Rutile Without Substrate Limitations: Top-Interface-Driven Crystallization of TiO<sub>2</sub>.

Jeon, Jihoon; Kim, Jongseo; Ye, Seungwan; Kim, Seong Keun · Adv Mater · 2026

basic_science · Level V

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Abstract

Controlling the polymorphic phases within the thermal budget of atomic layer deposition (ALD) is essential for integrating high-k dielectrics into dynamic random-access memory (DRAM) capacitors. Rutile TiO<sub>2</sub> offers a dielectric constant significantly higher than that of tetragonal ZrO<sub>2</sub> and anatase TiO<sub>2</sub>. However, its application on industry-standard TiN electrodes is impeded by the lack of rutile-compatible lattice matching. A top-interface-driven stabilization strategy is demonstrated, where a structurally compatible RuO<sub>2</sub> upper layer stabilizes rutile TiO<sub>2</sub> at 400°C regardless of the crystallinity of the underlying ZrO<sub>2</sub>/TiN stack. Thickness-dependent phase maps reveal an interfacial-energy-driven anatase-to-rutile transition for thin amorphous TiO<sub>2</sub> layers, enabling rutile formation even on amorphous ZrO<sub>2</sub>. The resulting TiO<sub>2</sub>/ZrO<sub>2</sub>/TiN capacitors exhibit a dielectric constant of approximately 80 and a reduced equivalent oxide thickness, comparable to that of ZrO<sub>2</sub>-based stacks. A methanol-assisted reduction-etching process allows selective removal of RuO<sub>2</sub> by O<sub>3</sub> with minimal TiN oxidation. This top-interface engineering concept offers a substrate-agnostic approach to rutile TiO<sub>2</sub> that is compatible with DRAM process windows and can be extended to other polymorphic oxides.