Surface plasmon-coupled emission and Fabry-Perot resonance in the sample layer: A theoretical approach

A theoretical approach is used to investigate the coupling of surface plasmon-coupled emission to Fabry-Perot resonance in the sample layer. Quantities investigated are emission angles, polarization, power levels, and fluorescence lifetimes. The results are compared to experimental findings. For comparison a layered structure without surface plasmons, possessing only dielectric Fabry-Perot resonances, is explored. This structure seems to be amenable to s-polarization only but is in principle loss-less and has more degrees of freedom for design and optimization.     

Multicolor directional surface plasmon-coupled chemiluminescence

In reports over the past several years, we have demonstrated the efficient collection of optically excited fluorophore emission by its coupling to surface plasmons on thin metallic films, where the coupled luminescence was highly directional and polarized. This phenomenon is referred to as surface plasmon-coupled emission (SPCE). In this current study, we have extended this technique to include chemiluminescing species and subsequentially now report the observation of surface plasmon-coupled chemiluminescence (SPCC), where the luminescence from chemically induced electronic excited states couples to surface plasmons in thin continuous metal films. The SPCC is highly directional and predominantly p-polarized, strongly suggesting that the emission is from surface plasmons instead of the luminophores themselves. This indicates that surface plasmons can be directly excited from chemically induced electronic excited states and excludes the possibility that the plasmons are created by incident excitation light. This phenomenon has been observed for a variety of chemiluminescent species in the visible spectrum, ranging from blue to red, and also on a variety of metals, namely, aluminum, silver, and gold. Our findings suggest new chemiluminescence sensing strategies on the basis of localized, directional, and polarized chemiluminescence detection, especially given the wealth of assays that currently employ chemiluminescence-based detection.     

Linearly polarized emission of an organic semiconductor nanobelt

Linearly polarized emission has been observed for the nanobelts fabricated from a perylene diimide molecule through both solution-based and surface-supported self-assembling. The measurement of polarized emission was performed over single nanobelts with use of a near-field scanning optical microscope (NSOM) adapted with emission polarization (by putting a planar polarizer before the detector). Rotating the emission polarizer (from 0 degrees to 180 degrees) changed the emission intensity in a way depending on the relative angle between the long axis of the belt and the polarizer with a minimum of intensity detected at ca. 78 degrees, which is indicative of the tilted stacking of molecules along the belt direction.     

Demonstration of a surface plasmon-coupled emission (SPCE)-based immunoassay in the absence of a spacer layer

The technique of surface plasmon-coupled emission (SPCE) involves the coupling of light which is emitted from a fluorophore into the surface plasmon of an adjacent thin metal film, giving rise to highly directional emission. We have combined the advantages of SPCE with the high light collection efficiency of supercritical angle fluorescence by carrying out an immunoassay on a paraboloid array biochip in the absence of the conventional SPCE spacer layer normally used to minimize metal quenching of the fluorescence. In this work, we have successfully demonstrated an SPCE-based assay by utilizing the protein assay layer as the spacer layer. A novel 3 × 3 injection molded polymer biochip with paraboloid elements was used. The paraboloid elements served to enhance the light collection efficiency while the top surface was coated with a gold layer to use excitation of surface plasmons and detection of SPCE emission. Theoretical modeling of the gold-protein layer structure showed that the surface plasmon resonance angles were located in the detection range of the paraboloid biochip. The polarization dependence of SPCE emission was also demonstrated. Finally, a human IgG sandwich immunoassay was carried out which exhibited a limit of detection of ~10 ng/ml using 3σ. The results demonstrate the potential of the SPCE-based paraboloid array biochip as a novel platform for high-throughput analysis of biomolecular interactions.     

Analysis of immunoarrays using a gold grating-based dual mode surface plasmon-coupled emission (SPCE) sensor chip

We have developed a novel dual mode immunoassay platform that combines the advantages of real-time, label free measurement of surface plasmon resonance (SPR) and the highly directional surface plasmon-coupled emission (SPCE) using a gold grating-based sensor chip. Since only fluorophore-labeled analyte molecules that are close to the metal surface of the sensor chip will couple to the surface plasmon, SPCE detection is highly surface-specific leading to background suppression and increased sensitivity. Theoretical calculations were done to find SPR and SPCE angles for a sensor chip optimized for Alexa Fluor 647. We have confirmed the SPR and SPCE responses on the dual mode sensor chip using Alexa Fluor 647 labeled anti-mouse IgG. Signal fluctuation of the dual mode sensor chip reader was below 1.2% and 0.8% for SPR and SPCE, respectively. The SPR response in this configuration showed a minimum detection level of 1 μg ml(-1), and the SPCE response showed a minimum detection level of 1 ng ml(-1) for the same sample. A range of human IgG concentrations in human serum was also analyzed with the dual mode sensor chip. The SPCE measurement is more sensitive than the SPR real-time measurement, and substantially extends the dynamic range of the assay platform, as well as enabling independent measurements of co-localized analytes on the same sensor chip region of interest. Since this assay platform is capable of measuring more than 1000 spatially encoded regions of interest on a 1 cm(2) sensor chip, it has the potential for high-content analyses of biological samples with both research and clinical applications.     

