Band Alignments, Electronic Structure, and Core-Level Spectra of Bulk Molybdenum Dichalcogenides (MoS<inf>2</inf>, MoSe<inf>2</inf>, and MoTe<inf>2</inf>)

A comprehensive study of bulk molybdenum dichalcogenides is presented with the use of soft and hard X-ray photoelectron (SXPS and HAXPES) spectroscopy combined with hybrid density functional theory (DFT). The main core levels of MoS2, MoSe2, and MoTe2 are explored. Laboratory-based X-ray photoelectron spectroscopy (XPS) is used to determine the ionization potential (IP) values of the MoX2 series as 5.86, 5.40, and 5.00 eV for MoSe2, MoSe2, and MoTe2, respectively, enabling the band alignment of the series to be established. Finally, the valence band measurements are compared with the calculated density of states which shows the role of p-d hybridization in these materials. Down the group, an increase in the p-d hybridization from the sulfide to the telluride is observed, explained by the configuration energy of the chalcogen p orbitals becoming closer to that of the valence Mo 4d orbitals. This pushes the valence band maximum closer to the vacuum level, explaining the decreasing IP down the series. High-resolution SXPS and HAXPES core-level spectra address the shortcomings of the XPS analysis in the literature. Furthermore, the experimentally determined band alignment can be used to inform future device work

Multi-Phase Sputtered TiO2-Induced Current–Voltage Distortion in Sb2Se3 Solar Cells

Despite the recent success of CdS/Sb2Se3 heterojunction devices, cadmium toxicity, parasitic absorption from the relatively narrow CdS band gap (2.4 eV) and multiple reports of inter-diffusion at the interface forming Cd(S,Se) and Sb2(S,Se)3 phases, present significant limitations to this device architecture. Among the options for alternative partner layers in antimony chalcogenide solar cells, the wide band gap, non-toxic titanium dioxide (TiO2) has demonstrated the most promise. It is generally accepted that the anatase phase of the polymorphic TiO2 is preferred, although there is currently an absence of analysis with regard to phase influence on device performance. This work reports approaches to distinguish between TiO2 phases using both surface and bulk characterization methods. A device fabricated with a radio frequency (RF) magnetron sputtered rutile-TiO2 window layer (FTO/TiO2/Sb2Se3/P3HT/Au) achieved an efficiency of 6.88% and near-record short–circuit current density (Jsc) of 32.44 mA cm−2, which is comparable to established solution based TiO2 fabrication methods that produced a highly anatase-TiO2 partner layer and a 6.91% efficiency device. The sputtered method introduces reproducibility challenges via the enhancement of interfacial charge barriers in multi-phase TiO2 films with a rutile surface and anatase bulk. This is shown to introduce severe S-shaped current–voltage (J–V) distortion and a drastic fill–factor (FF reduction in these devices

Self-Compensation in Transparent Conducting F-Doped SnO2

The factors limiting the conductivity of fluorine-doped tin dioxide (FTO) produced via atmospheric pressure chemical vapor deposition are investigated. Modeling of the transport properties indicates that the measured Hall effect mobilities are far below the theoretical ionized impurity scattering limit. Significant compensation of donors by acceptors is present with a compensation ratio of 0.5, indicating that for every two donors there is approximately one acceptor. Hybrid density functional theory calculations of defect and impurity formation energies indicate the most probable acceptor-type defects. The fluorine interstitial defect has the lowest formation energy in the degenerate regime of FTO. Fluorine interstitials act as singly charged acceptors at the high Fermi levels corresponding to degenerately n-type films. X-ray photoemission spectroscopy of the fluorine impurities is consistent with the presence of substitutional F O donors and interstitial F i in a roughly 2:1 ratio in agreement with the compensation ratio indicated by the transport modeling. Quantitative analysis through Hall effect, X-ray photoemission spectroscopy, and calibrated secondary ion mass spectrometry further supports the presence of compensating fluorine-related defects

A hard x-ray photoemission study of transparent conducting fluorine-doped tin dioxide

Fluorine-doped tin oxide (FTO) is a commercially successful transparent conducting oxide with very good electrical (resistivities < 1×103 Ω·cm) and optical properties (transmittance > 85%). These properties coupled with cheap and large-scale deposition on float-glass lines means FTO has found commercial use in, for example, low emissivity windows and solar cells. However, despite its widespread application, a detailed understanding is lacking of the doping and defects in FTO. Recent work [1] has suggested that the fluorine interstitial plays a major role in limiting the conductivity of FTO. Here we present synchrotron radiation high energy x-ray photoemission spectroscopy (XPS) of the fluorine 1s core level of FTO films without in situ surface preparation. This probes deeper than standard XPS and shows that the fluorine interstitial is present not just at the surface of the films and is not an artefact of argon ion sputtering for surface preparation

