H. S. Craft

Outdiffusion of La and Al from amorphous LaAlO3 in direct contact with Si (001)

We have evaluated the thermal stability of Al2O3/LaAlO3/Si (001) stacks with atomic force microscopy, x-ray diffraction, transmission electron microscopy, and secondary ion mass spectrometry using a back side polishing approach. Crystallization of the amorphous LaAlO3 film was found to occur for rapid thermal anneals (RTA) above 935 °C for 20 s, in flowing N2. Penetration of Al and La into the underlying Si (001) is clearly observed for RTA at or above 950 °C for 20 s in flowing N2.

MgO epitaxy on GaN (0002) surfaces by molecular beam epitaxy

We report on the epitaxial deposition of magnesium oxide films with [111] crystallographic orientation on (0002) GaN by molecular beam epitaxy. Specifically, we use an adsorption controlled growth mechanism to initiate the growth process. Electron diffraction shows a spotty intense pattern without intensity fluctuations during growth and evidence of in-plane twinning. X-ray diffraction reveals the films to be epitaxial with full width at half maximum values of 0.3°, 0.5°, and 1° in 2θ, ϕ, and χ circles, respectively. Wet etching of the GaN surface with a HCl:HF mixture prior to growth is critical for achieving high crystalline quality. Epitaxial growth is observed between room temperature and 650°C, with negligible changes in crystalline quality with increased temperature. Atomic force microscopy analysis shows grainy surfaces with feature sizes near 10nm and rms roughness values of 1.4A over 1μm2 areas. X-ray diffraction analysis suggests MgO film stability up to 850°C in ex situ air annealing.

Band offsets and growth mode of molecular beam epitaxy grown MgO (111) on GaN (0002) by x-ray photoelectron spectroscopy

MgO is a proposed dielectric for use as a tunneling barrier in devices integrating GaN and ferroelectric oxides. In this study, we present data regarding the growth mode and band offsets of MgO grown epitaxially on GaN (0002) surfaces using molecular beam epitaxy. Using in situ x-ray photoelectron spectroscopy (XPS) and molecular beam epitaxy, we determine, from sequential growth experiments, that the growth of MgO proceeds via the Volmer-Weber (three-dimensional) mode, and full coalescence of the film does not occur until approximately 12nm of MgO has been deposited. The observation of a three-dimensional growth mode is in agreement with previously published data. For the valence band offset, we find a value of 1.2±0.2eV, which corresponds to a 3.2eV conduction band offset. XPS measurements suggest a chemically abrupt interface and no effect on band lineup due to the slow coalescence behavior.

Thermal stability of amorphous LaScO3 films on silicon

The thermal stability of amorphous LaScO3 thin films deposited by molecular-beam deposition directly on (001) Si was investigated by high-resolution transmission electron microscopy (HRTEM), transmission infrared absorption spectroscopy (IRAS), and x-ray diffraction (XRD). IRAS indicated that the as-deposited films contained <0.1A of SiO2 at the interface between LaScO3 and silicon. XRD studies showed that the films remained amorphous after annealing in N2 at 700°C, although HRTEM showed structural order on an ∼1nm length scale even in the as-deposited films. By 800°C, the LaScO3 had started to crystallize and formed a ∼5nm thick Sc-deficient interlayer between it and silicon.

Surface water reactivity of polycrystalline MgO and CaO films investigated using x-ray photoelectron spectroscopy

The authors report a study comparing the surface reactivities of the alkaline earth oxides MgO and CaO with respect to water vapor under ultrahigh and high vacuum conditions. Using x-ray photoelectron spectroscopy and a series of in vacuo exposures spanning ∼10−10Torr vacuum, to 10−6Torr flowing oxygen, the extent of surface hydroxylation was investigated by monitoring the O 1s photoelectron line. After the most aggressive exposures, the MgO surface reacted to form a maximum hydroxyl coverage of ∼1.3 ML (monolayer), while the CaO surface reached a maximum coverage of ∼3.0 ML. Both surface hydroxides could be removed by in vacuo thermal anneals; exposure to 250 and 500°C were required for MgO and CaO, respectively. These results are framed in terms of the suitability of these oxides in complex oxide-compound semiconductor heteroepitaxial multifunctional devices and with respect to understanding the development of surface morphology in epitaxial 111-oriented CaO and MgO thin films.The authors report a study comparing the surface reactivities of the alkaline earth oxides MgO and CaO with respect to water vapor under ultrahigh and high vacuum conditions. Using x-ray photoelectron spectroscopy and a series of in vacuo exposures spanning ∼10−10Torr vacuum, to 10−6Torr flowing oxygen, the extent of surface hydroxylation was investigated by monitoring the O 1s photoelectron line. After the most aggressive exposures, the MgO surface reacted to form a maximum hydroxyl coverage of ∼1.3 ML (monolayer), while the CaO surface reached a maximum coverage of ∼3.0 ML. Both surface hydroxides could be removed by in vacuo thermal anneals; exposure to 250 and 500°C were required for MgO and CaO, respectively. These results are framed in terms of the suitability of these oxides in complex oxide-compound semiconductor heteroepitaxial multifunctional devices and with respect to understanding the development of surface morphology in epitaxial 111-oriented CaO and MgO thin films.

