EXAFS, conductivity and Hall coefficient measurements have been carried out for liquid As-Te mixtures. EXAFS analysis reveals the presence of chemical disorder marked by the existence of homopolar As-As and Te-Te pairs. At high temperature around 500 • C the network structure composed of threefold coordinated As atoms and twofold coordinated Te atoms is transformed into the twofold chain structure. The network-chain transformation is accompanied by the gradual semiconductor to metal transition which is demonstrated by the results for conductivity and Hall coefficient. The microscopic origin of the semiconductor to metal transition is discussed in connection with the structural modification.
Extended x-ray absorption fine structure measurements were performed on trigonal tellurium (t-Te) and tellurium nanoparticles in very thin films. Twofold coordinated chains, much like those in t-Te, exist even in the nanoparticles, but covalent bonds or intrachain interactions are stronger than those of t-Te as shown by a shorter bond length and higher Einstein temperature. The interchain coordination number of the nanoparticles is about half that of t-Te, suggesting reduction of interchain interactions.
The structure of amorphous Cu 2 GeTe 3 is investigated by a combination of anomalous x-ray scattering and extended x-ray absorption fine-structure experiments. The experimental data are analyzed with reverse Monte Carlo modeling, and they are interpreted in terms of short-range-order parameters as well as by using ring statistics and persistent homology to study the intermediate-range order. Based on this information, the structural relationship of the amorphous phase to the corresponding crystal is discussed. It is found that the amorphous network can be rationalized by small atomic displacements of the crystal structure, directed toward the intrinsic void regions. This structural similarity establishes the possibility of a fast phase-change process. On the other hand, the atomic rearrangements also lead to the formation of new chemical bonds and to distortions on the intermediate-range-order level. These are realized by a collapse and contraction of the strict hexagonal ring arrangements of the crystal and by the formation of small, triangular rings as well as Cu cluster configurations. These structural features allow for a new understanding of the phase-change property contrast of this material, especially concerning the density change and the optical contrast.
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