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Plasmon-phonon coupling between metamaterials and molecular vibrations provides a new path for studying mid-infrared light-matter interactions and molecular detection. So far, the coupling between the plasmonic resonances of metamaterials and the phonon vibrational modes of molecules has been realized under linearly polarized light. Here, mid-infrared chiral plasmonic metasurfaces with high circular dichroism (CD) in absorption over 0.65 in the frequency range of 50 to 60 THz are demonstrated to strongly interact with the phonon vibrational resonance of polymethyl methacrylate (PMMA) molecules at 52 THz, under both left-handed and right-handed circularly polarized (LCP and RCP) light. The mode splitting features in the absorption spectra of the coupled metasurface-PMMA systems under both circular polarizations are studied in PMMA layers with different thicknesses. The relation between the mode splitting gap and the PMMA thickness is also revealed. The demonstrated results can be applied in areas of chiral molecular sensing, thermal emission, and thermal energy harvesting.
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Effect of thermal annealing on aggregation of a squaraine thin film
This study aimed to investigate the effects of thermal annealing on a film of squaraine (SQ) molecules in a polymethyl methacrylate (PMMA) matrix. Molecular aggregation is inferred from in situ absorption measurements, and excited state dynamics are measured using a spatially encoded transient absorption (TA) spectroscopy. TA spectra were well-replicated using a kinetic model that evolves as a function of annealing time and extent of aggregation. While linear absorbance spectra indicate that the SQ molecules are primarily uncoupled or weakly-coupled when initially deposited in a PMMA matrix, the kinetic model shows that some pi-stacked aggregates are already present. Excitons are funnelled by energy transfer to these aggregates in just a few picoseconds. The amount of pi-stacked aggregates increases during thermal annealing, further increasing the population of excitons that end up in these aggregates.
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- Award ID(s):
- 1752129
- PAR ID:
- 10317166
- Date Published:
- Journal Name:
- MRS Advances
- ISSN:
- 2731-5894
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1557/s43580-022-00215-4
