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Title: Engineering metal-nanoantennae/dye complexes for maximum fluorescence enhancement

Authors:
; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC); Re-Defining Photovoltaic Efficiency Through Molecule Scale Control (RPEMSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1168075
DOE Contract Number:
SC0001085
Resource Type:
Journal Article
Resource Relation:
Journal Name: Optics Express; Journal Volume: 22; Related Information: RPEMSC partners with Columbia University (lead); Brookhaven National Laboratory; Purdue University
Country of Publication:
United States
Language:
English
Subject:
solar (photovoltaic), electrodes - solar, charge transport, materials and chemistry by design, optics, synthesis (novel materials)

Citation Formats

Meng, Xiang, Grote, Richard R., Dadap, Jerry I., Panoiu, Nicolae C., and Osgood, Richard M.. Engineering metal-nanoantennae/dye complexes for maximum fluorescence enhancement. United States: N. p., 2014. Web. doi:10.1364/OE.22.022018.
Meng, Xiang, Grote, Richard R., Dadap, Jerry I., Panoiu, Nicolae C., & Osgood, Richard M.. Engineering metal-nanoantennae/dye complexes for maximum fluorescence enhancement. United States. doi:10.1364/OE.22.022018.
Meng, Xiang, Grote, Richard R., Dadap, Jerry I., Panoiu, Nicolae C., and Osgood, Richard M.. Wed . "Engineering metal-nanoantennae/dye complexes for maximum fluorescence enhancement". United States. doi:10.1364/OE.22.022018.
@article{osti_1168075,
title = {Engineering metal-nanoantennae/dye complexes for maximum fluorescence enhancement},
author = {Meng, Xiang and Grote, Richard R. and Dadap, Jerry I. and Panoiu, Nicolae C. and Osgood, Richard M.},
abstractNote = {},
doi = {10.1364/OE.22.022018},
journal = {Optics Express},
number = ,
volume = 22,
place = {United States},
year = {Wed Sep 03 00:00:00 EDT 2014},
month = {Wed Sep 03 00:00:00 EDT 2014}
}
  • New technologies for direct solar energy conversion have gained more attention in the last few years. In particular, Dye Sensitized Solar Cells (DSSCs) are promising in terms of efficiency and low cost [1,2]. Benefited from systematic device engineering and continuous material innovation, a state of the art DSC with a ruthenium sensitizer has achieved a validated efficiency of 11.1%[3] measured under the air mass 1.5 global (AM1.5G) conditions.The optimized geometries of the 3, 4-Pyridinedicarbonitrile, 3-Aminophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile are shown in Fig. 1(a). The frontier molecular orbitals (MO) energies of the dyes 3, 4 Pyridinedicarbonitrile, 3-Nitrophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile aremore » shown in Fig. 1(b). The HOMO-LUMO gap of the dye 3, 4 Pyridinedicarbonitrile, 3-Aminophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile in vacuum is 5.96 eV, 5.54 eV, 5.57 eV, 5.76 eV respectively. The geometries, electronic structures, polarizabilities, and hyperpolarizabilities of dyes 3, 4-Pyridinedicarbonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile were studied by using density functional theory with hybrid functional B3LYP, and the UV-Vis spectra were investigated by using TDDFT methods. The NBO results suggest that 3, 4-Pyridinedicarbonitrile, 3-Aminophthalonitrile 4-Aminophthalonitrile and 4-Methylphthalonitrile are all (D-pi-A) systems. The calculated isotropic polarizability of 3, 4-Pyridinedicarbonitrile, 3-Aminophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile is. 85.76, 112.72, 26.63 and 115.13 a.u., respectively. The calculated polarizability anisotropy invariant of 3, 4-Pyridinedicarbonitrile, 3-Aminophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile is 74.451, 83.533, 62.653 and 88.526 a.u., respectively. The hyperpolarizabilities of 3, 4-Pyridinedicarbonitrile, 3-Aminophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile is 0.80628, 5.60646, 7.7979 and 1.86216 (in a.u.), respectively. The frequencies of strongest IR absorption for 3, 4-Pyridinedicarbonitrile, 3-Aminophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile are 1614 cm{sup -1}, 290 cm{sup -1}, 387 cm{sup -1} and 846 cm{sup -1} and the frequencies of strongest Raman activity for 3, 4-Pyridinedicarbonitrile, 3-Aminophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile are 2345 cm{sup -1}, 2338 cm{sup -1},2329 cm{sup -1}, 2337cm{sup -1}, respectively. The electronic absorption spectral features in visible and near-UV region were assigned based on the qualitative agreement to TDDFT calculations. The absorptions are all ascribed to {pi}{yields}{pi}* transition. The three excited states with the lowest excited energies of 3, 4-Pyridinedicarbonitrile, 3-Aminophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile are photoinduced electron transfer processes that contributes sensitization of photo-to-current conversion processes. The interfacial electron transfer between semiconductor TiO{sub 2} electrode and dye sensitizer 3, 4- Pyridinedicarbonitrile, 3-Aminophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile is electron injection process from excited dyes as donor to the semiconductor conduction band. Based on the comparative analysis of geometries, electronic structures, and spectrum properties between 3, 4-Pyridinedicarbonitrile, 3-Aminophthalonitrile, 4-Aminophthalonitrile and 4-Methylphthalonitrile the role of amide and methyl groups in phthalonitrile is as follows: it enlarged the distance between electron donor group and semiconductor surface, and decreased the timescale of the electron injection rate, resulted in giving lower conversion efficiency. This indicates that the choice of the appropriate conjugate bridge in dye sensitizer is very important to enhance the performance of DSSC.« less
  • Over the past decade metal-fluorophore interactions, metal-enhanced fluorescence, have attracted significant research attention, with the technology now becoming common place in life science applications. In this paper, we address the underlying mechanisms of metal-enhanced fluorescence (MEF) and experimentally show using chemiluminescence solutions that MEF is indeed underpinned by two complimentary mechanisms, consistent with the recent reports by Geddes and co-workers [Zhang et al., J. Phys. Chem. C 113, 12095 (2009)] and their enhanced fluorescence hypothesis.