L. F. J. Piper

Origin of the n-type conductivity of InN: The role of positively charged dislocations

As-grown InN is known to exhibit high unintentional n-type conductivity. Hall measurements from a range of high-quality single-crystalline epitaxially grown InN films reveal a dramatic reduction in the electron density (from low 1019 to low 1017cm−3) with increasing film thickness (from 50to12000nm). The combination of background donors from impurities and the extreme electron accumulation at InN surfaces is shown to be insufficient to reproduce the measured film thickness dependence of the free-electron density. When positively charged nitrogen vacancies (VN+) along dislocations are also included, agreement is obtained between the calculated and experimental thickness dependence of the free-electron concentration.

Transition from electron accumulation to depletion at InGaN surfaces

The composition dependence of the Fermi-level pinning at the oxidized (0001) surfaces of n-type InxGa1−xN films (0⩽x⩽1) is investigated using x-ray photoemission spectroscopy. The surface Fermi-level position varies from high above the conduction band minimum (CBM) at InN surfaces to significantly below the CBM at GaN surfaces, with the transition from electron accumulation to depletion occurring at approximately x=0.3. The results are consistent with the composition dependence of the band edges with respect to the charge neutrality level.The composition dependence of the Fermi-level pinning at the oxidized (0001) surfaces of n-type InxGa1−xN films (0⩽x⩽1) is investigated using x-ray photoemission spectroscopy. The surface Fermi-level position varies from high above the conduction band minimum (CBM) at InN surfaces to significantly below the CBM at GaN surfaces, with the transition from electron accumulation to depletion occurring at approximately x=0.3. The results are consistent with the composition dependence of the band edges with respect to the charge neutrality level.

The Nature of Electron Lone Pairs in BiVO4

The electronic structure of BiVO4 has been studied by x-ray photoelectron, x-ray absorption, and x-ray emission spectroscopies, in comparison with density functional theory calculations. Our results confirm both the direct band gap of 2.48 eV and that the Bi 6s electrons hybridize with O 2p to form antibonding “lone pair” states at the top of the valence band. The results highlight the suitability of combining s2 and d0 cations to produce photoactive ternary oxides.

Perovskite Sr‐Doped LaCrO3 as a New p‐Type Transparent Conducting Oxide

Epitaxial La1-x Srx CrO3 deposited on SrTiO3 (001) is shown to be a p-type transparent conducting oxide with competitive figures of merit and a cubic perovskite structure, facilitating integration into oxide electronics. Holes in the Cr 3d t2g bands play a critical role in enhancing p-type conductivity, while transparency to visible light is maintained because low-lying d-d transitions arising from hole doping are dipole forbidden.

Band structure of ZnO from resonant x-ray emission spectroscopy

Soft x-ray emission and absorption spectroscopy of the O K-edge are employed to investigate the electronic structure of wurtzite ZnO(0001). A quasiparticle band structure calculated within the GW approximation agrees well with the data, most notably with the energetic location of the Zn 3d-O 2p hybridized state and the anisotropy of the absorption spectra. Dispersion in the band structure is mapped using the coherent k-selective part of the resonant x-ray emission spectra. We show that a more extensive mapping of the bands is possible in the case of crystalline anisotropy such as that found in ZnO.

Clean wurtzite InN surfaces prepared with atomic hydrogen

Conventional methods of surface preparation for III–V semiconductors, such as thermal annealing and sputtering, are severely limited for InN, resulting in In-enrichment and the introduction of donorlike defects. This is explained in terms of the unusually low Γ-point conduction band minimum of InN with respect to its Fermi stabilization energy. Here, low energy atomic hydrogen irradiation is used to produce clean wurtzite InN surfaces without such detrimental effects. A combination of x-ray photoelectron spectroscopy (XPS) and high-resolution electron-energy-loss spectroscopy was used to confirm the removal of atmospheric contaminants. Low energy electron diffraction revealed a (1×1) surface reconstruction after cleaning. Finally, XPS revealed In∕N intensity ratios consistent with a predominantly In polarity InN film terminated by In-adlayers in analogy with c-plane GaN{0001}-(1×1) surfaces.

Photoluminescence spectroscopy of bandgap reduction in dilute InNAs alloys

Photoluminescence (PL) has been observed from dilute InNxAs1–x epilayers grown by molecular-beam epitaxy. The PL spectra unambiguously show band gap reduction with increasing N content. The variation of the PL spectra with temperature is indicative of carrier detrapping from localized to extended states as the temperature is increased. The redshift of the free exciton PL peak with increasing N content and temperature is reproduced by the band anticrossing model, implemented via a (5×5) k·p Hamiltonian.

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.