Methods of forming microelectronic structures using multilayer processes are disclosed. The methods comprise the use of a developer-soluble protective layer adjacent the substrate surface in a multilayer stack to protect the substrate during pattern transfer. After etching, the pattern is transferred into the developer-soluble protective layer using a developer instead of etching required by previous methods. Conventional developer-soluble anti-reflective coatings and gap-fill materials can be used to form the protective layer. Custom layers with developer solubility can also be prepared. Microelectronic structures formed by the above processes are also disclosed.