Microstructure development of sol-gel derived epitaxial LiNbO₃ thin films

Film growth and microstructural evolution were investigated for sol-gel derived LiNbO3 thin films deposited on lattice-matched single-crystal substrates. Epitaxial LiNbO3 films of about 100 nm nominal thickness were prepared by spin coating a solution of the lithium niobium ethoxide on sapphire (0001) substrates and anneaIing at 400 degrees C or 700 degrees C in a humidified oxygen atmosphere. These films exhibited an epitaxial relationship with the substrate of the type LiNbO3 (0001) parallel to alpha-Al2O3 (0001) and LiNbO3 [100] parallel to alpha-Al2O3 [100] as determined by x-ray pole figure analysis. Transmission electron microscopy indicated the epitaxial films annealed at 400 degrees C consisted of slightly misoriented similar to 5 nm subgrains and of numerous similar to 10 nm enclosed pores. The microstructure and orientation development of these films was consistent with a heteroepitaxial nucleation and growth mechanism, in which epitaxial nuclei form at the substrate surface and grow upward into an amorphous and porous intermediate film. Epitaxial films annealed at 700 degrees C contained larger 150-200 nm subgrains and pinhoIes. Misorientations between adjacent subgrains appeared to be significantly smaller in films annealed at 700 degrees C than those in films annealed at 400 degrees C. Hydrolysis of the alkoxide precursor solution prior to spin coating promoted the development of polycrystalline films on single-crystal sapphire substrates. Infrared spectra and thermal analysis indicated that, independent of the degree of the solution hydrolysis, nucleation of LiNbO3 was immediately preceded by decomposition of an amorphous carbonate intermediate phase.