A low-temperature (320–480 °C) 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 °C. In contrast, films grown at high oxygen flow (300 sccm) were metallic Ru below 400 °C. Above 400 °C, a phase transition was observed from Ru to RuOx (0 < x < 2.0) to RuO2 as the processing temperature was gradually increased to 480 °C.

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The challenges associated with producing next generation subnanometer films to meet conformality requirements on complex topographies and to improve semiconductor device performance characteristics have resulted in the consideration of a myriad of new materials, methods of deposition, and integration strategies.For many applications it has become apparent that atomic layer deposition (ALD) will become the method of choice for depositing films. Adoption of this technology is well underway for applications with aggressive architectures such as DRAM capacitors and electrodes, and it appears imminent for copper interconnect cladding applications. The time will soon come when every semiconductor device has at least one film that is generated by ALD.During the talk, an example of how Praxair has approached precursor development for interconnect barrier and seed applications will be illustrated, and how we have used a diverse series of learnings during development to benefit the ALD community at large.

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