ZnSe Etching of Zn‐Rich Cu2ZnSnSe4: An Oxidation Route for Improved Solar‐Cell Efficiency

Cu₂ZnSnSe₄ kesterite compounds are some of the most promising materials for low‐cost thin‐film photovoltaics. However, the synthesis of absorbers for high‐performing devices is still a complex issue. So far, the best devices rely on absorbers grown in a Zn‐rich and Cu‐poor environment. These off‐stoichiometric conditions favor the presence of a ZnSe secondary phase, which has been proved to be highly detrimental for device performance. Therefore, an effective method for the selective removal of this phase is important. Previous attempts to remove this phase by using acidic etching or highly toxic organic compounds have been reported but so far with moderate impact on device performance. Herein, a new oxidizing route to ensure efficient removal of ZnSe is presented based on treatment with a mixture of an oxidizing agent and a mineral acid followed by treatment in an aqueous Na₂S solution. Three different oxidizing agents were tested: H₂O₂, KMnO₄, and K₂Cr₂O₇, combined with different concentrations of H₂SO₄. With all of these agents Se^2? from the ZnSe surface phase is selectively oxidized to Se⁰, forming an elemental Se phase, which is removed with the subsequent etching in Na₂S. Using KMnO₄ in a H₂SO₄‐based medium, a large improvement on the conversion efficiency of the devices is observed, related to an improvement of all the optoelectronic parameters of the cells. Improvement of short‐circuit current density (J_sc) and series resistance is directly related to the selective etching of the ZnSe surface phase, which has a demonstrated current‐blocking effect. In addition, a significant improvement of open‐circuit voltage (V_oc), shunt resistance (R_sh), and fill factor (FF) are attributed to a passivation effect of the kesterite absorber surface resulting from the chemical processes, an effect that likely leads to a reduction of nonradiative‐recombination states density and a subsequent improvement of the p–n junction.     

Fractional Discrete-Time Signal Processing: Scale Conversion and Linear Prediction

A generalization of the linear prediction for fractional steps isreviewed, widening well-known concepts and results. This prediction isused to derive a causal interpolation algorithm. A reconstructionalgorithm for the situation where averages are observed is alsopresented. Scale conversion of discrete-time signals is studied takingas base the fractional discrete-time system theory. Some simulationresults to illustrate the behaviour of the algorithms will be presented.A new algorithm for performing the zoom transform is also described.     

Slow release of NO by microporous titanosilicate ETS-4

A novel approach to designing nitric oxide (NO) storage and releasing microporous agents based on very stable, zeolite-type silicates possessing framework unsaturated transition-metal centers has been proposed. This idea has been illustrated with ETS-4 [Na(9)Si(12)Ti(5)O(38)(OH)·xH(2)O], a titanosilicate that displays excellent NO adsorption capacity and a slow releasing kinetics. The performance of these materials has been compared to the performance of titanosilicate ETS-10, [(Na,K)(2)Si(5)TiO(13)·xH(2)O], of benchmark zeolites mordenite and CaA, and of natural and pillared clays. DFT periodic calculations have shown that the presence of water in the pores of ETS-4 promotes the NO adsorption at the unsaturated (pentacoordinated) Ti(4+) framework ions.     

Environmental Applications of Excitation-Emission Spectrofluorimetry: An In-Depth Review II

Abstract: This part is devoted to the environmental applications of excitation-emission spectrofluorimetry (EES): Characterization of chromophoric dissolved organic matter (CDOM) in drinking waters, rivers, fog waters, lakes, oceans, leachates, wastewaters, sluge, bioreactor membrane foulants, and soils; characterization of extracellular polymeric substances in sludges; study of interactions between CDOM and organic pollutants in soils; and quantification of organic pollutants in waters and soils. This part includes the pretreatment of samples, and the environmental applications of the technique are discussed, including its application to bioremediation of wastewaters.

More than 200 references (focusing mainly on the last 10 years) from all kinds of journals (environment, analytical chemistry, biotechnology) have been carefully revised and included in this part of the article.     

