In this study, the authors examined the effects of different annealing schemes on crystallinity in atomic layer deposition (ALD) grown Ti-containing metal gates and ultrathin ALD HfO2 high-k dielectric layers, and corresponding electrical results in metal oxide semiconductor capacitor (MOSCAP) devices. The authors investigated the effect of a postmetal deposition anneal (PMA) on the underlying HfO2, which was deposited using either a standard ALD process or a process which utilized a cyclical deposition and annealing scheme (termed DADA). The effect of the starting substrate surface, either chemically grown SiO2 or H-terminated Si, on HfO2 crystallinity was also studied. For 40 cycle ALD HfO2 (∼32 Å) with a TiN overlayer, a transition from an amorphous state to a cubic phase was observed with the application of a PMA treatment. Evidence of the orthorhombic phase of HfO2 with some level of texturing was observed for 40 cycle DADA processed films annealed with a TiN cap. Concomitantly a cubic (111) texture was observed for TiN deposited on DADA processed HfO2 and subjected to a PMA. Suppression of crystallinity for HfO2 deposited on H-terminated Si and annealed with a TiN layer was observed which illustrates the need for an adequate nucleation layer for uniform grain growth and increased atomic ordering. The authors also investigated metal gate stacks with a bilayer of TiN overlying Ti which showed reflections from both cubic TiN and hexagonal TiN0.3 in the as-deposited state and after annealing clear evidence of silicidation (TiSix) was observed. In MOSCAP structures with 40 cycle ALD HfO2 and a TiN overlayer subjected to a PMA, although the cubic phase of HfO2 was stabilized, there was no associated improvement in device scaling. This study highlights the importance of the initial crystalline state and nucleation of HfO2 as well as the thermal stability of the capping metal layer material when engineering dielectric layer crystallinity by means of a postmetal cap anneal. For ultrathin HfO2 integrated in advanced metal oxide semiconductor structures, the benefits of the stabilization of a higher-k phase through postmetal gate anneal may not be fully realized due to increased leakage along grain boundaries or decrease in effective k due to changes in the lower-k interfacial layer.
Nickel oxide (NiO) is one of few metal-oxide semiconductors showing a p-type conductivity and can be combined with an n-type semiconductor to fabricate a pn diode. In this study, isotype and anisotype heterojunction diodes were fabricated by ultraviolet (UV) oxidation at 350 °C of metallic Ni deposited on p- and n-Si substrates. The I-V characteristics of the NiO/p-Si diode do not show rectification, while those of the NiO/n-Si diode show rectification with a difference of two orders of magnitude between the currents at 2 and −2 V. The linear C−2 -V characteristics of the NiO/n-Si and secondary ion mass spectroscopy profile confirm that the UV oxidation temperature is low enough so as not to affect deep inside the Si. The NiO layers formed by the oxidation of Ni under UV illumination are found to be more conductive and more suitable for the diode fabrication than those by the thermal oxidation of Ni without UV illumination at the same temperature. Because the oxidation temperature is relatively low and can be further reduced, the UV oxidation can become an important process technology to form various metal-oxide semiconductors from printed metals for future printed flexible electronics.