Structure and Mechanism of Conduction of Semiconductor Glasses

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Abstract
The area of glass formation in the system GeO2‐P4O10‐V2O5 and the properties of the glasses in this area were determined. The glasses displayed electronic conduction at room temperature (25°C). Resistivity ranged from 500 ohm‐cm to 109 ohm‐cm at 25°C. Some of the glasses had unusual negative temperature coefficients of resistance of the order of ‐760,000 ppm °C−1 in the range 25° to ‐55°C. Volt‐ampere characteristics indicated nonlinearity suitable for thermistor application. Other unusual properties included high refractive indices from 1.6 to >2.0 and dielectric constants from 6 to 33 at 1 Mc and 25°C. Values of loss‐tangents, however, were high. Infrared spectra indicated that the V5+ ion existed in sixfold coordination in the glassy state as well as in the devitrified crystalline state. The normal vibrational frequency of the V–O bond at 1015 cm−1 was observed for all glasses in the system. Property versus composition curves indicated that density, refractive index, and dielectric constant of ternary glasses in the system do not obey the additivity rule. The density versus mole % V2O5 curve goes through a minimum. Derived quantities from experimental data indicate pronounced influence of V2O5 on oxygen packing in the system. Addition of SiO2, even in small quantities, destroys glass formation. The structure of these glasses, which differs from that of silicate glasses, is discussed. A mechanism of conduction is suggested, based on evidence from magnetic susceptibility, chemical analysis, activation energy, and infrared spectra.