as an extra enthalpy to help the self-assembly. Therefore, order disorder transition temperature of the block copolymer was dramatically increased.