Tungsten (W) thin film was deposited at 400 oC using pulsed chemical vapor deposition (pulsed CVD); film was then evaluated as a nucleation layer for W-plug deposition at the contact, with an ultrahigh aspect ratio of about 14~15 (top opening diameter: 240~250 nm, bottom diameter: 98~100 nm) for dynamic random access memory. The deposition stage of pulsed CVD has four steps resulting in one deposition cycle: (1) Reaction of WF6 with SiH4. (2) Inert gas purge. (3) SiH4 exposure without WF6 supply. (4) Inert gas purge while conventional CVD consists of the continuous reaction of WF6 and SiH4. The pulsed CVD-W film showed better conformality at contacts compared to that of conventional CVD-W nucleation layer. It was found that resistivities of films deposited by pulsed CVD were closely related with the phases formed and with the microstructure, as characterized by the grain size. A lower contact resistance was obtained by using pulsed CVD-W film as a nucleation layer compared to that of the conventional CVD-W nucleation layer, even though the former has a higher resistivity (~100 μΩ-cm) than that of the latter (~25 μΩ-cm). The plan-view scanning electron microscopy images after focused ion beam milling showed that the lower contact resistance of the pulsed CVD-W based W-plug fill scheme was mainly due to its better plug filling capability.
Aluminum oxide (Al2O3) thin films were grown by atomic layer deposition (ALD) using a new Al metalorganic precursor, dimethyl aluminum sec-butoxide (C12H30Al2O2), and water vapor (H2O) as the reactant at deposition temperatures ranging from 150 to 300 oC. The ALD process showed typical self-limited film growth with precursor and reactant pulsing time at 250 oC; the growth rate was 0.095 nm/cycle, with no incubation cycle. This is relatively lower and more controllable than the growth rate in the typical ALD-Al2O3 process, which uses trimethyl aluminum (TMA) and shows a growth rate of 0.11 nm/ cycle. The as-deposited ALD-Al2O3 film was amorphous; X-ray diffraction and transmission electron microscopy confirmed that its amorphous state was maintained even after annealing at 1000 oC. The refractive index of the ALD-Al2O3 films ranged from 1.45 to 1.67; these values were dependent on the deposition temperature. X-ray photoelectron spectroscopy showed that the ALD-Al2O3 films deposited at 250oC were stoichiometric, with no carbon impurity. The step coverage of the ALD-Al2O3 film was perfect, at approximately 100%, at the dual trench structure, with an aspect ratio of approximately 6.3 (top opening size of 40 nm). With capacitance-voltage measurements of the Al/ALD-Al2O3/p-Si structure, the dielectric constant of the ALDAl2O3 films deposited at 250 oC was determined to be ~8.1, with a leakage current density on the order of 10−8 A/cm2 at 1 V.