Planar polarized light emission from CdSe nanoparticle clusters

This paper describes synthesis and optical properties of planar clusters of CdSe nanocrystals. The clusters emit linearly polarized light in the plane of the cluster. The emission wavelength of the clusters can be adjusted between 568 and 639 nm with the size of the CdSe nanocrystals. Planar CdSe microclusters were synthesized by reaction of trioctylphosphine oxide-coated CdSe/CdS nanocrystals with 3-aminopropylsilyl-modified Ca(2)Nb(3)O(10) nanosheets in THF. The clusters are 3.92 +/- 1.18 mum length/width and 91 +/- 37 nm thickness, and they consist of alternating layers of Ca(2)Nb(3)O(10) to which CdSe nanocrystals are attached with densities of 5300 +/-310 particles per side of a single Ca(2)Nb(3)O(10) sheet. The chemical inertness of the clusters in coordinating solvents suggests covalent interactions between the aminopropyl groups and CdSe nanocrystals. Upon excitation at lambda(exc) = 400 nm, the clusters emit green (568 nm), orange (589 nm), or red (639 nm) light, depending on the size of the CdSe crystals. The light is emitted preferentially in the cluster plane and it is linearly polarized along the cluster edges. Combined fluorescence microscopy and atomic force microscopy reveal that the directional emission efficiency depends linearly on the thickness of the clusters, which varies between 70 and 180 nm. The ability to manipulate the direction and polarization of the photoemission of CdSe nanoparticles via assembly into 2D structures is of interest for applications of these and similar structures in advanced optical materials and devices.     

High-efficiency circularly polarized emission from liquid-crystalline platinum complexes

Realizing both a high emission efficiency and luminescence dissymmetry factor (g_lum) in circularly polarized solution processable organic light-emitting diodes (CP-OLEDs) remains a significant challenge. In this contribution, two chiral phosphorescent liquid crystals based on cyclometalated platinum complexes are prepared, in which the chiral s-2-methyl-1‑butyl group is introduced into the cyclometalating ligand and the mesogenic fragment is attached to the periphery of the ancillary ligand. The platinum complexes exhibit both smectic and chiral nematic phases as evidenced by polarized optical microscopy, differential scanning calorimetry and small-angle X-ray diffraction. Remarkably, a high photoluminescent quantum efficiency of over 78% and clear circularly polarized luminescent signal with g_PL of about 10^–2 are observed for the complexes. Further, solution-processed CP-OLEDs show maximum external quantum efficiencies (EQE) of over 15% and strong circularly polarized electroluminescent signals with a g_EL ≈ 10^–2. This research demonstrates that both liquid crystallinity and the number of chiral centers play key roles in improving the chiroptical property, paving the way for a new approach for the design of high-efficiency CPL emitters.     

Amplified spontaneous emission,optical waveguide and polarized emission based on 2,5-diaminoterephthalates

A series of 2,5-diaminoterephthalates with a simple structure were synthesized through one-step reaction, and their bar-shaped single crystals with a large size and a smooth surface have been obtained via the solvent-evaporation method. These crystals exhibit bright emission with fluorescence quantum yields higher than 0.2. They display the waveguide property, and low optical loss coefficients for waveguide have been determined for the crystal of one compound. In addition, the crystal can cause linear polarization of the light emitted from it, with a high polarization contrast of 0.70. Most importantly, these crystals can realize amplified spontaneous emission(ASE), including the red ASE, with appreciable energy thresholds of 72–198 k W/cm~2 and high gain coefficients, which suggests the potential of these crystals for the application in organic solid-state lasers.     

Highly polarized absorption and emission from polymer-stabilized smectic guest-host systems

ABSTRACT

The optical properties of luminescent molecules dissolved in liquid crystals have led to their proposed use in luminescent thin-film polarizers. These molecules are typically required to fulfil a range of criteria related to their absorption and emission properties, degree of alignment and stability; however, concurrently satisfying these requirements has proven a barrier in their practical use. We obtained highly polarized absorption and emission luminescent thin-film polarizer using reactive liquid crystalline monomers and highly dichroic luminescent dyes, both of which have polymerizable end groups. In situ photopolymerization of the liquid crystalline mixtures in the highly ordered SmB phase resulted in the formation of cross-linked polymeric networks in which the anisotropic absorption and emission of the film were fixed. The as-obtained product exhibited a high dichroic ratio (DR = 30) with a large fluorescence quantum yield (?_F = 0.77). The device is both cheap and easy to fabricate and has the potential to be used in practical electro-optic applications.     

