Publication
Materials Science Reports
Review

Electrical and optical properties of silicide single crystals and thin films

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Abstract

Electrical transport and optical properties of transition-metal silicides are reviewed. They are integrated with thermal properties of single-crystal silicides. Most of these compounds behave as metals while some of them behave as semiconductors. The former show an increasing electrical resistivity ρ with increasing temperature. Several of them show a non-classical deviation of ρ(T) from linearity in the high-temperature limit. This deviation, related to intrinsic properties of the compound, can be affected both in sign and in amount by the presence of foreign atoms (impurities) and structural defects. Moreover, defects dominate the electrical transport at low temperatures both in metallic and semiconducting compounds. Therefore, the interpretation of the electrical properties measured as a function of temperature may give a non-realistic description of silicide intrinsic properties. Since also other physical properties, like thermal and optical ones, can be strongly affected by impurities and defects, results about single-crystal silicides will be first illustrated. Single-crystal preparation and structural characterization are described in detail, with emphasis on crystalline quality in terms of residual resistivity ratio. The electrical quantities, resistivity and magnetoresistance, are measured as a function of temperature and along the main crystallographic directions. The effect of impurities and defects on the transport properties is then evaluated by examining the electrical transport of polycrystalline thin-film silicides. The different contributions to the total resistivity are measured by changing: (i) film stoichiometry, (ii) impurity concentration, (iii) texture growth and (iv) film thickness. Hall-coefficient measurements are briefly discussed with the main purpose to evidence that great caution is necessary when deducing mobility and charge-carrier density values from these data. The theoretical models currently used to interpret the low- and high-temperature resistivity behavior of the metallic silicides are presented and used to fit the experimental resistivity curves. The results of these studies reveal that in several cases there are well-defined temperature ranges in which a specific electron-phonon scattering mechanism dominates. This allows a more detailed study of the microscopic processes. The optical functions from the far-infrared to the vacuum ultraviolet, derived from Kramers-Krönig analysis of reflectance spectra or directly measured by spectroscopic ellipsometry, are presented and discussed for some significant metallic disilicides, both single crystals and polycrystalline films. Different physical phenomena are distinguished in the spectra: intraband transitions at the lowest photon energies, interband transitions at higher energies, and collective oscillations. In particular, the free-carrier response derived from this analysis is compared with the transport results. The interpretation of the experimental spectra is based on the calculated electronic structures or optical functions. Moreover, it is shown how the optical studies contribute to assess definitively the semiconducting character of some disilicides. Specific-heat measurements on single crystals between 0.1 and 8 K are reported. The Debye temperature and the density of electronics states at the Fermi surface are deduced from the lattice and electronic contributions, respectively. Some silicides have been found superconductors with small electron-phonon coupling constants. Emphasis is given to the comparison between the properties deduced from these studies and those obtained from the analysis of electrical transport data. The final part of this review is devoted to the calculation of some microscopic physical quantities, as for example the electron mean free path, the charge-carrier density, the Fermi velocity. The parameters of the best fit to the experimental resistivity curves, the free-carrier parameters obtained from infrared spectra and the density of electronic states at the Fermi surface determined from specific-heat measurements were used in such evaluations. © 1993.