A method of forming a microelectronic structure using directed self-assembly, said method comprising: providing a wafer stack, said stack comprising: a substrate having a surface; one or more optional intermediate layers on said substrate surface; spin coating a hardmask composition comprising a silicon-containing polymer dissolved or dispersed in a solvent, wherein said silicon-containing polymer comprises repeating units of alternating silicon and oxygen atoms and further comprises compatible moieties, wherein said spin coating is performed at a speed of 1,000 to 5,000 rpm for a time period of from 30 to 120 seconds to form a hardmask neutral layer adjacent said intermediate layers if present, or on said substrate surface if no intermediate layers are present; forming a pre-pattern comprising a plurality of raised features on top of said hardmask neutral layer, said raised features being spaced apart and each being defined by respective sidewalls and a top surface; and applying a self-assembling composition directly on top of said hardmask neutral layer in spaces between said raised features, wherein said self-assembling composition comprises materials containing two or more immiscible compounds or a self-assembling compound comprising at least two components having distinct characteristics which allows segregation and alignment of the two compounds or components in a rational manner and that facilitate selective removal of one compound or component, said self-assembling composition self-assembling into a self-assembled layer directly adjacent said hardmask neutral layer, wherein said self-assembled layer comprises a first self-assembled region and a second self-assembled region different from said first self-assembled region, with one of the first or second self-assembled regions being adjacent the raised feature sidewalls, and the other of the first or second self-assembled regions (16a, 16b) segregated away from the raised features, wherein there is an affinity between said compatible moiety and a component in said self-assembling composition, and wherein said affinity induces pattern formation during said self-assembling of said self-assembling composition. a substrate having a surface; one or more optional intermediate layers on said substrate surface; spin coating a hardmask composition comprising a silicon-containing polymer dissolved or dispersed in a solvent, wherein said silicon-containing polymer comprises repeating units of alternating silicon and oxygen atoms and further comprises compatible moieties, wherein said spin coating is performed at a speed of 1,000 to 5,000 rpm for a time period of from 30 to 120 seconds to form a hardmask neutral layer adjacent said intermediate layers if present, or on said substrate surface if no intermediate layers are present; forming a pre-pattern comprising a plurality of raised features on top of said hardmask neutral layer, said raised features being spaced apart and each being defined by respective sidewalls and a top surface; and applying a self-assembling composition directly on top of said hardmask neutral layer in spaces between said raised features, wherein said self-assembling composition comprises materials containing two or more immiscible compounds or a self-assembling compound comprising at least two components having distinct characteristics which allows segregation and alignment of the two compounds or components in a rational manner and that facilitate selective removal of one compound or component, said self-assembling composition self-assembling into a self-assembled layer directly adjacent said hardmask neutral layer, wherein said self-assembled layer comprises a first self-assembled region and a second self-assembled region different from said first self-assembled region, with one of the first or second self-assembled regions being adjacent the raised feature sidewalls, and the other of the first or second self-assembled regions (16a, 16b) segregated away from the raised features, wherein there is an affinity between said compatible moiety and a component in said self-assembling composition, and wherein said affinity induces pattern formation during said self-assembling of said self-assembling composition.