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TiO2 is an attractive material for photocatalytic water splitting, but its band gap is too large to allow for efficient absorption of solar photons. We present a comprehensive first-principles investigation of band-structure modifications induced by alloying TiO2 with TiS2. The band gap of TiO2(1−x)S2x alloys exhibits a dramatic decrease upon addition of even a low concentration of S. The optical absorption of visible light is attainable with sulfur concentrations less than x=0.25. We have verified that the band alignment in these alloys is favorable for photocatalytic applications: in particular, the conduction band exhibits only small shifts, while the majority of the band-gap change is due to an upward shift of the valence band.

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The effects of lanthanum incorporation into HfO2 dielectrics were studied using first-principles total energy calculations. The author’s computational result clearly showed that the formation energy of a neutral oxygen vacancy (VO0) in the vicinity of substitutional La atoms at Hf sites is 0.7eV larger than that in pure HfO2, indicating that the concentration of VO0’s is drastically reduced by La incorporation. This effect is understood to be caused by the decrease in the local dielectric constant κL around La atoms due to the strong ionic character of the La–O bond compared to the Hf–O bond.

The effect of using the transcorrelated variational Monte Carlo (TC-VMC) approach to construct a trial function for fixed node diffusion Monte Carlo (DMC) energy calculations has been investigated for the first-row atoms, Li to Ne. The computed energies are compared with fixed node DMC energies obtained using trial functions constructed from Hartree-Fock and density functional levels of theory. Despite major VMC energy improvement with TC-VMC trial functions, no improvement in DMC energy was observed using these trial functions for the first-row atoms studied. The implications of these results on the nodes of the trial wave functions are discussed.

The impact of TiN deposition on thin HfO2 films formed on Si substrates was studied using x-ray photoelectron spectroscopy and a monoenergetic positron beam. For the predeposition sample, the positrons implanted into Si were found to diffuse toward the HfO2∕Si interface under the influence of the electric field, suggesting the presence of negative charges in HfO2. After TiN was deposited by chemical vapor deposition, no large change in the defect species was observed. After TiN was deposited by physical vapor deposition, however, positive charges were introduced at the TiN∕HfO2 interface, which were associated with the incorporation of nitride into HfO2 and/or the plasma damage at the surface of HfO2, and the resultant formation of positively charged oxygen vacancies.

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We have theoretically shown that doping of N atoms increases the dielectric constant of the Hf silicates, enhancing both the electronic and lattice polarization contributions. The enhancement of the lattice contribution is dominant and is attributed to low-frequency vibration modes induced by the N doping. It is found that Hf and Si ions bonded to N atoms located at O vacancies largely vibrate in the modes and play a crucial role in the enhancement. Doped N atoms are shown to also improve the electric characteristic of the silicates, elevating O vacancy levels appearing in the band gap of the silicates.

The impact of nitridation on open volumes in thin HfSiOx films fabricated on Si substrates by atomic layer deposition was studied using monoenergetic positron beams. For HfSiOx, positrons were found to annihilate from the trapped state due to open volumes which exist intrinsically in an amorphous structure. After plasma nitridation, the size of open volumes decreased at a nitrogen concentration of about 20at.%. An expansion of open volumes, however, was observed after postnitridation annealing (PNA) (1050°C, 5s). We found that the size of open volumes increased with increasing nitrogen concentration in HfSiOx. The change in the size of open volumes was attributed to the trapping of nitrogen by open volumes, and an incorporation of nitrogen into the amorphous matrix of HfSiOx during PNA. We also examined the role of nitrogen in HfSiOx using x-ray photoelectron spectroscopy and first principles calculations.

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We studied effects of nitrogen incorporation into Hf-based high-k gate dielectrics on local insulating properties by conductive atomic force microscopy. Nitrogen-incorporated HfSiO/HfO2/SiO2 gate stacks exhibited excellent dielectric reliability, whereas we observed the creation of local leakage sites for untreated gate stacks, i.e., without nitridation. Both types of high-k dielectric layers were crystallized, and there was no relationship between the current leakage sites and surface morphology. These findings indicate that grain boundaries of the high-k films do not act as the leakage sites. Instead, we propose nitrogen incorporation as an important method for terminating the current leakage paths and discuss detailed mechanisms based on first-principles calculations.

The atomistic effects of N atoms on the leakage current through HfO2 high-k gate dielectrics have been studied from first-principles calculations within the framework of a generalized gradient approximation (GGA). It has been found that the intrinsic effects of N atoms drastically reduce the electron leakage current. N atoms couple favorably with oxygen vacancies (VO) in HfO2 and extract electrons from VO. As a result, VO energy levels are drastically elevated due to the charged-state change in VO from neutral (VO0) to positively charged (VO2+). Accordingly, N incorporation removes the electron leakage path mediated by VO related gap states.