Engineering Valence Band Dispersion for High Mobility p-Type Semiconductors

The paucity of high performance transparent p-type semiconductors has been a stumbling block for the electronics industry for decades, effectively hindering the route to efficient transparent devices based on p–n junctions. Cu-based oxides and subsequently Cu-based oxychalcogenides have been heavily studied as affordable, earth-abundant p-type transparent semiconductors, where the mixing of the Cu 3d states with the chalcogenide 2p states at the top of the valence band encourages increased valence band dispersion. In this article, we extend this mixing concept further, by utilizing quantum chemistry techniques to investigate ternary copper phosphides as potential high mobility p-type materials. We use hybrid density functional theory to examine a family of phosphides, namely, MCuP (M = Mg, Ca, Sr, Ba) which all possess extremely disperse valence band maxima, comparable to the dispersion of excellent industry standard n-type transparent conducting oxides. As a proof of concept, we synthesized and characterized powders of CaCuP, showing that they display high levels of p-type conductivity, without any external acceptor dopant. Lastly, we discuss the role of Cu-coordination in promoting valence band dispersion and provide design principles for producing degenerate p-type materials

Composition measurement of epitaxial Sc<inf>x</inf>Ga<inf>1-x</inf>N films

Four different methods for measuring the compositions of epitaxial ScxGa1-xN films were assessed and compared to determine which was the most reliable and accurate. The compositions of epitaxial ScxGa1-xN films with 0 ≤ x ≤ 0.26 were measured directly using Rutherford backscattering (RBS) and x-ray photoelectron spectroscopy (XPS), and indirectly using c lattice parameter measurements from x-ray diffraction and c/a ratio measurements from electron diffraction patterns. RBS measurements were taken as a standard reference. XPS was found to underestimate the Sc content, whereas c lattice parameter and c/a ratio were not reliable for composition determination due to the unknown degree of strain relaxation in the film. However, the Sc flux used during growth was found to relate linearly with x and could be used to estimate the Sc content

Resonant X ray photoelectron spectroscopy identification of atomic contributions to valence states

Valence electronic structure is crucial for understanding and predicting reactivity. Valence non resonant Xray photoelectron spectroscopy NRXPS provides a direct method for probing the overall valence electronic structure. However, it is often difficult to separate the varying contributions to NRXPS; for example, contributions of solutes in solvents or functional groups in complex molecules. In this work we show that valence resonant X ray photoelectron spectroscopy RXPS is a vital tool for obtaining atomic contributions to valence states. We combine RXPS with NRXPS and density functional theory calculations to demonstrate the validity of using RXPS to identify atomic contributions for a range of solutes both neutral and ionic and solvents both molecular solvents and ionic liquids . Furthermore, the one electron picture of RXPS holds for all of the closed shell molecules ions studied, although the situation for an open shell metal complex is more complicated. Factors needed to obtain a strong RXPS signal are investigated in order to predict the types of systems RXPS will work best for; a balance of element electronegativity and bonding type is found to be important. Additionally, the dependence of RXPS spectra on both varying solvation environment and varying local covalent bonding is probed. We find that RXPS is a promising fingerprint method for identifying species in solution, due to the spectral shape having a strong dependence on local covalency but a weak dependence on solvation environmen

An experimental and theoretical study into NaSbS &lt;sub&gt;2&lt;/sub&gt; as an emerging solar absorber

As photovoltaics have grown to become one of the dominant renewable energy generating technologies, attention has fallen upon thin-film materials as a route to lightweight, flexible and portable solar cells. NaSbS2 has recently been proposed as a non-toxic, earth abundant solar absorber for thin-film cells. In this study, we use a combined theoretical and experimental approach to characterize and assess the electronic and optical properties of NaSbS2 as an emerging solar absorber. Our results, utilising two theoretical efficiency metrics, demonstrate that NaSbS2 may be limited for use in single-junction cells by a forbidden band gap and slow absorption onset. Other features of its electronic structure, however, indicate that the material may still be promising in thermoelectric applications

An assessment of silver copper sulfides for photovoltaic applications: Theoretical and experimental insights

As the worldwide demand for energy increases, low-cost solar cells are being looked to as a solution for the future. To attain this, non-toxic earth-abundant materials are crucial, however cell efficiencies for current materials are limited in many cases. In this article, we examine the two silver copper sulfides AgCuS and Ag3CuS2 as possible solar absorbers using hybrid density functional theory, diffuse reflectance spectroscopy, XPS and Hall effect measurements. We show that both compounds demonstrate promising electronic structures and band gaps for high theoretical efficiency solar cells, based on Shockley–Queisser limits. Detailed analysis of their optical properties, however, indicates that only AgCuS should be of interest for PV applications, with a high theoretical efficiency. From this, we also calculate the band alignment of AgCuS against various buffer layers to aid in future device construction

Electronic and surface properties of Ga-doped In2O3 ceramics

The limit of solubility of Ga2O3 in the cubic bixbyite In2O3 phase was established by X-ray diffraction and Raman spectroscopy to correspond to replacement of around 6% of In cations by Ga for samples prepared at 1250 °C. Density functional theory calculations suggest that Ga substitution should lead to widening of the bulk bandgap, as expected from the much larger gap of Ga2O3 as compared to In2O3. However both diffuse reflectance spectroscopy and valence band X-ray photoemission reveal an apparent narrowing of the gap with Ga doping. It is tentatively concluded that this anomaly arises from introduction of Ga+ surface lone pair states at the top of the valence band and structure at the top of the valence band in Ga-segregated samples is assigned to these lone pair states. In addition photoemission reveals a broadening of the valence band edge. Core X-ray photoemission spectra and low energy ion scattering spectroscopy both reveal pronounced segregation of Ga to the ceramic surface, which may be linked to both relief of strain in the bulk and the preferential occupation of surface sites by lone pair cations. Surprisingly Ga segregation is not accompanied by the development of chemically shifted structure in Ga 2p core XPS associated with Ga+. However experiments on ion bombarded Ga2O3, where a shoulder at the top edge of the valence band spectra provide a clear signature of Ga+ at the surface, show that the chemical shift between Ga+ and Ga3+ is too small to be resolved in Ga 2p core level spectra. Thus the failure to observe chemically shifted structure associated with Ga+ is not inconsistent with the proposal that band gap narrowing is associated with lone pair states at surfaces and interfaces