Advanced Functional Materials, Vol.20, No.18, 2989-3003, 2010
Capacitors with an Equivalent Oxide Thickness of < 0.5 nm for Nanoscale Electronic Semiconductor Memory
The recent progress in the metal-insulator-metal (MIM) capacitor technology is reviewed in terms of the materials and processes mostly for dynamic random access memory (DRAM) applications. As TiN/ZrO2-Al2O3-ZrO2/TiN (ZAZ) type DRAM capacitors approach their technical limits, there has been renewed interest in the perovskite SrTiO3, which has a dielectric constant of >100, even at a thickness similar to 10 nm. However, there are many technical challenges to overcome before this type of MIM capacitor can be used in mass-production compatible processes despite the large advancements in atomic layer deposition (ALD) technology over the past decade. In the mean time, rutile structure TiO2 and Al-doped TiO2 films might find space to fill the gap between ZAZ and SrTiO3 MIM capacitors due to their exceptionally high dielectric constant among binary oxides. Achieving a uniform and dense rutile structure is the key technology for the TiO2-based dielectrics, which depends on having a dense, uniform and smooth RuO2 layer as bottom electrode. Although the Ru (and RuO2) layers grown by ALD using metal-organic precursors are promising, recent technological breakthroughs using the RuO4 precursor made a thin, uniform, and denser Ru and RuO2 layer on a TiN electrode. A minimum equivalent oxide thickness as small as 0.45 nm with a low enough leakage current was confirmed, even in laboratory scale experiments. The bulk dielectric constant of ALD SrTiO3 films, grown at 370 degrees C, was similar to 150 even with thicknesses <= 15 nm. The recent development of novel group II precursors made it possible to increase the growth rate largely while leaving the electrical properties of the ALD SrTiO3 film intact. This is an important advancement toward the commercial applications of these MIM capacitors to DRAM as well as to other fields, where an extremely high capacitor density and three-dimensional structures are necessary.