Thermionic emission properties of novel carbon nanostructures.

Materials with low work function values (\u3c 2 eV) are highly in demand for low temperature thermionic electron emission, which is a key phenomenon for waste heat recovery applications. Here we present the study of the thermionic emission of the hybrid structure phosphorus, (P) doped diamond nano crystals grown on conical carbon nanotubes (CCNTs). The CCNTs provide the conducting backbone for the P-doped diamond nanocrystals. In the first part of this thesis thermionic emission properties of conical carbon nanotubes (CCNTs) grown on platinum wires and planar graphite foils were investigated. The work function (Φ) values extracted from the thermionic emission data range from 4.1 to 4.7 eV. The range of Φ values is attributed to the morphological characteristics, such as tip radius, aspect ratio, density, and wall structure of CCNTs. The observed lower values for Φ are significantly smaller than that of multi-walled carbon nanotubes (MWNTs). The reduced Φ values are attributed to field penetration effect as a result of the local field enhancement from these structures having high aspect ratio and an excellent field enhancement factor. The high amplification of the external field at the apex of the nanostructures is capable of reducing both the barrier height and the width, in turn contributing to the improved emission current at lower temperatures. The ultraviolet photoemission spectroscopy data of CCNTs grown on Pt wires are in reasonable agreement with the thermionic emission data. In the next part of the thesis we present work function reduction of phosphorus (P) doped (i) diamond nanocrystals grown on conical carbon nanotubes (CCNTs) and (ii) diamond films grown on silicon substrates. Thermionic emission measurements from phosphorus doped diamond crystals on CCNTs resulted in work function value of 2.23 eV. The reduced work-function is interpreted as due to the presence of the surface states and midband-gap states and no evidence for negative electron affinity was seen. However, Ultraviolet photo-spectroscopy studies on phosphorus doped diamond films yielded a work function value of ~1.8 eV with a negative electron affinity (NEA) value of 1.2 eV. Detailed band diagrams are presented to support the observed values for both cases. In addition we determined the work function values of nanocrystalline P doped diamond films grown on W foil to be significantly lower, 1.0- 1.33 eV compared to the hybrid structure and polycrystalline film on Si substrates. We studied tungsten (W) nanowires as an alternative material in place of CCNT as the supporting and conducting channel for P doped diamond crystals in a new hybrid structure. We described the process of fabrication of arrays of vertical W nanowires by microwave plasma treatment and synthesis of P doped nanocrystalline diamond on top of the reduced W nanowires. Thermionic emission measurements from the alternative hybrid structure resulted in high value of the work function ~ 5.1 eV

Charge transfer equilibria in ambient-exposed epitaxial graphene on (0001¯) 6 H-SiC

Article discussing research on charge transfer equilibria in ambient-exposed epitaxial graphene on (0001) 6 H-SiC

Charge transfer equilibria in ambient-exposed epitaxial graphene on (0001) 6 H-SiC

Article discussing research on charge transfer equilibria in ambient-exposed epitaxial graphene on (0001) 6 H-SiC

Efficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction

Hydrogen evolution reaction is catalysed efficiently with precious metals, such as platinum; however, transition metal dichalcogenides have recently emerged as a promising class of materials for electrocatalysis, but these materials still have low activity and durability when compared with precious metals. Here we report a simple one-step scalable approach, where MoO(x)/MoS(2) core-shell nanowires and molybdenum disulfide sheets are exposed to dilute aqueous hydrazine at room temperature, which results in marked improvement in electrocatalytic performance. The nanowires exhibit ∼100 mV improvement in overpotential following exposure to dilute hydrazine, while also showing a 10-fold increase in current density and a significant change in Tafel slope. In situ electrical, gate-dependent measurements and spectroscopic investigations reveal that hydrazine acts as an electron dopant in molybdenum disulfide, increasing its conductivity, while also reducing the MoO(x) core in the core-shell nanowires, which leads to improved electrocatalytic performance