Electron beam evaporation of superconductor-ferromagnet heterostructures

We report on the electronic and magnetic properties of superconductor-ferromagnet heterostructures fabricated by electron beam evaporation on to unheated thermally oxidised Si substrates. Polycrystalline Nb thin films (5 to 50&#xA0;nm thick) were shown to possess reliably high superconducting critical temperatures ([Formula: see text]), which correlate well with the residual resistivity ratio (RRR) of the film. These properties improved during ex-situ annealing, resulting in [Formula: see text] and [Formula: see text]RRR increases of up 2.2&#xA0;K ([Formula: see text] 40% of the pre-annealed [Formula: see text]) and 0.8 ([Formula: see text] 60% of the pre-annealed RRR) respectively. Nb/Pt/Co/Pt heterostructures showed substantial perpendicular anisotropy in the ultrathin limit (&#x2264;&#x2009;2.5&#xA0;nm), even in the extreme limit of Pt(0.8&#xA0;nm)/Co(1&#xA0;nm)/Pt(0.6&#xA0;nm). These results point to the use of electron beam evaporation as route to line-of-sight deposited, low-thickness, high quality Nb-based superspintronic multilayers

Electron beam evaporation of superconductor-ferromagnet heterostructures

We report on the electronic and magnetic properties of superconductor-ferromagnet heterostructures fabricated by electron beam evaporation on to unheated thermally oxidised Si substrates. Polycrystalline Nb thin films (5 to 50 nm thick) were shown to possess reliably high superconducting critical temperatures ([Formula: see text] ), which correlate well with the residual resistivity ratio (RRR) of the film. These properties improved during ex-situ annealing, resulting in [Formula: see text] and [Formula: see text] RRR increases of up 2.2 K ([Formula: see text] 40% of the pre-annealed [Formula: see text] ) and 0.8 ([Formula: see text] 60% of the pre-annealed RRR) respectively. Nb/Pt/Co/Pt heterostructures showed substantial perpendicular anisotropy in the ultrathin limit (≤ 2.5 nm), even in the extreme limit of Pt(0.8 nm)/Co(1 nm)/Pt(0.6 nm). These results point to the use of electron beam evaporation as route to line-of-sight deposited, low-thickness, high quality Nb-based superspintronic multilayers

Ge 4s2 lone pairs and band alignments in GeS and GeSe for photovoltaics

The Engineering and Physical Sciences Research Council (EPSRC) is acknowledged for providing funding to M. J. S., J. E. N. S, and T. J. F. (Grant No. EP/L01551X/1), H. S. (Grant No. EP/N509693/1), L. A. H. J. (Grant No. EP/R513271/1), and V. R. D. and T. D. V. (Grant No. EP/N015800/1). JMS is supported by a UK Research and Innovation (UKRI) Future Leaders Fellowship (Grant No. MR/T043121/1), and previously held a University of Manchester Presidential Fellowship. The XRD facility was supported by the EPSRC under Grant No. EP/P001513/1. Diamond Light Source is acknowledged for providing beam time on beamline I09 under proposals SI21431-1 and SI23160-1. Computational modelling was performed on the UK Archer high-performance computing facility via membership of the UK Materials Chemistry Consortium, which is funded by the EPSRC (Grant No. EP/L000202, EP/R029431).Germanium sulfide and germanium selenide bulk crystals were prepared using a melt growth technique. X-ray photoemission spectroscopy (XPS) was used to determine ionisation potentials of 5.74 and 5.48 eV for GeS and GeSe respectively. These values were used with the previously-measured band gaps to establish the natural band alignments with potential window layers for solar cells and to identify CdS and TiO2 as sensible choices. The ionisation potential of GeS is found to be smaller than in comparable materials. Using XPS and hard X-ray photoemission (HAXPES) measurements in conjunction with density-functional theory calculations, we demonstrate that stereochemically active Ge 4s lone pairs are present at the valence-band maxima. Our work thus provides direct evidence for active lone pairs in GeS and GeSe, with important implications for the applications of these and related materials such as Ge-based perovskites.Publisher PDFPeer reviewe