J. C. Woicik

A Ferroelectric Oxide Made Directly on Silicon

Metal oxide semiconductor field-effect transistors, formed using silicon dioxide and silicon, have undergone four decades of staggering technological advancement. With fundamental limits to this technology close at hand, alternatives to silicon dioxide are being pursued to enable new functionality and device architectures. We achieved ferroelectric functionality in intimate contact with silicon by growing coherently strained strontium titanate (SrTiO3) films via oxide molecular beam epitaxy in direct contact with silicon, with no interfacial silicon dioxide. We observed ferroelectricity in these ultrathin SrTiO3 layers by means of piezoresponse force microscopy. Stable ferroelectric nanodomains created in SrTiO3 were observed at temperatures as high as 400 kelvin.

Oxygen vacancies in N doped anatase TiO2: Experiment and first-principles calculations

We have determined the electronic and atomic structure of N doped TiO2 using a combination of hard x-ray photoelectron spectroscopy and first-principles density functional theory calculations. Our results reveal that N doping of TiO2 leads to the formation of oxygen vacancies and the combination of both N impurity and oxygen vacancies accounts for the observed visible light catalytic behavior of N doped TiO2.

c-axis oriented epitaxial BaTiO3 films on (001) Si

c-axis oriented epitaxial films of the ferroelectric BaTiO3 have been grown on (001) Si by reactive molecular-beam epitaxy. The orientation relationship between the film and substrate is (001) BaTiO3‖(001) Si and [100] BaTiO3‖[110] Si. The uniqueness of this integration is that the entire epitaxial BaTiO3 film on (001) Si is c-axis oriented, unlike any reported so far in the literature. The thermal expansion incompatibility between BaTiO3 and silicon is overcome by introducing a relaxed buffer layer of BaxSr1−xTiO3 between the BaTiO3 film and silicon substrate. The rocking curve widths of the BaTiO3 films are as narrow as 0.4°. X-ray diffraction and second harmonic generation experiments reveal the out-of-plane c-axis orientation of the epitaxial BaTiO3 film. Piezoresponse atomic force microscopy is used to write ferroelectric domains with a spatial resolution of ∼100nm, corroborating the orientation of the ferroelectric film.

Chemical analysis of HfO2∕Si (100) film systems exposed to NH3 thermal processing

Nitrogen incorporation in HfO2∕SiO2 films utilized as high-k gate dielectric layers in advanced metal-oxide-semiconductor field effect transistors has been investigated. Thin HfO2 blanket films deposited by atomic layer deposition on either SiO2 or NH3 treated Si (100) substrates have been subjected to NH3 and N2 anneal processing. Several high resolution techniques including electron microscopy with electron energy loss spectra, grazing incidence x-ray diffraction, and synchrotron x-ray photoelectron spectroscopy have been utilized to elucidate chemical composition and crystalline structure differences between samples annealed in NH3 and N2 ambients as a function of temperature. Depth profiling of core level binding energy spectra has been obtained by using variable kinetic energy x-ray photoelectron spectroscopy with tunable photon energy. An “interface effect” characterized by a shift of the Si4+ feature to lower binding energy at the HfO2∕SiO2 interface has been detected in the Si 1s spectra; however,...

Local-structure origins of the sustained Curie temperature in (Ba,Ca)TiO3 ferroelectrics

While the lattice volume in the solid-solution Ba1−xCaxTiO3 decreases with increasing x, the Curie temperature remains unaffected, in contrast to Ba1−xSrxTiO3. We have determined the origin of this phenomenon by comparing the local structures in (Ba,Ca)TiO3 and (Ba,Sr)TiO3. Reverse Monte Carlo refinements of instantaneous atomic positions using simultaneous fitting of multiple types of experimental data (neutron total scattering, X-ray absorption fine structure, patterns of diffuse scattering in electron diffraction) reveal both ferroelectric Ca displacements and their amplification of the Ti off-centering, which mitigate the lattice-volume effects. The activity of Ca is triggered by the anomalously strained Ca-O bonds.

Nature of the metal insulator transition in ultrathin epitaxial vanadium dioxide.

We have combined hard X-ray photoelectron spectroscopy with angular dependent O K-edge and V L-edge X-ray absorption spectroscopy to study the electronic structure of metallic and insulating end point phases in 4.1 nm thick (14 units cells along the c-axis of VO2) films on TiO2(001) substrates, each displaying an abrupt MIT centered at ~300 K with width <20 K and a resistance change of ΔR/R > 10(3). The dimensions, quality of the films, and stoichiometry were confirmed by a combination of scanning transmission electron microscopy with electron energy loss spectroscopy, X-ray spectroscopy, and resistivity measurements. The measured end point phases agree with their bulk counterparts. This clearly shows that, apart from the strain induced change in transition temperature, the underlying mechanism of the MIT for technologically relevant dimensions must be the same as the bulk for this orientation.

Direct Observation of Electrostatically Driven Band Gap Renormalization in a Degenerate Perovskite Transparent Conducting Oxide

We have directly measured the band gap renormalization associated with the Moss-Burstein shift in the perovskite transparent conducting oxide (TCO), La-doped BaSnO_{3}, using hard x-ray photoelectron spectroscopy. We determine that the band gap renormalization is almost entirely associated with the evolution of the conduction band. Our experimental results are supported by hybrid density functional theory supercell calculations. We determine that unlike conventional TCOs where interactions with the dopant orbitals are important, the band gap renormalization in La-BaSnO_{3} is driven purely by electrostatic interactions.

La-doped BaSnO3—Degenerate perovskite transparent conducting oxide: Evidence from synchrotron x-ray spectroscopy

We report direct evidence of conduction band filling in 3% La-doped BaSnO3 using hard x-ray photoelectron spectroscopy. Direct comparisons with hybrid density functional theory calculations support a 3.2 eV indirect band gap. The use of hybrid DFT is verified by excellent agreement between our photoelectron spectra and O K-edge x-ray emission and absorption spectra. Our experimental and computational results demonstrate that the conduction band is primarily of Sn 5s orbital character with little O 2p contribution, which is a prerequisite for designing a perovskite-based transparent conducting oxide.

Origin of deep subgap states in amorphous indium gallium zinc oxide:Chemically disordered coordination of oxygen

The origin of the deep subgap states in amorphous indium gallium zinc oxide (a-IGZO), whether intrinsic to the amorphous structure or not, has serious implications for the development of p-type transparent amorphous oxide semiconductors. We report that the deep subgap feature in a-IGZO originates from local variations in the oxygen coordination and not from oxygen vacancies. This is shown by the positive correlation between oxygen composition and subgap intensity as observed with X-ray photoelectron spectroscopy. We also demonstrate that the subgap feature is not intrinsic to the amorphous phase because the deep subgap feature can be removed by low-temperature annealing in a reducing environment. Atomistic calculations of a-IGZO reveal that the subgap state originates from certain oxygen environments associated with the disorder. Specifically, the subgap states originate from oxygen environments with a lower coordination number and/or a larger metal-oxygen separation.

Extended x-ray absorption fine structure study of AlxGa(1−x)N films

Extended x-ray absorption fine structure above the Ga–K edge has been used to study the local structure of AlxGa1−xN films grown by metal organic chemical vapor deposition. With increasing Al content, x, the Ga–N bond length decreases, but much less than the average bond length. On the other hand, the x dependence of the Ga–Ga and Ga–Al distances does follow the variation of the average cation–cation distance. We conclude that bond angle distortions accommodate the differences between the Ga–N and Al–N bond lengths.