Disclosed herein is a method of forming
polymer structures comprising applying a solution of a diblock
copolymer assembly comprising at least one diblock
copolymer that forms lamellae, to a neutral surface of a substrate having a chemical pattern thereon, the chemical pattern comprising alternating pinning and neutral regions that are chemically distinct and which have a chemical pattern
spatial frequency given by the number of paired sets of pinning and neutral regions along a given direction on the substrate; and forming domains comprising blocks of the diblock
copolymer. The domains form by lateral segregation of the blocks. At least one domain has an affinity for the pinning regions and forms on the pinning region, the domains so formed on the pinning region are aligned with the underlying chemical pattern, and domains that do not form on the pinning region form adjacent to and are aligned with the domains formed on the pinning regions. In this way, a structure comprising repeating sets of domains is formed on the chemical pattern with a
spatial frequency given by the number of repeating sets of domains in the given direction, that is at least twice that of the chemical pattern
spatial frequency. Methods of forming the chemical patterns, and pattern transfer methods using patterned domains, are also disclosed.