Organic crystal fibers aligned into oriented bundles with polarized emission

We demonstrate a simple method for growing organic crystal fiber bundles as long as centimeters by controlling the shape and dimension of the evaporation channel of the chloroform solution of N,N'-bis(1-ethylpropyl)-3,4,9,10-perylenebis(dicarboximide) (EPPTC). The capillary effect induces a thin solution film (capillary film) on the wall of the evaporation channel, and fast evaporation of the solvent gives rise to a concentration gradient along the channel. Thus, the strong pi-stacking between the EPPTC molecules in the capillary film results in formation of crystal fibers. Nearly linearly polarized emission centered around 620 nm has been detected from these crystal fibers under optical excitation. Measurements of the electron diffraction pattern and optical microscopic properties show well-defined stacking of the molecules in the crystal fibers with excellent alignment.     

Soft X-ray radiation-induced electron emission from the surface of polarized ferroelectrics

Additional electron emission that reflects specific properties of ferroelectrics was detected after the negatively charged surface of these preliminarily polarized materials was exposed to soft X-radiation (hv) ≤3 kV). The properties of this emission, which is referred to as anomalous electron emission (AEE) and is excited in single-crystal and ceramic samples, are studied with a standard X-ray photoelectron spectrometer. It is shown that the parameters of AEE spectra correlate with the characteristics of the materials. The conclusions of the phenomenological theory of the phenomenon are in satisfactory agreement with the experimental results. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 6, pp. 1031–1036, November–December, 1998     

Cruciforms' polarized emission confirms disjoint molecular orbitals and excited states

Steady-state and time-resolved polarized spectroscopy studies reveal that electronic excitation to the third excited state of 1,4-distyryl-2,5-bis(arylethynyl)benzene cruciforms results in fluorescence emission that is shifted an angle of ca. 60°. This result is consistent with quantum chemical calculations of the lowest electronic excited states and their transition dipole moments. The shift originates from the disjointed nature of the occupied molecular orbitals being localized on the different branches of the cruciforms.     

Measurement of the asymmetry in the emission of bremsstrahlung by transversely polarized electrons

Bremsstrahlung emitted by transversely polarized electrons shows a “right-left” asymmetry in spatial distribution. Measurements and remeasurements of this asymmetry are presented using electrons of 300 and 128 keV, respectively, impinging on a gold target. Within the accuracy of the experiment there are no significant discrepancies to the partial wave calculations of Tseng and Pratt.     

Surface orientation of a liquid-crystalline polymer studied by polarized reflection spectroscopy

The polarized reflection spectrum was used to evaluate the surface orientation of extruded sheets of liquid-crystalline copolyester consisting of 73 mol % 4-hydroxybenzoic acid units and 27 mol % 2-hydroxy-6-naphthoic acid units. The anisotropy of absorption index was evaluated from the specular reflectance using the Fresnel equation and the Kramers-Kronig relation. An intense absorption and observed in the ultraviolet region was assigned to the π^* ←π transitions of the constituent monomeric units. The observed spectra of the liquidcrystalline polymer were successfully interpreted by use of the spectroscopic data on the monomers. The transition moment directions of the monomeric units were calculated by molecular orbital calculations within the framework of the CNDO/S-Cl approximation. The Surface orientation functions obtained from polarized reflection spectra were compared with the crystal orientation functions in the bulk, which were obtained from the azimuthal intensity distribution of wide-angle x-ray diffraction. The orientation behaviour at the surface of the liquid-crystalline polymer was shown to be equivalent to the orientation behaviour in the bulk at higher draw-down ratio.     

