Virginia R. Anderson

Waterless TiO2 atomic layer deposition using titanium tetrachloride and titanium tetraisopropoxide

The surface chemistry for TiO2 atomic layer deposition (ALD) typically utilizes water or other oxidants that can oxidize underlying substrates such as magnetic disks or semiconductors. To avoid this oxidation, waterless or oxidant-free surface chemistry can be used that involves titanium halides and titanium alkoxides. In this study, waterless TiO2 ALD was accomplished using titanium tetrachloride (TiCl4) and titanium tetraisopropoxide (TTIP). In situ transmission Fourier transform infrared (FTIR) studies were employed to study the surface species and the reactions during waterless TiO2 ALD. At low temperatures between 125 and 225  °C, the FTIR absorbance spectra revealed that the isopropoxide species remained on the surface after TTIP exposures. The TiCl4 exposures then removed the isopropoxide species and deposited additional titanium species. At high temperatures between 250 and 300  °C, the isopropoxide species were converted to hydroxyl species by β-hydride elimination. The observation of propene gaseous reaction product by quadrupole mass spectrometry (QMS) confirmed the β-hydride elimination reaction pathway. The TiCl4 exposures then easily reacted with the hydroxyl species. QMS studies also observed the 2-chloropropane and HCl gaseous reaction products and monitored the self-limiting nature of the TTIP reaction. Additional studies examined the waterless TiO2 ALD growth at low and high temperature. Quartz crystal microbalance measurements observed growth rates of ∼3 ng/cm2 at a low temperature of 150  °C. Much higher growth rates of ∼15 ng/cm2 were measured at a higher temperature of 250  °C under similar reaction conditions. X-ray reflectivity analysis measured a growth rate of 0.55 ± 0.05 A/cycle at 250  °C. X-ray photoelectron depth-profile studies showed that the TiO2 films contained low Cl concentrations <1 at. %. This waterless TiO2 ALD process using TiCl4 and TTIP should be valuable to prevent substrate oxidation during TiO2 ALD on oxygen-sensitive substrates.The surface chemistry for TiO2 atomic layer deposition (ALD) typically utilizes water or other oxidants that can oxidize underlying substrates such as magnetic disks or semiconductors. To avoid this oxidation, waterless or oxidant-free surface chemistry can be used that involves titanium halides and titanium alkoxides. In this study, waterless TiO2 ALD was accomplished using titanium tetrachloride (TiCl4) and titanium tetraisopropoxide (TTIP). In situ transmission Fourier transform infrared (FTIR) studies were employed to study the surface species and the reactions during waterless TiO2 ALD. At low temperatures between 125 and 225  °C, the FTIR absorbance spectra revealed that the isopropoxide species remained on the surface after TTIP exposures. The TiCl4 exposures then removed the isopropoxide species and deposited additional titanium species. At high temperatures between 250 and 300  °C, the isopropoxide species were converted to hydroxyl species by β-hydride elimination. The observation of propene gas...

Real-time Growth Study of Plasma Assisted Atomic Layer Epitaxy of InN Films by Synchrotron X-ray Methods

The temporal evolution of high quality indium nitride (InN) growth by plasma-assisted atomic layer epitaxy (ALEp) on a-plane sapphire at 200 and 248 °C was probed by synchrotron x-ray methods. The growth was carried out in a thin film growth facility installed at beamline X21 of the National Synchrotron Light Source at Brookhaven National Laboratory and at beamline G3 of the Cornell High Energy Synchrotron Source, Cornell University. Measurements of grazing incidence small angle x-ray scattering (GISAXS) during the initial cycles of growth revealed a broadening and scattering near the diffuse specular rod and the development of scattering intensities due to half unit cell thick nucleation islands in the Yoneda wing with correlation length scale of 7.1 and 8.2 nm, at growth temperatures (Tg) of 200 and 248 °C, respectively. At about 1.1 nm (two unit cells) of growth thickness nucleation islands coarsen, grow, and the intensity of correlated scattering peak increased at the correlation length scale of 8.0 a...

Plasma-assisted atomic layer epitaxial growth of aluminum nitride studied with real time grazing angle small angle x-ray scattering

Wide bandgap semiconducting nitrides have found wide-spread application as light emitting and laser diodes and are under investigation for further application in optoelectronics, photovoltaics, and efficient power switching technologies. Alloys of the binary semiconductors allow adjustments of the band gap, an important semiconductor material characteristic, which is 6.2 eV for aluminum nitride (AlN), 3.4 eV for gallium nitride, and 0.7 eV for (InN). Currently, the highest quality III-nitride films are deposited by metalorganic chemical vapor deposition and molecular beam epitaxy. Temperatures of 900 °C and higher are required to deposit high quality AlN. Research into depositing III-nitrides with atomic layer epitaxy (ALEp) is ongoing because it is a fabrication friendly technique allowing lower growth temperatures. Because it is a relatively new technique, there is insufficient understanding of the ALEp growth mechanism which will be essential to development of the process. Here, grazing incidence small...