High-fidelity optofluidic on-chip sensors using well-defined gold nanowell crystals

Recent advances in nanofabrication techniques have enabled the creation of various metallic nanostructures in order to engineer the location and properties of electromagnetic hot spots in a controlled manner. However, most previous methods usually require complicated and time-consuming techniques, and the integration of metallic nanostructures into simple, low-cost devices for chemical or biological sensing is still challenging. Here, we report a promising new strategy for the fabrication of large-area gold nanowell arrays with novel geometric features that makes use of the trapping of self-assembled colloidal particles on a polymer surface. Through both systematic experimental and theoretical analysis, we confirm that the strong plasmon resonances of the proposed nanowell structures are associated with localized surface plasmon resonance (LSPR) on the brims of the nanoholes in the top gold films as well as in the bottom gold disks. In addition, we demonstrate a novel optofluidic platform with built-in subwavelength nanowell arrays that exhibits strong plasmon resonances within microfluidic chips. In our optofluidic systems, the plasmon coupling between the brims and the disks of nanowells makes the plasmon resonance more sensitive to surrounding materials. The dependence of the plasmon resonance on the refractive index of the surrounding medium is found to be as high as 570 nm RIU(-1) (refractive index units). These data lead to a figure of merit (FOM), the slope of refractive index sensitivity in eV RIU(-1)/line width (eV), as high as 4.1.     

Localized surface plasmon resonance spectroscopy of single silver triangular nanoprisms

The plasmonic properties of single silver triangular nanoprisms are investigated using dark-field optical microscopy and spectroscopy. Two distinct localized surface plasmon resonances (LSPR) are observed. These are assigned as in-plane dipolar and quadrupolar plasmon excitations using electrodynamic modeling based on the discrete dipole approximation (DDA). The dipole resonance is found to be very intense, and its peak wavelength is extremely sensitive to the height, edge length, and tip sharpness of the triangular nanoprism. In contrast, the intensity of the quadrupole resonance is much weaker relative to the dipole resonance in the single particle spectra than in the ensemble averaged spectrum. Several parameters relevant to the chemical sensing properties of these nanoprisms have been measured. The dependence of the dipole plasmon resonance on the refractive index of the external medium is found to be as high as 205 nm RIU(-1) and the plasmon line width as narrow as approximately 0.17 eV. These data lead to a sensing figure of merit (FOM), the slope of refractive index sensitivity in eV RIU(-1)/line width (eV), as high as 3.3. In addition, the LSPR shift response to alkanethiol chain length was found to be linear with a slope of 4.4 nm per CH2 unit. This is the highest short-range refractive index sensitivity yet measured for a nanoparticle.     

Resonance quenching and guided modes arising from the coupling of surface plasmons with a molecular resonance

In this paper, we describe experimental and modeling results that illucidate the nature of coupling between surface plasmon polaritons in a thin silver film with the molecular resonance of a zinc phthalocyanine dye film. This coupling leads to several phenomena not generally observed when plasmons are coupled to transparent materials. The increased absorption coefficient near a molecular resonance leads to a discontinuity in the refractive index, which causes branching of the plasmon resonance condition and the appearance of two peaks in the p-polarized reflectance spectrum. A gap exists between these peaks in the region of the spectrum associated with the molecular resonance and reflects quenching of the plasmon wave due to violation of the resonance condition. A second observation is the appearance of a peak in the s-polarized reflection spectra. The initial position of this peak corresponds to where the refractive index of the adsorbate achieves its largest value, which occurs at wavelengths just slightly larger than the maximum in the molecular resonance. Although this peak initially appears to be nondispersive, both experimental data and optical modeling indicate that increasing the film thickness shifts the peak position to longer wavelengths, which implies that this peak is not associated with the molecular resonance but, rather, is dispersive in nature. Indeed, modeling shows that this peak is due to a guided mode in the film, which appears in these conditions due to the abnormally high refractive index of the film near the absorbance maximum. Results also show that, with increasing film thickness, numerous additional guided modes appear and move throughout the visible spectrum for both s- and p-polarized light. Notably, these guided modes are also quenched near the location of the molecular resonance. The quenching of both the plasmon resonance and the guided modes can be explained by a large decrease in the in-plane wave propagation length that occurs near the molecular resonance, which is a direct result of the film's large absorption coefficient.     

