Chemical vapor deposition of ruthenium and ruthenium oxide thin films for advanced complementary metal-oxide semiconductor gate electrode applications

A low-temperature (320-480 degreesC) metal-organic chemical vapor deposition (MOCVD) process was developed for the growth of ruthenium and ruthenium oxide thin films. The process used bis(ethylcyclopentadienyl)ruthenium [Ru(C5H4C2H5)(2)] and oxygen as, respectively, the ruthenium and oxygen sources. Systematic investigations of film formation mechanisms and associated rate limiting factors that control the nucleation and growth of the Ru and RuO2 phases led to the demonstration that the MOCVD process can be smoothly and reversibly modified to form either Ru or RuO2 through simple and straightforward modifications to the processing conditions-primarily oxygen flow and substrate temperature. In particular, films grown at low oxygen flows (50 sccm) exhibited a metallic Ru phase at processing temperatures below 480 degreesC. In contrast, films grown at high oxygen flow (300 sccm) were metallic Ru below 400 degreesC. Above 400 degreesC, a phase transition was observed from Ru to RuOx (0 < x < 2.0) to RuO2 as the processing temperature was gradually increased to 480 degreesC.