ABSTRACT
Heat treatment in an oxygen-containing medium is a necessary procedure in the technology of forming photodetectors and emitters based on lead chalcogenides. Lead chalcogenide layers (PbS, PbSe) were prepared via a chemical bath deposition method. Surface oxidation of lead chalcogenide layers was analyzed using X-ray diffraction and Raman spectroscopy methods, and thermodynamic analysis of the oxidation of PbSe and PbS layers was also performed. The calculated phase diagrams from 20 °C to 500 °C showed good agreement with the experimental results. According to the thermodynamic analysis, the oxidation products depend on the initial composition of the layers and temperature of the annealing. In some cases, the formation of a separate metallic phase Pb is possible along with the formation of lead oxide PbO and other oxides. The performed thermodynamic analysis makes it possible to substantiate the two-stage annealing temperature regimes which ensure an increase in the speed of photodetectors.
ABSTRACT
Metal-free 5,10,15,20-tetraferrocenylporphyrin and 5,10-bisferrocenyl-15,20-bisphenylporphyrin have been prepared and characterized by UV-Vis, MCD, (1)H, (13)C, and variable-temperature NMR, APCI- and ESI-MS, and Mössbauer spectroscopy, while their redox properties were investigated using electrochemical (cyclic voltammetry and differential pulse voltammetry), spectroelectrochemical, and chemical oxidation approaches. The electronic structure calculations at Density Functional Theory level reveal that both compounds adopt saddle conformations and the HOMOs in both complexes are predominantly metal-centered, while the LUMOs predominantly consist of porphyrin pi* orbitals. In spite of the rotational freedom of ferrocenyl substituents at room temperature, both metal-free 5,10,15,20-tetraferrocenylporphyrin and 5,10-bisferrocenyl-15,20-bisphenylporphyrin are able to form mixed-valence states upon the successive ferrocene-based two- and one-electron oxidations, respectively, as confirmed by UV-Vis, MCD, Mössbauer, electro-, and spectroelectrochemical methods, and thus, the earlier suggested (Boyd et al. Chem. Commun., 1999, 637) requirements for the formation of mixed-valence states in ferrocene-containing porphyrins should be revised.
