Embodiments according to the present invention relate generally to PAG bilayer and PAG-doped unilayer structures using sacrificial polymer layers that incorporate a photoacid generator having a concentration gradient therein. Said PAG concentration being higher in a upper portion of such structures than in a lower portion thereof. Embodiments according to the present invention also relate to a method of using such bilayers and unilayers to form microelectronic structures having a three-dimensional space, and methods of decomposition of the sacrificial polymer within the aforementioned layers.