Isotopic phonon effects in LaB6-LaB6 do not possess cubic symmetry and show a non-random isotope distribution.

The isotopic phonon effects in LaB(6) are investigated on the Raman spectra of a series of high-quality single crystals with systematically varied contents of (10)B and (11)B isotopes. A detailed group theoretical analysis enlightens the correlation between distortions of the B(6) octahedra and the splitting or broadening of phonon modes. It is evident that LaB(6) does not have cubic symmetry as assumed so far. A further symmetry reduction of the B(6) octahedra occurs in isotopically mixed crystals. There, the distribution of isotopes is not random as commonly assumed; the probability of associating equal isotopes increases with their mass decreasing.

Isotopic phonon effects in ß-rhombohedral boron--non-statistical isotope distribution.

On the basis of the spectra of IR- and Raman-active phonons, the isotopic phonon effects in ß-rhombohedral boron are analysed for polycrystalline (10)B- and (11)B-enriched samples of different origin and high-purity (nat)B single crystals. Intra- and inter-icosahedral B-B vibrations are harmonic, hence meeting the virtual crystal approximation (VCA) requirements. Deviations from the phonon shift expected according to the VCA are attributed to the anharmonic share of the lattice vibrations. In the case of icosahedral vibrations, the agreement with calculations on α-rhombohedral boron by Shirai and Katayama-Yoshida is quite satisfactory. Phonon shifts due to isotopic disorder in (nat)B are separated and determined. Some phonon frequencies are sensitive to impurities. The isotopic phonon effects yield valuable specific information on the nature of the different phonon modes. The occupation of regular boron sites by isotopes deviates significantly from the random distribution.

Superconductivity in boron carbide? Clarification by low-temperature MIR/FIR spectra.

The electronic structure and phonon density of B(13)B(2) boron carbide calculated by Calandra et al (2004 Phys. Rev. B 69 224505) defines this compound as metallic, and the authors predict superconductivity with T(C)s up to 36.7 K. Their results are affected by the same deficiencies as former band structure calculations on boron carbides based on hypothetical crystal structures deviating significantly from the real ones. We present optical mid IR/far IR (MIR/FIR) spectra of boron carbide with compositions between B(4.3)C and B(10.37)C, evidencing semiconducting behaviour at least down to 30 K. There is no indication of superconductivity. The spectra yield new information on numerous localized gap states close to the valence band edge.

Raman scattering and isotopic phonon effects in dodecaborides.

The Raman spectra of numerous dodecaborides have been measured on high-quality single crystals at ambient conditions with high spectral resolution and signal-to-noise ratio. Besides the strong Raman-active modes, numerous Raman-inactive modes occur in the spectra, indicating distortions of the structures. Ab initio calculation of the phonon spectra on ZrB(12) excellently agrees with the experimental results. Force constants are theoretically calculated and force parameters are estimated from the Raman frequencies. The influence of the surface range on the Raman spectra is evident. The different isotopic effects (virtual crystal approximation, the polarization effect and the effect of isotopic disorder) on the phonon frequencies are determined, separated and discussed.

On surface Raman scattering and luminescence radiation in boron carbide.

The discrepancy between Raman spectra of boron carbide obtained by Fourier transform Raman and conventional Raman spectrometry is systematically investigated. While at photon energies below the exciton energy (1.560 eV), Raman scattering of bulk phonons of boron carbide occurs, photon energies exceeding the fundamental absorption edge (2.09 eV) evoke additional patterns, which may essentially be attributed to luminescence or to the excitation of Raman-active processes in the surface region. The reason for this is the very high fundamental absorption in boron carbide inducing a very small penetration depth of the exciting laser radiation. Raman excitations essentially restricted to the boron carbide surface region yield spectra which considerably differ from bulk phonon ones, thus indicating structural modifications.

Isotopic effects on the phonon modes in boron carbide.

The effect of isotopes ((10)B-(11)B; (12)C-(13)C) on the infrared- and Raman-active phonons of boron carbide has been investigated. For B isotopes, the contributions of the virtual crystal approximation, polarization vector and isotopical disorder are separated. Boron and carbon isotope effects are largely opposite to one another and indicate the share of the particular atoms in the atomic assemblies vibrating in specific phonon modes. Some infrared-active phonons behave as expected for monatomic boron crystals.

Are there bipolarons in icosahedral boron-rich solids?

The charge transport of boron carbide, often incorrectly denoted as B(4)C, has been controversially discussed. It is shown that the bipolaron hypothesis is not compatible with numerous experimental results. In particular, the determined real microstructure of boron carbide and its related electronic properties disprove several assumptions, which are fundamental to the bipolaron hypothesis. In contrast, the actual energy band scheme derived mainly from optical investigations is confirmed by careful evaluation of the high-temperature electrical conductivity, and allows a consistent description at most of the experimental results.