First-principles study of the optoelectronic properties and photovoltaic absorber layer efficiency of Cu-based chalcogenides

Cu-based chalcogenides are promising materials for thin-film solar cells with more than 20% measured cell efficiency. Using first-principles calculations based on density functional theory, the optoelectronic properties of a group of Cu-based chalcogenides Cu$_2$-II-IV-VI$_4$ is studied. They are then screened with the aim of identifying potential absorber materials for photovoltaic applications. The spectroscopic limited maximum efficiency (SLME) introduced by Yu and Zunger is used as a metric for the screening. After constructing the current-voltage curve, the maximum spectroscopy dependent power conversion efficiency is calculated from the maximum power output. The role of the nature of the band gap, direct or indirect, and also of the absorptivity of the studied materials on the maximum theoretical power conversion efficiency is studied. Our results show that Cu$_2$-II-GeSe$_4$ with II=Cd and Hg, and Cu$_2$-II-SnS$_4$ with II=Cd and Zn have a higher theoretical efficiency compared to the materials currently used as absorber layer

Synthesis, characterization and thermochemistry of synthetic Pb–As, Pb–Cu and Pb–Zn jarosites

The enthalpy of formation from the elements of well characterized Pb-As, Pb-Cu, and Pb-Zn synthetic jarosites, corresponding to chemical formulas (H3O)0.68±0.03Pb0.32±0.002Fe2.86±0.14(SO4)1.69±0.08(AsO4)0.31±0.02(OH)5.59±0.28(H2O)0.41±0.02, (H3O)0.67±0.03Pb0.33±0.02Fe2.71±0.14Cu0.25±0.01(SO4)2±0.00(OH)5.96±0.30(H2O)0.04±0.002 and (H3O)0.57±0.03Pb0.43±0.02Fe2.70±0.14Zn0.21±0.01(SO4)2±0.00(OH)5.95±0.30(H2O)0.05±0.002, was measured by high temperature oxide melt solution calorimetry and gave ΔH°f = -3691.2 ± 8.6 kJ/mol, ΔH°f = -3653.6 ± 8.2 kJ/mol, and ΔH°f = -3669.4 ± 8.4 kJ/mol, respectively. Using estimated entropies, the standard Gibbs free energy of formation from elements at 298 K ΔG°f of the three compounds were calculated to be -3164.8 ± 9.1 kJ/mol, -3131.4 ± 8.7 kJ/mol, and -3153.6 ± 8.9 kJ/mol, respectively. Based on these free energies, their logKsp values are -13.94 ± 1.89, -4.38 ± 1.81 and -3.75 ± 1.80, respectively. For this compounds, a log10{Pb2+} - pH diagram is presented. The diagram shows that the formation of Pb-As jarosite may decrease aqueous arsenic and lead concentrations to meet drinking water standards. The new thermodynamic data confirm that transformation of Pb-As jarosite to plumbojarosite is thermodynamically possible

Defects and impurities in jarosite: A computer simulation study

Computer modelling techniques involving a rigid ion model have been used to investigate the defect structure and impurity site preferences in end-member K-jarosite. Calculated intrinsic vacancy energies show that the K2SO4 neutral cluster, with an energy per species of 1.34 eV, will be the most common defect in the pure phase. Defect reactions leading to vacancies on the Fe site have high energies, in excess of 4.0 eV per species, and are thus unlikely to occur in great numbers. However, the calculations show that divalent metal cations can be incorporated onto the Fe site via solution reactions with oxides leading to the formation of goethite. Calculated solution reactions are exothermic and thus predicted to be highly favourable. At K sites substitutions occur in the order Cd > Zn > Cu, but will be limited due to endothermic solution energies and structural considerations

Tournament leave-pair-out cross-validation for receiver operating characteristic analysis

Receiver operating characteristic analysis is widely used for evaluating diagnostic systems. Recent studies have shown that estimating an area under receiver operating characteristic curve with standard cross-validation methods suffers from a large bias. The leave-pair-out cross-validation has been shown to correct this bias. However, while leave-pair-out produces an almost unbiased estimate of area under receiver operating characteristic curve, it does not provide a ranking of the data needed for plotting and analyzing the receiver operating characteristic curve. In this study, we propose a new method called tournament leave-pair-out cross-validation. This method extends leave-pair-out by creating a tournament from pair comparisons to produce a ranking for the data. Tournament leave-pair-out preserves the advantage of leave-pair-out for estimating area under receiver operating characteristic curve, while it also allows performing receiver operating characteristic analyses. We have shown using both synthetic and real-world data that tournament leave-pair-out is as reliable as leave-pair-out for area under receiver operating characteristic curve estimation and confirmed the bias in leave-one-out cross-validation on low-dimensional data. As a case study on receiver operating characteristic analysis, we also evaluate how reliably sensitivity and specificity can be estimated from tournament leave-pair-out receiver operating characteristic curves.</p

Computer simulations of the interactions of the (012) and (001) surfaces of jarosite with Al, Cd, Cu2+ and Zn

Jarosite is an important mineral on Earth, and possibly on Mars, where it controls the mobility of iron, sulfate and potentially toxic metals. Atomistic simulations have been used to study the incorporation of Al3+, and the M2+ impurities Cd, Cu and Zn, in the (0 1 2) and (0 0 1) surfaces of jarosite. The calculations show that the incorporation of Al on an Fe site is favorable on all surfaces in which terminal Fe ions are exposed, and especially on the (0 0 1) [Fe3(OH)3]6+ surface. Incorporation of Cd, Cu or Zn on a K site balanced by a K vacancy is predicted to stabilize the surfaces, but calculated endothermic solution energies and the high degree of distortion of the surfaces following incorporation suggest that these substitutions will be limited. The calculations also suggest that incorporation of Cd, Cu and Zn on an Fe site balanced by an OH vacancy, or by coupled substitution on both K and Fe sites, is unfavorable, although this might be compensated for by growth of a new layer of jarosite or goethite, as predicted for bulk jarosite. The results of the simulations show that surface structure will exert an influence on uptake of impurities in the order Cu > Cd > Zn, with the most favorable surfaces for incorporation being (0 1 2) [KFe(OH)4]0 and (0 0 1) [Fe3(OH)3]6+

Evidence of random magnetic anisotropy in ferrihydrite nanoparticles based on analysis of statistical distributions

We show that the magnetic anisotropy energy of antiferromagnetic ferrihydrite depends on the square root of the nanoparticles volume, using a method based on the analysis of statistical distributions. The size distribution was obtained by transmission electron microscopy, and the anisotropy energy distributions were obtained from ac magnetic susceptibility and magnetic relaxation. The square root dependence corresponds to random local anisotropy, whose average is given by its variance, and can be understood in terms of the recently proposed single phase homogeneous structure of ferrihydrite.Comment: 6 pages, 2 figure