A composite dielectric material including an early transition metal or metal oxide base material and a dopant, co-deposited, alloying or layering secondary material, selected from among Nb, Ge, Ta, La, Y, Ce, Pr, Nd, Gd, Dy, Sr, Ba, Ca, and Mg, and oxides of such metals, and alumina as a dopant or alloying secondary material. Such composite dielectric material can be formed by vapor deposition processes, e.g., ALD, using suitable precursors, to form microelectronic devices such as ferroelectric high k capacitors, gate structures, DRAMs, and the like.