Electroluminescence (EL) on
normalZnS
was studied in aqueous solutions containing various redox species. For species able to generate strongly oxidizing intermediates, such as peroxydisulfate or hydrogen peroxide, bright blue luminescence was observed during cathodic polarization at potentials near to or negative of flatband potential
false(VFBfalse)
of
normalZnS
. For solutions containing supporting electrolyte alone at various pH's, no emission was detectable even at potentials 7V negative of
VFB
. This suggests that minority carrier (hole) injection is responsible for the initiation of EL. The peak energy of the EL spectrum was much smaller (by 1 eV) than the bandgap of
normalZnS
, suggesting that the radiative recombination is through intermediate luminescent centers. Under steady‐state conditions, the EL intensity was proportional to the square of the current, suggesting that EL intensity is dominated by the recombination of electron hole pairs at luminescent centers. In the early part of a potential pulse (especially the first pulse), the growth behavior of EL intensity was strongly affected by the electron trapping of the empty upper luminescent states. The location of the EL spectra depended on the current density and EL intensity; with increasing EL intensity, a significant blue shift of the emission peak was observed. These results suggest that the overall radiative recombination rate might be limited by electron transfer (through a tunneling mechanism) from the occupied upper luminescent states to the empty lower luminescent states. An EL efficiency of 0.2% can be achieved by operating at a current density of 25 mA/cm2.
The stability of n-Si vacuum-coated with metal-free phthalocyanine (H2Pc) and copper phthalocyanine (CuPc) was studied as a function of the light intensity and redox couple in aqueous solutions. Although the photocurrent at an n-Si coated with H2Pc or CuPc decayed slowly at low light intentsities (1 mW/cm1 2), photopassivation was rapid at higher light intensities (100 mW/cm2). The magnitude of photocurrent and the inhibition of photocorrosion depended upon the solution conditions. Addition of iodine, which is a dopant for the Pc layer, led to larger photoeffects and a lower rate of photopassivation, although the electrode was still unstable after longer irradiation times. Further improvement in stability was observed in the presence of the highly concentrated electrolyte, 11 M LiCl.
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