Characterization and nanoindentation testing of thin ZrO 2 films synthesized using layer-by-layer (LbL) deposited organic templates

Abstract

Thin organic LbL (layer-by-layer) films with negatively charged surface were used as templates for biomimetic deposition of ZrO 2 on Si wafers by hydrolysis of Zr(SO 4) 2 solution. The as-deposited ceramic layers were fully amorphous and were composed of the mixture of zirconia and zirconium sulfate. During transmission electron microscopy (TEM) examination, the amorphous ZrO 2 crystallized almost instantaneously to tetragonal (t) ZrO 2 under the electron beam. The ≤110 nm thick as-deposited layers were crack-free and adhered well to the LbL surface. Annealing at 500 °C led to complete crystallization of amorphous ZrO 2 to nanocrystalline t-ZrO 2. Further heating to 900 °C resulted in transformation to monoclinic ZrO 2, complete removal of sulfur and twofold shrinkage of the ceramic layer thickness. Both the nanohardness and elastic modulus of the deposited zirconia layers were significantly improved following the heat treatments.