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Register a new userThe occupied electronic structure of ultrathin boron doped diamond
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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.
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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 energy level alignment at organic/inorganic (o/i) semiconductor interfaces is crucial for any light-emitting or -harvesting functionality. Essential is the access to both occupied and unoccupied electronic states directly at the interface, which is often deeply buried underneath thick organic films and challenging to characterize. We use several complementary experimental techniques to determine the electronic structure of p-quinquephenyl pyridine (5P-Py) adsorbed on ZnO(10-10). The parent anchoring group, pyridine, significantly lowers the work function by up to 2.9 eV and causes an occupied in-gap state (IGS) directly below the Fermi level $E_text{F}$. Adsorption of upright-standing 5P-Py also leads to a strong work function reduction of up to 2.1 eV and to a similar IGS. The latter is then used as an initial state for the transient population of three normally unoccupied molecular levels through optical excitation and, due to its localization right at the o/i interface, provides interfacial sensitivity, even for thick 5P-Py films. We observe two final states above the vacuum level and one bound state at around 2 eV above $E_text{F}$, which we attribute to the 5P-Py LUMO. By the separate study of anchoring group and organic dye combined with the exploitation of the occupied IGS for selective interfacial photoexcitation this work provides a new pathway for characterizing the electronic structure at buried o/i interfaces.
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.
We apply first-principles calculations to study the electronic structure of boron nitride nanocones with disclinations of different angles $theta=npi/3$. Nanocones with odd values of $n$ present antiphase boundaries that cause a reduction of the work function of the nanocones, relative to the bulk BN value, by as much as 2 eV. In contrast, nanocones with even values of $n$ do not have such defects and present work functions that are very similar to the BN bulk value. These results should have strong consequences for the field emission properties of boron nitride nanocones and nanotubes.
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.
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