Thermal and Remote Plasma ALD of Ru from CpRu(CO)2Et and O2

Ruthenium (Ru) is regarded as an electrode candidate on ultrahigh-k SrTiO3 dielectric films for future high-density trench capacitors. To achieve conformal film growth, atomic layer deposition (ALD) of Ru is investigated. To this end, the use of an oxidizing reactant is desired to avoid electronic degradation of the interface properties of SrTiO3 as found when using a NH3 plasma for Ru ALD or when using thermal ALD TiN as electrode. Thermal ALD of Ru using O2 gas, however, generally results in a pronounced nucleation delay and high surface roughness. The current work aims at developing ALD of Ru using an O2 plasma in order to improve the film nucleation and to try to obtain smoother films. Using the novel CpRu(CO)2Et precursor and O2, both thermal and remote plasma ALD of Ru were studied in the same reactor at wafers up to 200 mm. Unlike thermal ALD, the Ru film growth by remote plasma ALD does not rely on the dissociative chemisorption of O2 on the Ru surface and good film nucleation is expected by providing O radicals from the gas phase. In situ spectroscopic ellipsometry, x-ray reflectometry and diffractometry, and electrical measurements clearly show this benefit of the O2 plasma. The Ru films almost immediately nucleate for the plasma-based process, whereas the thermal process showed a nucleation delay of approximately 100 cycles. Once the film growth has started, the growth per cycle (1 Å/cycle), the electrical properties (20 µOcm for >5 nm films), and the polycrystalline structure are similar for both ALD processes. However, despite the drastically improved nucleation, the remote plasma ALD Ru films show higher roughness values than the thermal ALD Ru films (roughness of 13 nm and 8 nm for 20 nm thick films, respectively). To elucidate this unexpected phenomenon, the film nucleation and surface reactions were examined. Mass spectrometry provided insight into the reaction products (CO, CO2 and H2O mainly) and, therefore, into the surface chemistry ruling both ALD processes. Optical emission spectroscopy delivered information on the species created during plasma exposure. A reaction mechanism will be proposed for these oxygen-based ALD Ru processes that accounts not only for the differences in nucleation, but also relates to the roughness development of the Ru films