Spectroscopic analysis of the epitaxial CaO (111)–GaN (0002) interface

We report an x-ray photoelectron spectroscopy (XPS) study of the CaO∕GaN interface. Epitaxial films of CaO (111) were grown on GaN (0002) and analyzed in situ using XPS. We observe Stranski–Krastanov growth, in which CaO coalesces rapidly, then converts to a three-dimensional mode. Data suggest coalescence within the first nanometer of film growth, indicating growth behavior different from published reports of the analogous MgO–GaN system. We find 1.0±0.2eV for the valence band offset and a 2.5±0.2eV conduction band offset. The results are discussed in terms of their utility in oxide-nitride electronic devices.

Barrier layer mechanism engineering in calcium copper titanate thin film capacitors through microstructure control

A peak permittivity greater than 10 000 has been achieved for calcium copper titanate (CCT) thin films by engineering a thin film microstructure that maximizes space charge contributions to polarizability. This permittivity is an order of magnitude greater than previous polycrystalline thin film efforts. This unique microstructure control is accomplished using a chemical solution deposition process flow that produces highly dense parallel layers ∼100 nm in thickness. We observe a thickness dependent permittivity where the entire film thickness constitutes the conducting region of a barrier layer capacitor despite the presence of multiple grain boundaries within that thickness. The model predictions are in good agreement with experimental data and are consistent with existing literature reports. These trends in permittivity with dielectric thickness raise new questions regarding the nature of barrier layers in CCT—and specifically, these results suggest that grain boundaries may not always participate as h...

Spectroscopic measurements of the surface stoichiometry of chemical vapor deposited GaN

We report on the surface stoichiometry of Ga-polar GaN films grown by metalorganic chemical vapor deposition as studied by x-ray photoelectron spectroscopy. GaN film surfaces are found to be Ga-rich, with Ga:N ratios ranging from 1.3:1 to 3.2:1. In vacuo ion-beam sputter/annealing studies show that these treatments drive the apparent Ga:N surface composition farther from unity, either through a decrease in surface contamination, oxidation of the surface, or both. Simple annealing experiments decrease the Ga:N ratio. The measured GaN ratio is correlated with the GaN growth time, suggesting that residual Ga precursor after growth interacts with the GaN surface as it cools.

Epitaxial PbxZr1−xTiO3 on GaN

Epitaxial integration of PbxZr1−xTiO3 (PZT) (111) with GaN (0002) presents the possibility of polarity coupling across a functional-oxide/nitride heteropolar interface. This work describes the synthesis and characterization of such thin film heterostructures by magnetron sputtering, with specific attention given to process optimization. Using x-ray diffraction and electrical characterization, the growth of epitaxial PZT (∼250 nm) on GaN and PZT on MgO/GaN stacks was verified. A two-stage growth process was developed for epitaxial PZT with a deposition temperature of 300 °C and an ex-situ anneal at 650 °C, which was effective in mitigating interfacial reactions and promoting phase-pure perovskite growth. Electrical analysis of interdigital capacitors revealed a nonlinear and hysteretic dielectric response consistent with ferroelectric PZT. Piezoresponse force microscopy (PFM) characterization shows clear evidence of ferroelectric switching, and PFM hysteresis loop analysis shows minimal evidence for direct...

Molecular beam epitaxy of Sm2O3, Dy2O3, and Ho2O3 on Si (111)

We report on the epitaxial deposition of Sm2O3, Dy2O3, and Ho2O3 films on Si (111) substrates as progress towards developing a predictive model for gate oxide selection. To date, films have been characterized by reflection high-energy electron diffraction, x-ray diffraction (XRD), and x-ray photoemission spectroscopy (XPS). In the case of Sm2O3, difficulty was encountered in achieving the growth of phase pure films; growth of the desired bixbyite oxide phase was accompanied by significant amounts of monoclinic oxide as detected by XRD. Dy2O3 and Ho2O3 films can be produced free of unwanted phases when deposited using a background pressure of 1×10−6torr O2∕O3 and a substrate temperature between 425 and 550°C. Dy2O3 films with an x-ray peak width of 0.6° in ω were obtained. XPS studies of the Dy2O3∕Si interface are in progress, and verify the phase purity of the films.