Face-Fusion of Icosahedral Boron Hydride Increases Affinity to γ-Cyclodextrin: closo,closo-[B21H18]− as an Anion with Very Low Free Energy of Dehydration

The supramolecular recognition of closo,closo-[B₂₁H₁₈]⁻ by cyclodextrins (CDs) has been studied in aqueous solution by isothermal titration calorimetry and nuclear magnetic resonance spectroscopy. These solution studies follow up on previous mass-spectrometric measurements and computations, which indicated the formation and stability of CD ⋅ B₂₁H₁₈⁻ complexes in the gas phase. The thermodynamic signature of solution-phase binding is exceptional, the association constant for the γ-CD complex with B₂₁H₁₈⁻ reaches 1.8×10⁶ M⁻¹, which is on the same order of magnitude as the so far highest observed value for the complex between γ-CD and a metallacarborane. The nature of the intermolecular interaction is also examined by quantum-mechanical computational protocols. These suggest that the desolvation penalty, which is particularly low for the B₂₁H₁₈⁻ anion, is the decisive factor for its high binding strength. The results further suggest that the elliptical macropolyhedral boron hydride is another example of a CD binder, whose extraordinary binding affinity is driven by the chaotropic effect, which describes the intrinsic affinity of large polarizable and weakly solvated chaotropic anions to hydrophobic cavities and surfaces in aqueous solution.     

Apparently complex high-pressure phase of gallium as a simple modulated structure

The phase of gallium GaII, with symmetry C222(1) and 104 atoms per unit cell, has been recently reported as an example of structural complexity under high pressure. It is shown here that this phase is a simple modulated distortion of an average structure of Fddd symmetry with all atoms structurally equivalent. The modulation can be described with only 4 parameters and satisfies symmetry properties described by a centrosymmetric superspace group. The structural distortion is dominated by a frozen transversal mode associated with a single irreducible representation of Fddd, with a wave vector on the line Q, at an edge of the Brillouin zone. The average structure can be related with an hcp configuration through simple sliding of hcp layers, reminiscent of the hcp-bcc Bürgers mechanism.     

Non-monotonic response of waxy oil gel strength to cooling rate

The oil at high temperatures in the reservoir loses heat to the surroundings and is submitted to different shear stresses while it is produced and transported. Thermal and shear histories have great influence on the rheological characteristics of waxy oils at low temperature. Wax crystals precipitate during cooling, building up a percolated matrix that entraps the oil and consequently, forms a gel-like structure. One of the main parameters that affect the crystals’ morphology and therefore the gel strength is the cooling rate. Although the oil static cooling has been widely studied in the literature, many questions are still open. The current work analyzes the influence of the cooling rate on the gel strength and on the dynamic moduli (G′ and G″) of a waxy model oil. Microscopic images of wax crystals were obtained and a hypothesis to explain the non-monotonic response of the rheological parameters as a function of the cooling rate is proposed based on the crystals’ morphology.     

“Geländer” macrocycles: Synthesis,chirality and racemisation barriers

A new class of axially-chiral o,o′-bridged biphenyls containing etheroxime chains was obtained in good yields by the macrocyclisation reaction of o,o′-diformylbiphenyl dioxime with several ditosylated or dibrominated reagents. In all cases the enantiomers of the compounds were separated by HPLC using a chiral column (Chiralpack IC) and the stability of the enantiomers (barriers of racemisation) was investigated employing chiral HPLC or chiral Dynamic HPLC techniques. A slight influence on the barrier to rotation was noticed when the enantiomerisation was performed in the presence of suitable alkali cations.     

Kinetics of the deprotonation of methylnitroacetate by amines: unusually high intrinsic rate constants for a nitroalkane

A kinetic study of the reversible deprotonation of methylnitroacetate (4H) by primary aliphatic amines, secondary alicyclic amines, hydroxide ion, and water in water at 25 degrees C and in 50% DMSO/50% water (v/v) at 20 degrees C is reported. Intrinsic rate constants, k0, determined by extrapolation or interpolation of Br?nsted plots have been determined. In comparison to proton transfers involving other nitroalkanes, the intrinsic rate constants for 4H are exceptionally high; for example, log k0 for the reaction of 4H with secondary alicyclic amines in water (1.22) is 1.81 log units higher than log k0 for nitromethane (-0.59), while in 50% DMSO/50% water, log k0 for 4H (2.44) is 1.71 log units higher than that for nitromethane (0.73). A general discussion of the factors affecting intrinsic rate constants of proton transfer from nitroalkanes is presented; it provides the context for an understanding as to why k0 is so high for the proton transfers from 4H. The correlation between intrinsic rate constants for the addition of nucleophiles to alkenes of the type R'R' 'C=CXY and the intrinsic rate constants of proton transfers from carbon acids of the type H2CXY is also discussed as a general proposition as well as with specific reference to the Ph(SMe)C=C(NO2)CO2Me/H2C(NO2)CO2Me pair.