Semiconducting Al-transition-metal quasicrystals -: art. no. 165202

We report on a class of icosahedral aluminum-transition-metal (Al-TM) alloys with true semiconducting behavior. Our description of the structure of these icosahedral quasicrystals is based on the six-dimensional Katz-Gratias-Boudard (KGB) model of the face-centered-icosahedral (fci) quasicrystal and its rational approximants. The shell structure of the atomic surfaces in perpendicular space defines the chemical order of aluminum and transition-metal (TM) atoms leading to semiconducting transport properties. In transition-metal aluminides the hybridization between the Al(s,p) and transition-metal d orbitals is responsible for the formation of a semiconducting gap in the electronic spectrum. We have analyzed the electronic charge distribution and observed an enhanced charge density along the Al-TM bonds that is characteristic of covalent bonding. The existence of an energy gap in the electronic spectrum at or in the vicinity of the Fermi level is explicitly demonstrated for several low-order approximants in the hierarchy of Fibonacci approximants which converges to the icosahedral quasicrystals of the fci class, to which also the i-AlPdRe belongs. We predict existence of truly semiconducting quasicrystalline 1/1-approximants. Our results also lead to the prediction of the existence of new semiconducting quasicrystals with specified Al-TM compositions. The possibility of the existence of a semiconducting band gap suggests an explanation for the anomalously high resistivity of the icosahedral AlPdRe quasicrystals. We demonstrate that substitutional defects violating the ideal Al-TM ordering predicted by the KGB model lead to the formation of localized states in the band gap. A real sample of i-AlPdRe thus seems to be a semiconductor with a band gap filled by the localized states.