Degradation and rejuvenation studies of AC electroluminescent ZnS:Cu,Cl phosphors

We report detailed degradation and rejuvenation studies of AC electroluminescence (EL) of the phosphor ZnS:Cu,Cl, aiming to better understand the physical mechanisms that control EL emission. We find that the AC EL emission spectra vary considerably with the AC driving frequency but all spectra can be fit to a sum of four Gaussians. During degradation, although there is a large overall decrease in amplitude, the shape of the emission spectra measured at a given AC frequency does not change. Annealing the samples after they are significantly degraded can rejuvenate the phosphors with a maximum rejuvenation occurring (for fixed annealing times) near 180 °C. Further, these test cells can be degraded and rejuvenated multiple times. However studies at slightly higher annealing temperatures (240 °C) show significant thermal degradation and, perhaps more importantly, a change in the spectral shape; this likely indicates that two distinct mechanisms are then operative. In extended x-ray absorption fine structure (EXAFS) experiments we find that the CuS nanoprecipitates in the ZnS host (∼ 75% of the Cu is in the CuS precipitates) do not change significantly after the 240 °C anneal; these experiments also provide a more detailed comparison of the local structure about Cu in pure CuS, and in ZnS:Cu,Cl. In addition, the EXAFS experiments also place an upper limit on the fraction of possible interstitial Cu sites, proposed as a blue emission center, at less than 10%. The combined experiments place strong constraints on the mechanisms for degradation and rejuvenation and suggest that EL degradation is most likely caused by either Cu or Cl diffusion under high E-fields, while thermal diffusion at slightly elevated temperatures without E-fields present, re-randomizes the (isolated) dopant distributions. Higher T anneals appear to damage the sharp tips on the precipitates.