By O. G. Karpinskii, B. A. Evseev (auth.), Academician N. N. Sirota (eds.)
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Extra info for Chemical Bonds in Solids: Volume 4: Semiconductor Crystals, Glasses, and Liquids
Since a valence of 2- is characteristic of chalcogen ions, the excess electron brings about the metallic conductivity in these compounds. According to the hypothesis of several authors, the conduction band is formed by the d states of the RE and the valence band by the p states of the chalcogen [3,4]. To the second type may be assigned the compounds with semiconductor conductivity formed according to the laws of chemical valence (Bp/BT < 0, Eg ::::; 1-3 eV), which contain an RE having a valence of 2+.
M. Koshkin and L. G. Manyukova An additivity rule is formulated for diamond-type semiconductors. According to this rule. the energies of individual bonds in covalent crystals make additive contributions to the melting point. The application of this rule makes it possible to calculate the melting points of binary crystals with similar chemical bonding. It is shown that the validity of the additivity rule is basically related to the short-range nature of the covalent forces. A quantitati ve agreement is obtained between the thermodynamic data and the proposed chemical bonding schemes.
This also explains the fact that a sample of composition 3 has the highest diamagnetism. Composition 5 has the lowest diamagnetic susceptibility. It has been shown above that when 1 mol. %Sb20 3 is added most of the Sb ions are pentavalent. In this case, the defect concentration is sharply increased; this is due to the fact that the X=f(T) curve for this composition is higher than the other curves. In addition to this, since the pentavalent Sb ion is present (for composition 5), the radius of which is considerably less than that of Zn2+, Sb3+, and Sn'+, the diamagnetic component of the susceptibility is much lower; this is confirmed by the nature of the dependence of the magnetic susceptibility on the antimony concentration.