MXenes, a new class of two-dimensional (2D) materials, have recently demonstrated impressive optoelectronic properties associated with its ultrathin layered structure. Particularly, Ti3C2Tx, the most studied MXene by far, was shown to exhibit intense surface plasmons (SPs), i.e. collective oscillations of free charge carriers, when excited by electromagnetic waves. However, due to the lack of information about the spatial and energy variation of those SPs over individual MXene flakes, the potential use of MXenes in photonics and plasmonics is still marginally explored. Hence, the main objective of this dissertation is to shed the light upon the plasmonic behavior of MXenes at the nanoscale and extend their use beyond their typical electrochemical applications.
To fulfill our objective, we first elucidated the underlying characteristics governing the plasmonic behavior of MXenes. Then, we revealed the existence of various tunable SP modes supported by different MXenes, i.e. Ti3C2Tx and Mo2CTx, and investigated their energy and spatial distribution over individual flakes. Further, we fabricated an array of MXene-based flexible photodetectors that only operate at the resonant frequency of the SPs supported by MXenes. We also unveiled the existence of tunable SPs supported by another 2D nanomaterial (i.e. MoO2) and juxtaposed its plasmonic behavior with that of MXenes, to underline the uniqueness of the latter. Noteworthy, as in the case of MXenes, this was the first progress made on studying specific SP modes supported by MoO2 nanostructures. In this part of the dissertation, we were able to identify and tailor multipolar SPs supported by MoO2 and illustrate their dependence on their bulk band structure.
In the end, we show that, on the contrary, SPs in MXenes are mainly controlled by the surface band structure. To confirm this, we selectively altered the subsurface band structure of Ti3C2Tx and modulated its work function (from 4.37 to 4.81 eV) via charge transfer doping. Interestingly, thanks to the unchanged surface stoichiometry of Ti3C2Tx, the plasmonic behavior of Ti3C2Tx was not affected by its largely tuned electronic structure. Notably, the ability to attain MXenes with tunable work functions, yet without disrupting their plasmonic behavior, is appealing to many application fields.
|Date of Award
|Nov 18 2020
- Physical Sciences and Engineering
|Husam Alshareef (Supervisor)
- Surface Plasmons
- Plasmonic Photodetection
- Charge Transfer Doping
- Ultrafast Plasmon Dynamics
- Tunable Plasmonic Behavior