Understanding the Role of Copper Vacancies in Photoelectrochemical CO2 Reduction on Cuprous Oxide.

Controlling the electronic and photoexcited properties of cuprous oxide (Cu2O) through slight modifications of the synthesis method can impact a wide range of emerging technologies. Herein, we consider copper vacancies in Cu2O as a prototype of a p-type oxide semiconductor for studying the impact of crystal and electronic structure on carbon dioxide photoreduction. Oriented films of copper vacancy modulated Cu2O consisting of nano twin structures are electrodeposited by changing the potential in an aqueous alkaline copper(II)-lactate solution. The copper vacancies introduce tail states inside the band gap, improving the hole concentration and facilitating the charge separation and transfer in the Cu2O photocathode. This study gives an in-depth view of how a cation-deficient structure regulates and promotes photoelectrochemical activity toward CO2 reduction.

Controlling the Phase Segregation in Mixed Halide Perovskites through Nanocrystal Size.

Mixed halide perovskites are one of the promising candidates in developing solar cells and light-emitting diodes (LEDs), among other applications, because of their tunable optical properties. Nonetheless, photoinduced phase segregation, by formation of segregated Br-rich and I-rich domains, limits the overall applicability. We tracked the phase segregation with increasing crystalline size of CsPbBr3-x I x and their photoluminescence under continuous-wave laser irradiation (405 nm, 10 mW cm-2) and observed the occurrence of the phase segregation from the threshold size of 46 ± 7 nm. These results have an outstanding agreement with the diffusion length (45.8 nm) calculated also experimentally from the emission lifetime and segregation rates. Furthermore, through Kelvin probe force microscopy, we confirmed the correlation between the phase segregation and the reversible halide ion migration among grain centers and boundaries. These results open a way to achieve segregation-free mixed halide perovskites and improve their performances in optoelectronic devices.

Hidden energy levels? Carrier transport ability of CdS/CdS1-xSex quantum dot solar cells impacted by Cd-Cd level formation.

In quantum dot sensitized solar cells (QDSSC), a cascade energy level structure controlled by assembly of cadmium-chalcogenide quantum dots can remarkably improve the sunlight harvesting and charge carrier lifetime. Despite the advantages of using co-sensitizers, energy conversion efficiencies are still low. An increased understanding of the causes of the low photoconversion efficiency (PCE) will contribute to the development of a straightforward approach to improve solar cell performance by exploiting co-sensitization. Herein we discuss how an excess of cadmium causes structural disorder and defect levels impacting the PCE of QDSSC devices. Thus, outer CdS1-xSex/inner CdS QD-co-sensitized B,N,F-co-doped-TiO2 nanotubes (BNF-TNT) were prepared. Chalcogenides were deposited by the SILAR method on BNF-TNT, varying the load of CdS as the inner sensitizer, while for CdS1-xSex, five SILAR cycles were used (5-CdS1-xSex), controlling the nominal S/Se molar ratio of the ternary alloy. Cd defects named as Cd-Cd energy levels were observed during CdS sensitization. Although incorporation of outer CdS1-xSex provides a tunable band gap to achieve good band alignment for carrier separation, Cd-Cd energy levels in the sensitizers act as recombination centers, limiting the overall electron flow at the BNF-TNT/CdS/CdS1-xSex interface. A maximum PCE of 2.58% was reached under standard AM 1.5G solar illumination at 100 mW cm-2. Additional limitations of SILAR as a deposition strategy of QDs are also found to influence the PCE of QDSSC.

On the reactivity of sulfosalts in cyanide aqueous media: structural, bonding and electronic aspects.

The reactivity of the ruby silver minerals proustite (3Ag(2)S⋅As(2)S(3)) and pyrargyrite (3Ag(2)S⋅Sb(2)S(3)) was studied with two types of electrodes: a carbon-paste electroactive electrode (CPEE) and a paraffin-impregnated graphite electrode (PIGE). Polycrystalline samples of α-Ag(2)S (acanthite), As(2)S(3) (orpiment), Sb(2)S(3) (stibnite), Ag(3)AsS(3) (proustite), Ag(3)SbS(3) (pyrargyrite), and three samples of the proustite-pyrargyrite solid solution series were synthesized from pure elements by a solid-state reaction method. Phase identification of samples was carried out by XRD and chemical homogeneity was checked by SEM-EDS. Besides, sulfosalts were characterized by diffuse reflectance spectroscopy (DRS). Flat-band and formal potentials of sulfosalts were determined by the Mott-Schottky method and differential pulse abrasive stripping voltammetry, respectively. Band structure, bonding and solid-state structure are considered to investigate the oxidation and reduction of the solids. A ligand-to-metal charge transfer (LMCT) transition from the AsS(3) (or SbS(3)) group to Ag is related to ease of reducing the pyrargyrite-proustite series. Despite the increase in the amount of As (Sb) in Ag(3)SbS(3) (Ag(3)AsS(3)), reactivity is similar due to the similarity of the solid-state structures, and the same oxidation states of S, As, Sb and Ag species in the lattice. However, the nature of the pnictogen (As or Sb) changes the position of the conduction and valence band edges and modulates the reactivity of the pyrargyrite-proustite series. Anodic dissolution occurs by hole transfer from the top of the valence band that is formed mainly by the states of the AsS(3) and SbS(3) groups. Meanwhile, silver reduction occurs by electron transfer from the Ag 5s orbitals located at the bottom of the conduction band. The difficulty in dissolving proustite and pyrargyrite in cyanide is related to the presence of pyramidal AsS(3) and SbS(3) groups in these sulfosalts.