T. D. Veal

Conductivity in transparent oxide semiconductors

Despite an extensive research effort for over 60 years, an understanding of the origins of conductivity in wide band gap transparent conducting oxide (TCO) semiconductors remains elusive. While TCOs have already found widespread use in device applications requiring a transparent contact, there are currently enormous efforts to (i) increase the conductivity of existing materials, (ii) identify suitable alternatives, and (iii) attempt to gain semiconductor-engineering levels of control over their carrier density, essential for the incorporation of TCOs into a new generation of multifunctional transparent electronic devices. These efforts, however, are dependent on a microscopic identification of the defects and impurities leading to the high unintentional carrier densities present in these materials. Here, we review recent developments towards such an understanding. While oxygen vacancies are commonly assumed to be the source of the conductivity, there is increasing evidence that this is not a sufficient mechanism to explain the total measured carrier concentrations. In fact, many studies suggest that oxygen vacancies are deep, rather than shallow, donors, and their abundance in as-grown material is also debated. We discuss other potential contributions to the conductivity in TCOs, including other native defects, their complexes, and in particular hydrogen impurities. Convincing theoretical and experimental evidence is presented for the donor nature of hydrogen across a range of TCO materials, and while its stability and the role of interstitial versus substitutional species are still somewhat open questions, it is one of the leading contenders for yielding unintentional conductivity in TCOs. We also review recent work indicating that the surfaces of TCOs can support very high carrier densities, opposite to the case for conventional semiconductors. In thin-film materials/devices and, in particular, nanostructures, the surface can have a large impact on the total conductivity in TCOs. We discuss models that attempt to explain both the bulk and surface conductivity on the basis of bulk band structure features common across the TCOs, and compare these materials to other semiconductors. Finally, we briefly consider transparency in these materials, and its interplay with conductivity. Understanding this interplay, as well as the microscopic contenders for providing the conductivity of these materials, will prove essential to the future design and control of TCO semiconductors, and their implementation into novel multifunctional devices.

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.

Universality of electron accumulation at wurtzite c- and a-plane and zinc-blende InN surfaces

Electron accumulation is found to occur at the surface of wurtzite (112¯0), (0001), and (0001¯) and zinc-blende (001) InN using x-ray photoemission spectroscopy. The accumulation is shown to be a universal feature of InN surfaces. This is due to the low Г-point conduction band minimum lying significantly below the charge neutrality level.

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.

Electronic and optical properties of single crystal SnS2: an earth-abundant disulfide photocatalyst

Tin disulfide is attractive as a potential visible-light photocatalyst because its elemental components are cheap, abundant and environmentally benign. As a 2-dimensional semiconductor, SnS2 can undergo exfoliation to form atomic layer sheets that provide high surface areas of photoactive material. In order to facilitate the deployment of this exciting material in industrial processes and electrolytic cells, single crystals of phase pure SnS2 are synthesised and analysed with modern spectroscopic techniques to ascertain the values of relevant semiconductor properties. An electron affinity of 4.16 eV, ionisation potential of 6.44 eV and work function of 4.81 eV are found. The temperature dependent band gap is also reported for this material for the first time. We confirm the valence band is formed predominately by a mixture S 3p and Sn 5s, while the conduction band consists of a mixture of Sn 5s and 5p orbitals and comment on the agreement between experiment and theory for values of band gaps.

Growth and properties of GaSbBi alloys

Molecular-beam epitaxy has been used to grow GaSb 1− x Bi x alloys with x up to 0.05. The Bi content, lattice expansion, and film thickness were determined by Rutherford backscattering and x-ray diffraction, which also indicate high crystallinity and that >98% of the Bi atoms are substitutional. The observed Bi-induced lattice dilation is consistent with density functional theory calculations. Optical absorption measurements and valence band anticrossing modeling indicate that the room temperature band gap varies from 720 meV for GaSb to 540 meV for GaSb 0.95Bi0.05, corresponding to a reduction of 36 meV/%Bi or 210 meV per 0.01 A change in lattice constant.

Valence band offset of the ZnO/AlN heterojunction determined by x-ray photoemission spectroscopy

The valence band offset of ZnO/AlN heterojunctions is determined by high resolution x-ray photoemission spectroscopy. The valence band of ZnO is found to be 0.43±0.17 eV below that of AlN. Together with the resulting conduction band offset of 3.29±0.20 eV, this indicates that a type-II (staggered) band line up exists at the ZnO/AlN heterojunction. Using the III-nitride band offsets and the transitivity rule, the valence band offsets for ZnO/GaN and ZnO/InN heterojunctions are derived as 1.37 and 1.95 eV, respectively, significantly higher than the previously determined values.

Growth, disorder, and physical properties of ZnSnN2

We examine ZnSnN2, a member of the class of materials contemporarily termed “earth-abundant element semiconductors,” with an emphasis on evaluating its suitability for photovoltaic applications. It is predicted to crystallize in an orthorhombic lattice with an energy gap of 2 eV. Instead, using molecular beam epitaxy to deposit high-purity, single crystal as well as highly textured polycrystalline thin films, only a monoclinic structure is observed experimentally. Far from being detrimental, we demonstrate that the cation sublattice disorder which inhibits the orthorhombic lattice has a profound effect on the energy gap, obviating the need for alloying to match the solar spectrum.

Polarity effects in the x-ray photoemission of ZnO and other wurtzite semiconductors

Significant polarity-related effects were observed in the near-surface atomic composition and valence band electronic structure of ZnO single crystals, investigated by x-ray photoemission spectroscopy using both Al Kα (1486.6 eV) and synchrotron radiation (150 to 1486 eV). In particular, photoemission from the lowest binding energy valence band states was found to be significantly more intense on the Zn-polar face compared to the O-polar face. This is a consistent effect that can be used as a simple, nondestructive indicator of crystallographic polarity in ZnO and other wurtzite semiconductors.

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.