The exploration of novel functional carbon polymorphs is an enduring topic of scientific investigations. In this paper, we present simulations demonstrating metastable carbon phases as the result of pressure induced carbon nanotube polymerization. The configuration, bonding, electronic, and mechanical characteristics of carbon polymers strongly depend on the imposed hydrostatic/non-hydrostatic pressure, as well as on the geometry of the raw carbon nanotubes including diameter, chirality, stacking manner, and wall number. Especially, transition processes under hydrostatic/non-hydrostatic pressure are investigated, revealing unexpectedly low transition barriers and demonstrating sp(2)→sp(3) bonding changes as well as peculiar oscillations of electronic property (e.g., semiconducting→metallic→semiconducting transitions). These polymerized nanotubes show versatile and superior physical properties, such as superhardness, high tensile strength and ductility, and tunable electronic properties (semiconducting or metallic).

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Compressed carbon nanotubes: A family of new multifunctional carbon allotropes

Carbon under pressure

The insufficient data on a structure of the boron-doped diamond (BDD) has frustrated efforts to fully understand the fascinating electronic properties of this material and how they evolve with doping. We have employed X-ray diffraction and Raman scattering for detailed study of the large-sized BDD single crystals. We demonstrate a formation of boron-carbon (B-C) nanosheets and bilayers in BDD with increasing boron concentration. An incorporation of two boron atoms in the diamond unit cell plays a key role for the B-C nanosheets and bilayer formation. Evidence for these B-C bilayers which are parallel to {111} planes is provided by the observation of high-order, super-lattice reflections in X-ray diffraction and Laue patterns. B-C nanosheets and bilayers minimize the strain energy and affect the electronic structure of BDD. A new shallow acceptor level associated with B-C nanosheets at ~37 meV and the spin-orbit splitting of the valence band of ~6 meV are observed in electronic Raman scattering. We identified that the superconducting transitions occur in the (111) BDD surfaces only. We believe that the origin of Mott and superconducting transitions is associated with the two-dimensional (2D) misfit layer structure of BDD. A model for the BDD crystal structure, based on X-ray and Raman data, is proposed and confirmed by density functional theoretical calculation.

/pdf/formation-of-boron-carbon-nanosheets-and-bilayers-in-boron-16q96chhkc.pdf

Formation of Boron-Carbon Nanosheets and Bilayers in Boron-Doped Diamond: Origin of Metallicity and Superconductivity

Diamond is known as a promising electrode material in the fields of cell stimulation, energy storage (e.g., supercapacitors), (bio)sensing, catalysis, etc. However, engineering its surface and electrochemical properties often requires costly and complex procedures with addition of foreign material (e.g., carbon nanotube or polymer) scaffolds or cleanroom processing. In this work, we demonstrate a novel approach using laser-induced periodic surface structuring (LIPSS) as a scalable, versatile, and cost-effective technique to nanostructure the surface and tune the electrochemical properties of boron-doped diamond (BDD). We study the effect of LIPSS on heavily doped BDD and investigate its application as electrodes for cell stimulation and energy storage. We show that quasi-periodic ripple structures formed on diamond electrodes laser-textured with a laser accumulated fluence of 0.325 kJ/cm2 (800 nm wavelength) displayed a much higher double-layer capacitance of 660 μF/cm2 than the as-grown BDD (20 μF/cm2) and that an increased charge-storage capacity of 1.6 mC/cm2 (>6-fold increase after laser texturing) and a low impedance of 2.74 Ω cm2 turn out to be appreciable properties for cell stimulation. Additional morphological and structural characterization revealed that ripple formation on heavily boron-doped diamond (2.8 atom % [B]) occurs at much lower accumulated fluences than the 2 kJ/cm2 typically reported for lower doping levels and that the process involves stronger graphitization of the BDD surface. Finally, we show that the exposed interface between sp2 and sp3 carbon layers (i.e. the laser-ablated diamond surface) revealed faster kinetics than the untreated BDD in both ferrocyanide and RuHex mediators, which can be used for electrochemical (bio)sensing. Overall, our work demonstrates that LIPSS is a powerful single-step tool for the fabrication of surface-engineered diamond electrodes with tunable material, electrochemical, and charge-storage properties.

Laser-Induced Periodic Surface Structures (LIPSS) on Heavily Boron-Doped Diamond for Electrode Applications.

High pressure–high temperature synthesis of diamond from single-wall pristine and iodine doped carbon nanotube bundles

Boron distribution in the subsurface region of heavily doped IIb type diamond

Raman spectra of single-wall nanotubes under high pressure combined with shear deformation are investigated in situ in a diamond cell. Shear deformation applied under 35 GPa led to pressure multiplication up to 60 GPa, and increased the intensity of Raman bands more than ten times without essential change of G-mode position while causing its essential broadening. The G-mode remained broad after pressure unloading and shifted to 1534 cm −1 . The hardness of the superhard material was 58±6 GPa, comparable to the hardness of carbo-boro-nitride. A broad band appeared in the photoluminescence spectrum with a maximum at about 2 eV, which allowed to assume a high content of sp 3 -bonds in the sample. The large dispersion of the G-mode almost vanished after pressure unloading. However, a noticeable dispersion of the D-mode was found, which is a sign of certain ordering in the superhard phase. TEM study of the superhard phase detected clusters with graphene sheets with a size about 1 nm.

D.M. Popova

Papers

Boron distribution in the subsurface region of heavily doped IIb type diamond

Nanostructured superhard carbon phase obtained under high pressure with shear deformation from single-wall nanotubes HiPco

Spectroscopic and first-principles studies of boron-doped diamond: Raman polarizability and local vibrational bands