Tuning of localized surface plasmon resonance of well-ordered Ag/Au bimetallic nanodot arrays by laser interference lithography and thermal annealing

A novel hybrid approach to fabricate large-area well-ordered Ag/Au bimetallic nanodot arrays and its potential applications for biosensing is investigated. With the combination of laser interference lithography and the thermal annealing technique, Ag/Au bimetallic nanodots about ~50 nm are formed inside periodic nanodisk arrays at a dimension of ~530 nm on quartz substrates. Extinction spectra of the fabricated nanostructures show their localized surface plasmon resonance (LSPR) can be well controlled by Au concentration, which offers a means to flexibly tune the optical properties of the nanodot arrays. To study the sensitivity of the nanodot arrays, resonance wavelength changes per refractive index unit (RIU) are performed in different surrounding environments. This shows a 94% increase in peak shift per refractive index unit (nanometers/RIU) compared to the nanodot arrays formed only by thermal annealing. These results demonstrate a feasible approach to improve LSPR-based biosensor performance.     

Effect of solvent refractive index on the surface plasmon resonance nanoparticle optical absorption

Optical properties of plasmon coupled silver and gold nanoparticles were studied as a function of the refractive index of the surrounding medium. Our studies confirmed that the effect of changes in the refractive index of the surrounding medium was more difficult to demonstrate from an experimental point of view, because of the very high susceptibility of nanoparticles to aggregate in aqueous and organic solvents. Whereas the position of the absorption bands of triiodide in these solvents shows a clear dependence on medium's refractive index, the surface plasmon band position of silver and gold nanoparticles do not exhibit the same dependence. This is attributed to a non-negligible interaction of these solvents with nanoparticle surfaces.     

Characterization of high refractive index semiconductor films by surface plasmon resonance

Si-based surface plasmon resonance (SPR) in the Kretschmann-Raether geometry is considered as a platform for the optical measurement of high refractive index films. The implementation of the SPR effect becomes possible due to the relatively high index of refraction of Si compared to most materials. As examples we study the SPR responses for some important semiconductor-based films, including laser-ablated porous silicon and thin germanium films. Using SPR data, we determine the refractive indices of these films for different parameters (thickness and porosity) and ambiences. We also discuss novel SPR biosensor architectures with the use of these solid films.     

Surface plasmon resonance sensor using an optical fiber with an inverted graded-index profile

A new optical fiber sensor based on surface plasmon resonance is described. It uses an optical fiber with an inverted graded-index profile. A theoretical analysis of the optical propagation when a point light source was used and a computation of the optical power transmitted by the fiber were performed. Experiments were carried out to measure changes of the transmitted power caused by refractive-index variations of the surrounding dielectric medium. Both the simulation and experiments have shown that the sensor exhibits high sensitivity for changes of the surrounding medium in a refractive index range from 1.33 to 1.39.     

Incident-angle-modulated molecular plasmonic switches: a case of weak exciton-plasmon coupling

We have designed an angularly tunable plasmonic system that consists of Au nanodisks in combination with molecules of photoswitchable resonance, spiropyran, to gain new insights into weak exciton-plasmon couplings. In the weak exciton-plasmon coupling regime, switching molecular resonance can induce localized surface plasmon resonance (LSPR) peak shifts due to the change in the refractive index of the molecular materials. On the basis of the angle-resolved spectroscopic study of the nanodisk-spiropyran system both with and without UV irradiation, we reveal an unusual "zigzag" curve for the LSPR peak shifts (due to the photoswitching of the molecular resonance) as a function of the original LSPR peak wavelength. A further theoretical analysis attributes the "zigzag" curve to two significant competing effects that depend on the incident angle of the probe light: plasmon-enhanced molecular resonance absorption and LSPR sensitivity to the surroundings' refractive index.     

Application of two-dimensional spectral surface plasmon resonance to imaging of pressure distribution in elastohydrodynamic lubricant films

What we believe to be a novel two-dimensional spectral surface plasmon resonance imaging technique determining pressure distribution in elastohydrodynamic lubricant films is presented. This technique makes use of the spectral characteristics associated with the surface plasmon resonance (SPR) effect, and it provides more spectral information in refractive index mapping than conventional contrast SPR imaging. Two-dimensional imaging is demonstrated and applied to a highly pressurized liquid lubricant trapped inside an elastohydrodynamic lubrication (EHL) dimple. The hydrostatic pressure inside the EHL dimple causes a localized change of the refractive index of the lubrication oil. This also results in a shift in the spectral SPR absorption dip. By monitoring the color changes within the SPR image and calibrating with lubricants of known refractive index profiles, we can obtain a direct measurement of the refractive index distribution within the EHL dimple. PB 2400 lubricant dimples were studied in our experiments. The proposed SPR imaging approach is irrespective of the absolute lubricant film thickness h, therefore overcoming the major limitations of a conventional optical interference technique. With further development of the two-dimensional refractive index mapping technique, widespread applications in various fields are possible, including high-throughput sensors and the detection of bioaffinity interactions.     

