Toward Plasmon-Induced Photoexcitation of Molecules

Nabika, Hideki; Takase, Mai; Nagasawa, Fumika; Murakoshi, Kei

doi:10.1021/jz100914r

Cited by 99 publications

(78 citation statements)

References 94 publications

(179 reference statements)

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“…All these effects are based on the same phenomenon, which is the interaction of fluorophores (dipoles) with resonant or non-resonant plasmons on the metal nanoparticles or surfaces [28-31]. These interactions can occur during both excitation, via the high light-induced fields, or during emission by changes in the radiative decay rate [32-35]. Fluorophore-plasmon coupling offers the opportunity to combine fluorescence with the rapidly developing field of plasmonics [36-39].…”

Section: Introductionmentioning

confidence: 99%

Radiative decay engineering 7: Tamm state-coupled emission using a hybrid plasmonic–photonic structure

Badugu

Descrovi

Lakowicz

2014

Analytical Biochemistry

106

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There is a continuing need to increase the brightness and photostability of fluorophores for use in biotechnology, medical diagnostics and cell imaging. One approach developed during the past decade is to use metallic surfaces and nanostructures. It is now known that excited state fluorophores display interactions with surface plasmons, which can increase the radiative decay rates, modify the spatial distribution of emission and result in directional emission. One important example is Surface Plasmon-Coupled Emission (SPCE). In this phenomenon the fluorophores at close distances from a thin metal film, typically silver, display emission over a small range of angles into the substrate. A disadvantage of SPCE is that the emission occur at large angles relative to the surface normal, and at angles which are larger than the critical angle for the glass substrate. The large angles make it difficult to collect all the coupled emission and have prevented use of SPCE with high-throughput and/or array applications. In the present report we describe a simple multi-layer metal-dielectric structure which allows excitation with light that is perpendicular (normal) to the plane and provides emission within a narrow angular distribution that is normal to the plane. This structure consist of a thin silver film on top of a multi-layer dielectric Bragg grating, with no nanoscale features except for the metal or dielectric layer thicknesses. Our structure is designed to support optical Tamm states, which are trapped electromagnetic modes between the metal film and the underlying Bragg grating. We used simulations with the transfer matrix method to understand the optical properties of Tamm states and localization of the modes or electric fields in the structure. Tamm states can exist with zero in-plane wavevector components and can be created without the use of a coupling prism. We show that fluorophores on top of the metal film can interact with the Tamm state under the metal film and display Tamm state-coupled emission (TSCE). In contrast to SPCE, the Tamm states can display either S- or P-polarization. The TSCE angle is highly sensitive to wavelength which suggests the use of Tamm structures to provide both directional emission and wavelength dispersion. Metallic structures can modify fluorophore decay rates but also have high losses. Photonic crystals have low losses, but may lack the enhanced light-induced fields near metals. The combination of plasmonic and photonic structures offers the opportunity for radiative decay engineering to design new formats for clinical testing and other fluorescence-based applications.

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Section: Introductionmentioning

confidence: 99%

Radiative decay engineering 7: Tamm state-coupled emission using a hybrid plasmonic–photonic structure

Badugu

Descrovi

Lakowicz

2014

Analytical Biochemistry

106

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“…Highly confined fields proposed in these advanced studies could be applied to establish novel selection rules of the electronic excitation in the LSPR field, leading to the generation of excited electrons and holes with distinct electrochemical potentials in materials. In the field of chemistry, modifying electronic excitation by light leads to changes in the framework of photoenergy conversion [4]. Although the control of the photoexcitation process has not been achieved yet, the investigation of single-site SERS provides abilities beyond ultrasensitive spectroscopy to explore novel systems with advanced photofunctionalities.…”

Section: Future Expectationsmentioning

confidence: 99%

“…The positioning of matter in this field results in an apparent modification of the interaction between matter and light, compared with the general situation observed under light illumination of matter [4]. A highly localized field generates a huge gradient of field intensity over a distance smaller than 10 nm.…”

Section: Introductionmentioning

confidence: 96%

Single-site surface-enhanced Raman scattering beyond spectroscopy

2016

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Recent progress in the observation of surface-enhanced Raman scattering (SERS) is reviewed to examine the possibility of finding a novel route for the effective photoexcitation of materials. The importance of well-controlled SERS experiments on a single molecule at a single site is discussed based on the difference in the information obtained from ensemble SERS measurements using multiple active sites with an uncontrolled number of molecules. A single-molecule SERS observation performed at a mechanically controllable breaking junction with a simultaneous conductivity measurement provides clear evidence of the drastic changes both in the intensity and in the Raman mode selectivity of the electromagnetic field generated by localized surface plasmon resonance. Careful control of the field at a few-nanometer-wide gap of a metal nanodimer results in the modification of the selection rule of electronic excitation of an isolated single-walled carbon nanotube. The examples shown in this review suggest that a single-site SERS observation could be used as a novel tool to find, develop, and implement applications of plasmon-induced photoexcitation of materials.

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“…[6][7][8] Although the intrinsic crosssection of molecules for interaction with photons limits the probability of the electronic excitation, recent attempts to use localized plasmons for photoexcitation of molecules suggest the possibility of modifying the cross-section. 9,10 By changing the structure of the metal at the nanometer scale, the localization, energy, phase, and wave vector of the electromagnetic field of localized plasmons can be controlled. Such highly localized fields are expected to change the photoexcitation process of the electrons in the electronic states, because highly localized polarization less than the size of molecules breaks the symmetry of wavefunctions.…”

Section: ¹1mentioning

confidence: 99%

Molecule Manipulation at Electrified Interfaces using Metal Nanogates

et al. 2014

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Previously documented results on molecule manipulation using metal nanogates are comprehensively reviewed to conclude novel characteristics, which could be widely used for the developments of the systems at electrified interfaces. Novel systems to segregate molecules from self-spreading lipid bilayers in electrolyte solutions have been developed by using metal nanogate structures on solid surfaces. The spatial distribution of target molecules in the lipid bilayer changes depending on the molecule characteristics, such as charge, size, and flexibility. Energy dissipation during the spreading of the molecules on the surface contributes to the compression of the lipid bilayer at the nanogate, leading to the formation of a gradient of the electrochemical potential of the bilayer system including the target molecule in the vicinity of the nanogate (<100 nm from the gate). The gradient results in a segregation force being applied to target molecules in the order of 10 −15 N per molecule. The segregation property can be tuned by changing the electrolytes, lipid molecules, temperature, and the width and surface hydrophobicity of the metal nanogate. Introduction of asymmetry to the nanogate leads to further effective diffusion control in a direction perpendicular to the spreading. It has been demonstrated that target molecules with a different number of glycolipid per protein in the lipid bilayer are effectively separated based on the Brownian ratchet mechanism.

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Toward Plasmon-Induced Photoexcitation of Molecules

Cited by 99 publications

References 94 publications

Radiative decay engineering 7: Tamm state-coupled emission using a hybrid plasmonic–photonic structure

Radiative decay engineering 7: Tamm state-coupled emission using a hybrid plasmonic–photonic structure

Single-site surface-enhanced Raman scattering beyond spectroscopy

Molecule Manipulation at Electrified Interfaces using Metal Nanogates

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