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Theses Doctoral

Optical Spectroscopy of Excitons at the Interfaces of Nanostructures

Raja, Archana

Atomically thin quasi-two-dimensional materials like graphene and transition metal dichalcogenide (TMDC) layers exhibit extraordinary optical and electrical properties. They have not only been used as testing grounds for fundamental research but also show promise for their viability in optoelectronics, photovoltaics and photocatalysis, to name a few technological applications. In practice, seldom are these materials used in isolation. One often finds them as part of a multicomponent structure, or heterostructure. In a similar spirit as the influence of solvents on the properties of molecular complexes, nanomaterials are also affected by their dielectric environment. Engineering the effect of the surroundings on the excitations in these materials is both a challenge and an opportunity. Moreover, understanding the transport of energy and charge through these heterostructures is crucial for device design. In this dissertation I will explore the properties of excitations in zero-dimensional and two-dimensional nanostructures and their dependence on the details of the environment using optical spectroscopy. Here, I discuss three of the projects that I undertook during my graduate studies.
The first project concerns the efficient near-field, non-radiative energy transfer (NRET) of photo-excited carriers from semiconductor nanocrystals to graphene and a TMDC, molybdenum disulfide. Photoluminescence quenching of single quantum dots and time-resolved photoluminescence were used to quantify the rate of energy transfer. The NRET rate exhibited surprisingly opposite trends with increasing number of layers of the acceptor 2D sheet. The rate increased with increasing thickness of adjacent graphene layers but decreased with increasing thickness of MoS₂. A model based on classical electromagnetism could successfully explain the countervailing trends in terms of the competition between the dissipative channels and reduction of the electric field within the 2D material.
In the next project, the exciton binding energy and band gap in another TMDC, monolayer WS₂, were tuned via dielectric screening from the environment. Monolayers of WS₂ were capped with graphene layers of varying thickness (1 – 4 layers). The excitonic states of WS₂ in the resulting heterostructures were detected using reflectance contrast spectroscopy and theoretically studied by a semi-classical model. The binding energy of the exciton was halved to 150 meV by placement of a single layer of graphene adjacent to the WS₂. Furthermore, this dramatic decrease in the binding energy is accompanied by a reduction of the band gap by the same amount. Additionally, the average spacing between the graphene and WS₂ was also identified to be a critical parameter with respect to dielectric screening of the electron - hole interaction. This offers a flexible alternative for the external manipulation of the Coulomb interaction.
In the final part, I study how excitons in WS₂ couple and scatter with the excitations of the lattice or phonons. The importance of this study stems from the contribution of the scattering rates to the spectral width of the excitonic feature, the dephasing dynamics and thermal transport. The transition from direct to indirect band gap semiconductor from mono- to bilayer is expected to add an additional scattering channel via phonon emission. Through temperature dependent reflectance contrast and photoluminescence spectroscopy, the scattering rate for the phonon emission and absorption processes have been quantified. Comparing the results to data reported in the literature, it is understood that the striking change for the scattering rates is expected only at the mono- to bilayer transition for WS₂. The results suggest material thickness as a handle for engineering exciton - phonon interactions at the nanoscale.


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More About This Work

Academic Units
Chemical Physics
Thesis Advisors
Heinz, Tony F.
Ph.D., Columbia University
Published Here
April 15, 2016