We have investigated the effects of deliberate heavy metals contamination on dark current and image defects in CMOS Image Sensors (CIS). Analysis of dark current in these imager dice has revealed different behaviors among most important 3d metals present in the process line. We have implanted directly in 3 Mega array pixels the following metals: Cr, V, Cu, Ni, Fe, Ti, Mo, W, Al and Zn. Analyzing the dark current "spectrum" as obtained for fixed integration periods of time by means of standard image-testing equipment, these impurities can be identified and detected with a sensitivity of ∼ 10 9 traps/cm 3 or higher.
The concentration of rare-earth elements and yttrium (REY) was investigated in dissolved phase, suspended particulate matter, and seafloor sediments of the western coastal area of the Gulf of Thailand. The samples show Eu and Gd positive anomalies in the shale-normalized REY patterns, especially in the suspended particulate matter. On the other hand, a very high REE content was detected in the coastal waters, probably due to the weathering produced by the Mae Klong river waters on rare-earth element (REE)-rich accessory minerals coming from terrains and mineral deposits cropping out in the studied area. The shale-normalized patterns of yttrium and REE estimated for the dissolved phase show an enrichment of medium rare-earth elements (MREE), characteristic of extensive water-rock interactions and weathering occurring in the continental environment. The REE concentrations of suspended particulate, normalized to the REE concentrations in each sediment sampled from the tidal flat, show the same behaviour of the experimentally determined apparent REE bulk distribution coefficients [1] for pH values ranging from about 5.5 to 6.2. Since the REY concentration of the water masses is controlled by the oceanographic features of the studied area, riverine inputs, and ionic straight, we suppose that the dissolved phase represents a mix of truly dissolved and colloidal pool (<0.2 µm) in which REY were enriched during the rock-water interactions of continental environment. In the estuarine system, the salt-induced coagulation of colloidal pool takes place and an authigenic fraction of suspended matter is formed, assuming the typical REE behaviour due to rock-water interactions.
Various measurement techniques are compared and the most suitable methods for contamination detection are identified. The results of this study show that it is not possible to define a unique recipe that can be applied in all cases. Concerning metal contaminants, the stratigraphic in-depth distribution and hence the diffusivity of contaminants determines the most effective approach. Iron and palladium are chosen as the examples of fast diffusers, molybdenum and tungsten as slow diffusers. Fast diffusers like iron and palladium diffuse through several hundred microns during an ordinary thermal treatment. Minority carrier lifetime measurements are probably the best choice to detect these contaminants. Molybdenum and tungsten do not diffuse deep enough to be efficiently revealed by recombination lifetime measurements, but are easily revealed in the silicon volume by DLTS. Because of their low diffusivity, a very small amount of these elements per unit surface may result in a significant concentration in the near-surface region where devices are built. Ion implantation is confirmed to be an important source of metal contamination. It is shown that ion implantation can be responsible both for iron contamination and for contamination by slow diffusers, such as molybdenum and tungsten. A procedure for monitoring molybdenum and tungsten contamination in ion implantation processes by DLTS is defined and calibrated. Finally, the efficiency of some gettering techniques in reducing iron, molybdenum and tungsten contamination is discussed. Gettering is found to be active at relatively high contaminant concentrations, but low contamination levels are not gettered under our experimental conditions. Carbon implantation showed partial efficiency in gettering molybdenum and tungsten, whereas gettering did not take place after silicon implantation.
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