Fluorene‐based liquid crystalline networks with linearly polarized blue emission

A series of fluorene‐based luminophores containing methacrylic end groups have been prepared and incorporated into uniaxially oriented liquid crystalline films by in situ photopolymerization. Various structural modifications on the 2‐(4‐cyanophenyl)fluorene core, which include alkyl chains at the 9‐position and elongation of the rigid core with one additional phenyl ring, have been investigated to generate emitters with adjusted liquid crystal compatibility, improved luminescence and dichroic properties. Polarized blue‐emitting films were produced that had an acceptable photostability, and it was found that the polarization emission was better for samples with low (5%) cross‐linker contents. Polarization of the luminescence was favored by the liquid crystalline properties of the luminophore. In addition, the detrimental effect of the alkyl substituent at the fluorene core on the mesomorphism and on the emission polarization can be overcome by lengthening the π‐system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4804–4817, 2007     

Polarization and fluence dependence of the polarized emission in nanosecond laser-induced breakdown spectroscopy

Several studies have appeared in the past two years reporting that the continuum emission produced by the laser ablation of solid materials is strongly polarized. In a paper that appears to conflict with these findings, Asgill et al. report that they did not observe a significant amount of polarization produced by nanosecond laser excitation of nitrogen gas and laser ablation of copper and steel ( M.E. Asgill, H.Y. Moon, N. Omenetto, D.W. Hahn, Investigation of polarization effects for nanosecond laser-induced breakdown spectroscopy, Spectrochim. Acta Part B (2010) xxx-xxx [7]). Here we show that the apparent discrepancy is resolved when laser fluence and polarization are taken into account. Using a 532 nm Nd:YAG laser to ablate Al samples in air, we find that the degree of polarization, P, of the continuum is greater for s- vs. p-polarized excitation and that P decreases with increasing fluence. We show that P would be < 10% under the conditions of Asgill et al., whereas P > 60% is obtained at low fluences with s-polarized excitation. We also confirm that at high fluence the polarization of the discrete emission is much smaller than that of the continuum.     

Determination of the molecular distribution in anisotropic media by polarized absorption and emission spectroscopy

A theory for the interpretation of polarized absorption and emission spectra of uniaxially oriented samples, including overlap of different polarized transitions in both processes, is described. Using this method for the interpretation of experimental data, the distribution of molecules possessing different geometrical anisotropy, incorporated in stretched polyethylene films, and the partial contribution of different polarized transitions to the total emission intensity can be estimated.     

Electric field assisted surface plasmon-coupled directional emission: an active strategy on enhancing sensitivity for DNA sensing and efficient discrimination of single base mutation

We have demonstrated the proof-of-principle of electric field assisted surface plasmon-coupled directional emission (E-SPCDE). The combination of SPCDE and electric field control produced a significant synergistic effect to amplify the right signal and suppress the wrong signal intelligently in an active strategy. A novel hairpin structured DNA biosensor based on the quenching and enhancing of fluorescence in SPCDE has been designed. With modulation of the fluorescence coupling efficiency, a high discrimination ratio up to more than 20-fold has been achieved by enhancing the signal of match and suppressing that of mismatch. E-SPCDE has shown a successful application in DNA sensing, eliminating false positives and false negatives in the detection. E-SPCDE should provide an opportunity to create a new generation of miniaturized high-performance sensing platforms especially in chip-based microarrays and to make the manipulation of the nanometer-scale processes more accessible and detectable.     

Ultra-thin emissive molecular devices: polarized emission of Ln(III) complex films

Abstract  On ultra-thin films, Tb(III) shows polarized ff-emission in the visible wavelength region induced by intramolecular energy transfer from the photoexcited organic ligand, such as phenanthroline. Pr(III) causes polarized ππ* emission from the chromophore in the ultra-thin film (Langmuir–Blodgett film). Here, the unique optical properties of molecular devices with lanthanide complexes are summarized. Graphical Abstract        

Three-primary-color molecular cocrystals showing white-light luminescence,tunable optical waveguide and ultrahigh polarized emission

Three-primary-color luminescent materials are highly desirable to construct white-light emitting resource,multi-color optical displays,and tunable photonic applications.However,the efficient strategy to establish the three-primary-color systems with unique photofunctionalities is still rather limited,particularly for molecular materials.Herein,we developed a molecular cocrystal route to obtain three-primary-color emissive materials by tuning different donor-acceptor units based on the same chromophore(4,4′-bis(2,5-dimethylstyryl)biphenyl,Bdb).The warm and cold white-light together with multi-color emission in most of visible region can be highly adjusted by rationally tuning different mixture components of three-primary-color cocrystals through an energy transfer mechanism.Furthermore,the blue/green/red emitters endow Bdb molecular cocrystals novel colortunable photonic properties(such as one-dimensional(1D)/2D optical waveguide,polarized fluorescence,up-conversion luminescence,and amplified spontaneous emission),benefitting from their well-defined micro/nanostructures and high crystallinity.Particularly,the high luminescence quantum yield(82.49%)and polarized anisotropy(0.723)outperform most of state-ofthe-art molecular crystalline materials.Therefore,this work supplies an effective way to fabricate new types of three-primarycolor phosphors through luminescent cocrystals,which have promising applications in the fields of full-color displays,whitelight irradiation,low-dimensional optical polarization,and micro/nanophotonics.