Acid-sensitive, developer-soluble bottom anti-reflective coating compositions are provided, along with methods of using such compositions and microelectronic structures formed thereof. The compositions preferably comprise a crosslinkable polymer dissolved or dispersed in a solvent system. The polymer preferably comprises recurring monomeric units having adamantyl groups. The compositions also preferably comprise a crosslinker, such as a vinyl ether crosslinking agent, dispersed or dissolved in the solvent system with the polymer. In some embodiments, the composition can also comprise a photoacid generator (PAG) and/or a quencher. The bottom anti-reflective coating compositions are thermally crosslinkable, but can be decrosslinked in the presence of an acid to be rendered developer soluble.