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Carbon Dots Plasmonics Coupling Enables Energy Transfer and Provides Unique Chemical Signatures Lihi Efremushkin, Susanta Kumar Bhunia, Raz Jelinek, and Adi Salomon J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.7b02778 • Publication Date (Web): 29 Nov 2017 Downloaded from http://pubs.acs.org on December 1, 2017
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The Journal of Physical Chemistry Letters
Carbon Dots Plasmonics Coupling Enables Energy Transfer and Provides Unique Chemical Signatures Lihi Efremushkin†∥, Susanta Kumar Bhunia‡∥ §, Raz Jelinek‡, Adi Salomon†* ∥
†
Equal contributions
Department of Chemistry, Institute of Nanotechnology and Advanced Materials (BINA), BarIlan University, Ramat-Gan 5290002, Israel. ‡
Department of Chemistry, Ben Gurion University of the Negev, Beer Sheva 84105, Israel.
AUTHOR INFORMATION §
Current address: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa
32000, Israel Corresponding Author *E-mail:
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ABSTRACT
Plasmonic nanostructures and carbon dots (C-dots) are fascinating optical materials, utilized in imaging, sensing, and color generation. Interaction between plasmonic materials and C-dots may lead to new hybrid materials with controllable optical properties. Herein, we demonstrate for the first time coupling between plasmonic modes and C-dots deposited upon a plasmonic silver hole array. The coupling leads to a remarkable visual attenuation and shifts of the plasmonic wavelengths (i.e. color tuning). In particular, the C-dots-plasmon couplings and pertinent color transformations depend both upon the C-dots' fluorescence emission wavelengths and functional residues displayed upon the C-dots' surface. This optical modulation corresponds to energy level alignment and consequent energy transfer between the C-dots and the plasmonic silver hole array. Notably, the energy coupling observed in the C-dot/plasmonic hybrid system allows distinguishing between C-dots species exhibiting similar optical properties, albeit displaying different functional residues.
TOC GRAPHICS
KEYWORDS: C-dots, energy transfer, color generators, plasmonics, molecular-plasmonics
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The Journal of Physical Chemistry Letters
Photonic modes can interact with emitters to form mixed states with controllable optical properties, leading to development of ultrafast optical switches.1–7 During the past decade, such interactions between the two sub-systems were realized also in room temperature and ambient conditions, by using plasmonic systems.1,4,8–11 The advantage of plasmonic systems over conventional photonics is their ability to confine electromagnetic (EM) fields to a deep subwavelength volume, thereby enhancing light-matter interaction.11–13 Various plasmonic systems such as hole arrays, nanoparticles, grooves and cavities were shown to strongly interact with either dye molecules or quantum dots (Q-dots), following exchange of energy between them, faster than any other competing process present in the emitter.8,10,13–19 Such couplings significantly perturb the emitter systems; new states are consequently formed, separated by the so-called Rabi splitting, leading to new energy relaxation pathways and varying the dynamics of the emitter photochemical processes.1,2,14 Two different regimes of interaction are noted in the literature, namely, the weak and strong coupling regimes. While the latter refers to discrete level systems, the weak coupling regime involves a continuum of states.3,14 In such a case, the states are not mixed, but the emitter lifetime is reduced due to a large density of photonic modes (for more information see Figure S1). Regardless of the coupling strength, the physical properties of the emitter play a pivotal role, whereas the chemical properties surprisingly found to have lesser effects. That is, chemical signature of any molecular system is excluded, as well as chemical interaction between the molecule and the metallic surface. The molecular system is mostly treated as a two-level system, and the same behavior was observed both in case of Q-dots and dye molecules, though these systems are not analogous.16,20 Nevertheless, few studies addressed the differences in coupling behavior to these two different sub-systems (emitters).12
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C-dots are carbon nanoparticles (diameters
