Epitaxial Growth of CaTiO3 Thin Films by Metal Organic Vapor Phase Epitaxy for Potential Applications in Memristive Devices

Cryst Growth Des. 2025 May 23;25(11):3654-3664. doi: 10.1021/acs.cgd.4c01412. eCollection 2025 Jun 4.

Abstract

Calcium titanate thin films with high structural quality were grown heteroepitaxially on perovskite oxide substrates using the liquid-delivery spin metal-organic vapor phase epitaxy (MOVPE) technique. To determine the growth window, suitable metal-organic precursors were selected, and their evaporation conditions were established. Initially, the thermal decomposition behavior of the precursors was studied using thermogravimetric analysis, which showed that full pyrolysis at 460 °C is possible for both the Ca and Ti precursors. This enabled the growth of fully strained, stoichiometric CaTiO3 films on SrTiO3 and NdGaO3 substrates, and potentially on other perovskite oxide substrates, within the diffusion-limited regime. The influence of vaporization temperatures, substrate temperature, oxygen-to-argon ratio, and Ca-to-Ti ratio on the structural properties of the CaTiO3 thin films was investigated using high-resolution X-ray diffraction, atomic force microscopy, and transmission electron microscopy. Structural analysis was ultimately correlated with electrical properties measured via IV curves. Intrinsic resistive switching was observed for stoichiometric and slightly off-stoichiometric CaTiO3 films grown on SrTiO3 substrates with ≈2.2% tensile strain. Relative to our previous work on resistive switching in SrTiO3 (Baki., Sci. Rep., 2021, 11 (1), 1-11), the underlying mechanism is discussed in the context of CaTiO3. This highlights the potential of CaTiO3 for technological applications such as resistive random-access memory (ReRAM) and neuromorphic computing.

Keywords: MOVPE; epitaxial CaTiO3 films; resistive switching.