Interaction of metal particles with adsorbed dye molecules: absorption and luminescence

Glass, A. M.; Liao, P. F.; Bergman, J. G.; Olson, David H.

doi:10.1364/ol.5.000368

Cited by 286 publications

(138 citation statements)

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“…al. in 1980 and later confirmed by other groups [23][24][25]. When a lumophore is placed near metal, there is a very strong net absorption effect, a result of the coupling of the molecular dipoles with the localized electromagnetic field of the metallic particle's surface plasmon resonance [12].…”

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confidence: 97%

Metal-enhanced S2 fluorescence from azulene

Zhang

Aslan

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et al. 2006

Chemical Physics Letters

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In this paper, we report the first observation of metal-enhanced S 2 emission at room and low temperature (77K). The S 2 emission intensity of Azulene is enhanced by close proximity to Silver island films (SiFs). In this regard, a ≈ 2-fold higher S 2 fluorescence intensity of Azulene was observed from SiFs as compared to a glass control sample. This suggests that S 2 excited states can couple to surface plasmons and enhance S 2 fluorescence yields, a helpful observation in our understanding the interactions between plasmons and lumophores, and our continued efforts to develop a unified plasmon-lumophore/fluorophore theory. KeywordsS 2 emission; Metal-Enhanced S 2 Fluorescence; Radiative Decay Engineering; Surface Enhanced Fluorescence; Plasmon Controlled Fluorescence; Radiating Plasmons; Azulene; Metal-Enhanced Fluorescence IntroductionThe location of electronic energy levels in molecules and the probability and polarization of radiative transitions between ground and excited state can be accurately predicted by quantum mechanical theory [1]. For most molecules, no excited singlet states (S 2 , S 3 …) have been observed to emit light upon excitation, the same being true for triplet states (T 2 , T 3 …). This is summarized in Kasha's rule: The emitting electronic level of a given multiplicity is the lowest excited level of that multiplicity [2].As the first authentic example of a molecule which violates Kasha's rule, azulene has been the subject of numerous spectroscopic and photophysical investigations [3][4][5][6]. Beer and LonguetHiggins discovered the second excited level emits light upon excitation, producing the anomalous (S 2 to S 0 ) fluorescence of azulene in 1955 [6], whereas that normal S 1 to S 0 fluorescence and T 1 to T 0 phosphorescence were much too weak to be observed. The absence of S 1 to S 0 fluorescence suggests that S 1 to S 0 internal conversion is a very rapid progress in Azulene, this supposition being confirmed by the lifetime of the S 1 state being determined as 1.9 psec [7]. Compared with the analogous spacing of the isomer Naphthalene, Azulene has much wider spacing between its zero -point levels of the first two excited singlet states (S 1 , *Corresponding Author E-mail: geddes@umbi.umd.edu Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. [19], and the application of metallic surfaces to amplified (ultra fast and sensitive) assay detection [20]. Our laboratorys' current interpretation of MEF has been explained by a model whereby non-radiative energy transfer occurs from excited distal fluorophores, to the surface plasmon electrons in n...

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confidence: 97%

Metal-enhanced S2 fluorescence from azulene

Zhang

Aslan

Previte

et al. 2006

Chemical Physics Letters

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“…Such change must be attributed to strong interaction of the metal clusters with the adsorbed molecules that have absorption bands in the same frequency range as the plasma frequency of the metal nanoclusters. 6 Moreover, a large redshift of 5 nm is observed when the 11th bilayer is deposited, indicating that the optimal condition for absorbance enhancement is obtained. The behavior of the enhancement factor is more readily observed by taking the relative percentage increment of absorbance data in Fig.…”

Section: Resultsmentioning

confidence: 96%

“…Wang and Kerker 5 reported that the enhanced absorption of dye-coated particles depends on the particle size, the optical properties of the core ͑silver, gold, and dielectric͒, the coating thickness, the spheroid eccentricity, and the interaction of metal particles with adsorbed dye molecules. Glass et al 6 also found the strong coupling between the metal and the dye that has absorption bands in the same frequency range as the plasma frequency of the particle, and that this strong coupling can greatly modify the plasma resonance of the particles. In order to exhibit strong enhancement of absorbance, judicious selection of the molecules and synthesis of the extremely small particles for different applications should be considered.…”

Section: Resultsmentioning

confidence: 98%

Strong enhancement of optical absorbance from ionic self-assembled multilayer thin films of nanocluster Pt and polymer dye

Liu

Claus

1999

Journal of Applied Physics

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The observation of unusually enhanced optical absorbance spectra of ionic self assembled multilayer (ISAM) thin films composed of alternating layers of Pt nanoclusters (<1 nm dimension) and polymer dye is reported. The first bilayer absorbance is found to be considerably larger than that of several succeeding bilayers even though there is no difference in composition for each bilayer. A layer-by-layer-dependent redshift in maximum wavelength position due to the strong coupling of metals and polymer molecules is observed. The saturation absorption is obtained for the first time when the required thickness of the ISAM film is deposited. The large and unusual enhancement effects are attributed to both the charge-transfer mechanism and very large local fields and collective phenomena near the surface of the small metal clusters/electrolytes and at the interfaces between the cluster/polymer multilayers.

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“…A!llong others, surface enhancement of one-photon [27] and multiphoton [9] excited luminescence,hyper Raman scattering [28], third harmonic generation [29], and four-wave mixing [29] have also been seen. In most cases, the actual enhancement factor is difficult to measure because the signal from a smooth surface is far from being detectable as one would predict from estimates.…”

Section: Surface Enhanced Nonlinear Optical Effectsmentioning

confidence: 99%

Nonlinear Optical Techniques for Surface Studies

Shen

1990

Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry

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Recent effort in developing nonlinear optical techniques for surface studies is reviewed. Emphasis is on monolayer detection of adsorbed molecules on surfaces. It is shown that surface coherent antiStokes Raman scattering (CARS) with picosecond pulses has the sensitivity of detecting submonolayer of molecules. On the other hand, second harmonic or sum-frequency generation is also sensitive enough to detect molecular monolayers. Surface-enhanced nonlinear optical effects on some rough metal surfaces have been observed. This facilitates the detection of molecular monolayers on such surfaces, and makes the study of molecular adsorption at a liquid-metal interface feasible. Advantages and disadvantages of the nonlinear optical techniques for surface studies are discussed.

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Interaction of metal particles with adsorbed dye molecules: absorption and luminescence

Cited by 286 publications

References 3 publications

Metal-enhanced S2 fluorescence from azulene

Metal-enhanced S2 fluorescence from azulene

Strong enhancement of optical absorbance from ionic self-assembled multilayer thin films of nanocluster Pt and polymer dye

Nonlinear Optical Techniques for Surface Studies

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