Advances in Structural Analysis by D.R. UHLMANN and N.J. KREIDL (Eds.)

By D.R. UHLMANN and N.J. KREIDL (Eds.)

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1983), leaving the Ge-Ge shell in the glass much diminished compared to the crystal (Fig. 8). These important observations point to the tetrahedral G e 0 2 unit being far more rigid in aG e 0 2 than in the crystal, but less rigidly connected. Sayers et al. (1975) suggest this stems from the loss of mesomeric bonding in the glass. Regular mesomeric configurations in the crystalline structure will be reduced in a continuous random network, as we have seen in a-As. However, because of the symmetrical tetrahedral geometry in a-Ge0 2 , a shortening of the primary covalent bond is neither expected nor observed.

35A). However, unlike a-Ge, hydrogenated Si—both glow discharge and sputtered films—have a coordination number significantly lower than 4. 7(2) for a film containing 21% hydrogen. Menelle et al. (1986) quote a similar reduction. Interestingly, the amorphous film density, pg, judged from the height of the Si K-edge, also decreases compared to c-Si. The fall in Ng/Nc and pjpc is also accompanied by some static disorder, A//2 ~ 2 to 5 10 _3 A 2 , which, as we have seen, is comparable with the thermal disorder in c-Si at room temperature.

In the case of annealed glass, these are small and reversible but for thin films—particularly if these are deposited obliquely to the substrate—much larger effects are seen and these are usually irreversible. One intriguing irreversible effect that also displays technological promise is photodiffusion. I shall describe this in more detail at the end of this chapter (Section VILA). Compared to tetrahedral networks such as a-Si or a-Ge where all valence electrons are incorporated into hybridized bonds, in chalcogenides—like pnictides discussed earlier—the average coordination number is lower than four, which results in a fraction of electrons occupying lone-pair states at the top of the valence band.

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