No Arabic abstract
We report evidence of a non-adiabatic Kohn anomaly in boron-doped diamond, using a joint theoretical and experimental analysis of the phonon dispersion relations. We demonstrate that standard calculations of phonons using density functional perturbation theory are unable to reproduce the dispersion relations of the high-energy phonons measured by high-resolution inelastic x-ray scattering. On the contrary, by taking into account non-adiabatic effects within a many-body field-theoretic framework, we obtain excellent agreement with our experimental data. This result indicates a breakdown of the Born-Oppenheimer approximation in the phonon dispersion relations of boron-doped diamond.
Diamond has outstanding physical properties: the hardest known material, a wide band gap, the highest thermal conductivity, and a very high Debye temperature. In 2004, Ekimov et al. discovered that heavily boron-doped (B-doped) diamond becomes a superconductor around 4 K. Our group successfully controlled the boron concentration and synthesized homoepitaxially grown superconducting diamond films by a CVD method. By CVD method, we found that superconductivity appears when the boron concentration (nB) exceeds a metal-insulator transition concentration of 3.0x10^20 cm^-3 and its Tczero increases up to 7.4 K with increasing nB. We additionally elucidated that the holes formed at the valence band are responsible for the metallic states leading to superconductivity. The calculations predicted that the hole doping into the valence band induces strong attractive interaction and a rapid increase in Tc with increasing boron concentration. According to the calculations, if substitutional doped boron could be arranged periodically or the degree of disorder is reduced, a Tc of approximately 100 K could be achieved via minimal percent doping. In this work, we have successfully observed zero resistivity above 10 K and an onset of resistivity reduction at 25.2 K in heavily B-doped diamond film. However, the effective carrier concentration is similar to that of superconducting diamond with a lower Tc. We found that the carrier has a longer mean free path and lifetime than previously reported, indicating that this highest Tc diamond has better crystallinity compared to that of other superconducting diamond films. In addition, the susceptibility shows a small transition above 20 K in the high quality diamond, suggesting a signature of superconductivity above 20 K. These results strongly suggest that heavier carrier doped defect-free crystalline diamond could give rise to high Tc diamond.
Boron-doped single crystal diamond films were grown homoepitaxially on synthetic (100) Type Ib diamond substrates using microwave plasma assisted chemical vapor deposition. A modification in surface morphology of the film with increasing boron concentration in the plasma has been observed using atomic force microscopy. Use of nitrogen during boron doping has been found to improve the surface morphology and the growth rate of films but it lowers the electrical conductivity of the film. The Raman spectra indicated a zone center optical phonon mode along with a few additional bands at the lower wavenumber regions. The change in the peak profile of the zone center optical phonon mode and its downshift were observed with the increasing boron content in the film. However, shrinkage and upshift of Raman line was observed in the film that was grown in presence of nitrogen along with diborane in process gas.
The discoveries of superconductivity in heavily boron-doped diamond (C:B) in 2004 and silicon (Si:B) in 2006 renew the interest in the superconducting state of semiconductors. Charge-carrier doping of wide-gap semiconductors leads to a metallic phase from which upon further doping superconductivity can emerge. Recently, we discovered superconductivity in a closely related system: heavily-boron doped silicon carbide (SiC:B). The sample used for that study consists of cubic and hexagonal SiC phase fractions and hence this lead to the question which of them participates in the superconductivity. Here we focus on a sample which mainly consists of hexagonal SiC without any indication for the cubic modification by means of x-ray diffraction, resistivity, and ac susceptibility.
Using angle-resolved photoelectron spectroscopy, we compare the electronic band structure of an ultrathin (1.8 nm) {delta}-layer of boron-doped diamond with a bulk-like boron doped diamond film (3 {mu}m). Surprisingly, the measurements indicate that except for a small change in the effective mass, there is no significant difference between the electronic structure of these samples, irrespective of their physical dimensionality. While this suggests that, at the current time, it is not possible to fabricate boron-doped diamond structures with quantum properties, it also means that nanoscale doped diamond structures can be fabricated which retain the classical electronic properties of bulk-doped diamond, without a need to consider the influence of quantum confinement.
In 2004 the discovery of superconductivity in heavily boron-doped diamond (C:B) led to an increasing interest in the superconducting phases of wide-gap semiconductors. Subsequently superconductivity was found in heavily boron-doped cubic silicon (Si:B) and recently in the stochiometric mixture of heavily boron-doped silicon carbide (SiC:B). The latter system surprisingly exhibits type-I superconductivity in contrast to the type-II superconductors C:B and Si:B. Here we will focus on the specific heat of two different superconducting samples of boron-doped SiC. One of them contains cubic and hexagonal SiC whereas the other consists mainly of hexagonal SiC without any detectable cubic phase fraction. The electronic specific heat in the superconducting state of both samples SiC:B can be described by either assuming a BCS-type exponentional temperature dependence or a power-law behavior.