An electron microprobe study of luminescence centers in cassiterite

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Virginia Polytechnic Institute

An electron microprobe equipped with a device for making luminescence measurements has been used to determine the concentration of luminescence activators in zoned cassiterites of hydrothermal origin. Micron-scale growth zones contain variable amounts of Ti, Fe, W and other impurities. The impurity ions replace Sn⁴⁺ to produce luminescence centers. The relative intensity of cathodoluminescence and the amount and kind of impurity activators were simultaneously measured while scanning the growth zones with a micro-focussed electron beam.

Two distinct emission bands were observed, a yellow-green (λ ~ 565 mµ) band for Ti-activation and a blue (λ ~ 440 mµ) band for W-activation. Measurements made on a heated sample show strong thermal quenching of the Ti-activated cathodoluminescence. The decay time for the Ti-activated emission, which is independent of temperature from 21°c to 275°C, is 0.168 msec. The cathodoluminescence spectrum for W-activation closely resembles that of self-activated CaWO₄ (Leverenz, 1946) although a higher oxygen coordination (VI) for W in cassiterite is to be expected, Fe occurring with Ti appears to enhance the Ti-activated emission. Fe occurring with W or Si quenches luminescence.