Physical and electrical characteristics of atomic-layer deposition-HfO2 films deposited on Si substrates having different silanol Si-OH densities

Abstract

In this work, ultrathin HfO2 films, less than 6 nm in thickness, are deposited by atomic-layer deposition (ALD) on Si substrates that have a variable density of silanol (Si-OH) chemical bonds after oxidizing the Si surface using hot H2O2. Given the surface chemistry needed for proper ALD growth of HfO2, OH-last surfaces are needed in order to react with the Hf-based precursor during half-cycle of this reaction. The later is important for proper nucleation and uniform growth of ultrathin HfO2 by ALD. Depending on the immersion time of an initially HF-last Si surface in hot H2O2, ultrathin and nonstoichiometric chemical oxides SiOx are formed presenting a variable density of Si-OH bonds which are measured after Fourier-transform infra red spectroscopy. Following SiOx formation, HfO2 is directly deposited on these surfaces by ALD using water (H2O) and tetrakis-dimethylamino-hafnium as precursors. Metal–insulator–semiconductor (MIS) capacitors are then formed using both HfO2/Si and HfO2/SiOx/Si stacked structures and their electrical characteristics are evaluated. It is found that a variable density of Si-OH chemical bonds have an impact on the physical and electrical characteristics of these MIS structures by reducing their atomic surface roughness (Rrms) and gate leakage current density (Jg), and at the same time, increasing their flat band voltage (Vfb) for the same immersion times in H2O2. Obtaining the lowest Rrms, Jg, and Vfb are possible by using intermediate H2O2 immersion times between 4 and 8 min, which is also directly related to an intermediate Si-OH bond density.