Effects of residual hydrogen in sputtering atmosphere on structures and properties of amorphous In-Ga-Zn-O thin films
We investigated the effects of residual hydrogen in sputtering atmosphere on subgap states and carrier transport in amorphous In-Ga-Zn-O (a-IGZO) using two sputtering systems with different base pressures of ∼10-4 and 10-7 Pa (standard (STD) and ultrahigh vacuum (UHV) sputtering, respectively), which produce a-IGZO films with impurity hydrogen contents at the orders of 1020 and 1019 cm-3, respectively. Several subgap states were observed by hard X-ray photoemission spectroscopy, i.e., peak-shape near-valence band maximum (near-VBM) states, shoulder-shape near-VBM states, peak-shape near-conduction band minimum (near-CBM) states, and step-wise near-CBM states. It was confirmed that the formation of these subgap states were affected strongly by the residual hydrogen (possibly H2O). The step-wise near-CBM states were observed only in the STD films deposited without O2 gas flow and attributed to metallic In. Such step-wise near-CBM state was not detected in the other films including the UHV films even deposited without O2 flow, substantiating that the metallic In is segregated by the strong reduction effect of the hydrogen/H2O. Similarly, the density of the near-VBM states was very high for the STD films deposited without O2. These films had low film density and are consistent with a model that voids in the amorphous structure form a part of the near-VBM states. On the other hand, the UHV films had high film densities and much less near-VBM states, keeping the possibility that some of the near-VBM states, in particular, of the peak-shape ones, originate from -OH and weakly bonded oxygen. These results indicate that 2% of excess O2 flow is required for the STD sputtering to compensate the effects of the residual hydrogen/H2O. The high-density near-VBM states and the metallic In segregation deteriorated the electron mobility to 0.4 cm2/(V s).