Surfactant-mediated variation of band-edge emission in CdS nanocomposites

The optical-structural characteristics of the direct optical band-gap semiconducting series of surfactant template-mediated laminar (CdS)x(CdCl2)y(CnH2n+4N)z nanocomposites are reported. X-ray diffraction measurements of the nanocomposites exhibited interlaminar distances in the range 2.9-3.6 nm with observations of eighth order {0 0 l} diffraction planes indicative of a high degree of laminarity and crystallographic order. Diffuse reflectance measurements have determined that the profile of their emission spectrum is that of a direct band-gap with absorption edges in the range 2.11-2.40 eV, depending on the CdS mole fraction in the nanocomposite. Photoluminescence (PL) excitation and time-resolved PL spectroscopies give an estimate of the maximum relative absorbance of the nanocomposites at ∼420 nm while the minimum was observed at ∼560 nm. The main emission was observed at ∼700 nm with emission from doubly ionized sulphur vacancies observed at ∼615 nm at room temperature. The CdS-containing nanocomposite is thus a surfactant-mediated modular system with variable band-gap energy emission.

Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius

In this paper, we use density functional theory corrected for on-site Coulomb interactions (DFT + U) and hybrid DFT (HSE06 functional) to study the defects formed when the ceria (110) surface is doped with a series of trivalent dopants, namely, Al3+, Sc3+, Y3+, and In 3+. Using the hybrid DFT HSE06 exchange-correlation functional as a benchmark, we show that doping the (110) surface with a single trivalent ion leads to formation of a localized MCe / + O O • (M = the 3+ dopant), O- hole state, confirming the description found with DFT + U. We use DFT + U to investigate the energetics of dopant compensation through formation of the 2MCe ′ +VO ̈ defect, that is, compensation of two dopants with an oxygen vacancy. In conjunction with earlier work on La-doped CeO2, we find that the stability of the compensating anion vacancy depends on the dopant ionic radius. For Al3+, which has the smallest ionic radius, and Sc3+ and In3+, with intermediate ionic radii, formation of a compensating oxygen vacancy is stable. On the other hand, the Y3+ dopant, with an ionic radius close to that of Ce4+, shows a positive anion vacancy formation energy, as does La3+, which is larger than Ce4+ (J. Phys.: Condens. Matter 2010, 20, 135004). When considering the resulting electronic structure, in Al3+ doping, oxygen hole compensation is found. However, Sc 3+, In3+, and Y3+ show the formation of a reduced Ce3+ cation and an uncompensated oxygen hole, similar to La3+. These results suggest that the ionic radius of trivalent dopants strongly influences the final defect formed when doping ceria with 3+ cations. In light of these findings, experimental investigations of these systems will be welcome.