Wide-bandgap semiconductors are exploited in several technological fields such as electron emission devices, energy conversion, high-power high-temperature electronics, and electrocatalysis. Their electronic properties vary significantly depending on the functionalization of the surface. Here, we investigated as a proof-of-concept the modulation of the electronic properties of one of the most common widebandgap semiconductors, that is, diamonds, to show the tunability of their properties by modifying the surface termination. Photoelectron spectroscopy was used to demonstrate the availability of a wide window of band bending, work function, and electron affinity. The band bending and work function were found to change by up to 360 meV and 2 eV, respectively, by varying the surface from hydrogen-to oxygenterminated. Because of the negative electron affinity of diamonds, we were able to experimentally show the rigid shift of the whole band structure.
Diamond-based thermionic emission devices could provide a means to produce clean and renewable energy through direct heat-to-electrical energy conversion. Hindering progress of the technology are the thermionic output current and threshold temperature of the emitter cathode. In this report, we study the effects on thermionic emission caused by in situ exposure of the diamond cathode to beta radiation. Nitrogen-doped diamond thin films were grown by microwave plasma chemical vapor deposition on molybdenum substrates. The hydrogen-terminated nanocrystalline diamond was studied using a vacuum diode setup with a 63 Ni beta radiation source-embedded anode, which produced a 2.7-fold increase in emission current compared to a 59 Ni-embedded control. The emission threshold temperature was also examined to further assess the enhancement of thermionic emission, with 63 Ni lowering the threshold temperature by an average of 58 ± 11 °C compared to the 59 Ni control. Various mechanisms for the enhancement are discussed, with a satisfactory explanation remaining elusive. Nevertheless, one possibility is discussed involving excitation of preexisting conduction band electrons that may skew their energy distribution toward higher energies.
Polycrystalline graphene was transferred onto differently terminated epitaxial layers of boron-doped diamond deposited onto single crystal substrates. Chemical and electronic characterisation was performed using energy-filtered photoemission electron microscopy and angle-resolved photoemission spectroscopy. Electronic interaction between the diamond and graphene was observed, where doping of the graphene on the hydrogen and oxygen terminated diamond was n-doping of 250 meV and 0 meV respectively. We found that the wide window of achievable graphene doping is effectively determined by the diamond surface dipole, easily tuneable with a varying surface functionalisation. A Schottky junction using the graphene-diamond structure was clearly observed and shown to reduce downward band bending of the hydrogen terminated diamond, producing a Schottky barrier height of 330 meV.
Material band structures of occupied electronic states are obtainable using conventional angle‐resolved photoemission experiments, leaving the unoccupied states far less explored. Here, an alternative approach is built on and expanded to investigate thermalized photoelectrons emitted from crystal surfaces. A model for electron emission is constructed and reveals the material unoccupied state band structure. Potentially applicable to any material and independent from the secondary electron generation mechanism, it is demonstrated on diamond and copper using different light sources. Moreover, the diamond indirect band gap is directly observed and the transverse effective mass at the conduction band minimum can be experimentally obtained, mt = (0.21 ± 0.015) me. This offers a convenient path for angle‐resolved photoemission data interpretation and empty‐state information extraction.
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