Evanescent field in surface plasmon resonance and surface plasmon field-enhanced fluorescence spectroscopies

The highly sensitive nature of surface plasmon resonance (SPR) spectroscopy and surface plasmon field-enhanced fluorescence spectroscopy (SPFS) are governed by the strong surface plasmon resonance-generated evanescent field at the metal/dielectric interface. The greatest evanescent field amplitude at the interface and the maximum attenuation of the reflectance are observed when a nonabsorbing dielectric is employed. An absorbing dielectric decreases the evanescent field enhancement at the interface. The SPR curve of an absorbing dielectric is characterized by a greater reflectance minimum and a broader curve, as compared to those of the nonabsorbing dielectric with the same refractive index. For a weakly absorbing dielectric, such as nanometer-thick surface-confined fluorophores, the absorption is too small to induce a significant change in the SPR curve. However, the presence of a minute amount of the fluorophore can be detected by the highly sensitive SPFS. The angle with the maximum fluorescence intensity of an SPFS curve is always smaller than the resonance angle of the corresponding SPR curve. This discrepancy is due to the differences of evanescent field distributions and their decay characteristics within the metal film and the dielectric medium. The fluorescence intensity in an SPFS curve can be expressed in terms of the evanescent field amplitude. Excellent correlations between the experimentally measured fluorescence intensities and the evanescent field amplitudes are observed.     

Einfluss der Oberflächenmorphologie auf die Performance von Low‐E Schichtsysteme

The influence of roughness of plastic substrate was investigated regarding low e functional film properties. Using a rough surface results in increased absorption in the visible spectral range. This absorption is mainly caused by surface plasmon excitation. In order to achieve high transmittance (T_vis) – which is required for the application in insulating glass units – it is required to use smooth substrate surfaces. An appropriate pre conditioning of the substrate can provide improved surface conditions. The strength and spectral position of the plasmon resonance is also determined by the dielectric material surrounding the silver. A high refractive index material is required to anti‐reflect the silver properly. But on rough surfaces this may result in increased absorption. One possibility to overcome the strong absorption is applying an intermediate layer with lower index next to the silver.     

Using direct nanoimprinting of ferroelectric films to prepare devices exhibiting bi-directionally tunable surface plasmon resonances

In this paper, we describe an imprint method for the fabrication of bi-directionally tunable surface plasmon resonance (SPR) filters. A periodic metal/ferroelectric film stack exhibiting SPR phenomena was directly imprinted using a sharp mold without the need for a polymer-based resist. Both the refractive index of the surrounding lead zirconate titanate (PZT) films and the period of the textured PZT/metal/PZT structure were dependent upon both the absolute value and sign of the applied potential. The SPR wavelength of the PZT/gold/PZT-based tunable filter varied over a range of greater than 100?nm when applying potentials ranging from 0 to -15?V. This imprinting method has great potential for use in the fabrication of tunable optical filters without the need for complicated processes or specific materials.     

Local plasmon resonance at metal wedge

A local plasmon resonance on a metal wedge is studied by using the Meixner approach [J. Meixner, IEEE Trans. Antennas Propag.AP-20, 442 (1972)]. It is found that the singular field behavior of a local plasmon resonance as a function of the distance from the edge of the wedge is sensitive to the wavelength and wedge angle, and ranges from a dramatic increase in amplitude close to its theoretical limit to pure oscillatory behavior with only minor amplitude variation. Field singularities for gold, silver, and aluminum wedges are calculated. It is shown that, unlike an ideal-conductor wedge, the real part of the power index of the electric field singularity does not decrease monotonically as a function of the wedge angle, but has a minimum for some angle depending on the wavelength and material parameters. If the dielectric surrounding the wedge has a positive permittivity equal to the absolute value of that of the metal, and hence satisfies the plasmon resonance condition, then the electric field has a peculiar behavior for a wedge whose shape is close to the flat surface.     

Target dependence of the sensitivity in periodic nanowire-based localized surface plasmon resonance biosensors

We investigate the target dependence of the sensitivity in a localized surface plasmon resonance (LSPR) biosensor and compare it with that of a conventional thin-film-based plasmon resonance structure. An LSPR biosensor was modeled as subwavelength periodic nanowires on a metal/dielectric substrate and targets either as bulk refractive index changes or as a biomolecular interaction that forms a monolayer. The results found that significant target-dependent variation arises in sensitivity and sensitivity enhancement by LSPR. The variation is attributed to the nonlinearity in the plasmon dispersion relation as well as the effective permittivity due to strong LSPR signals. The target dependence suggests that an LSPR structure be designed based on estimated index changes induced by target interactions. Associated broadening of resonance width can be controlled by way of profile engineering, which is discussed in connection with experimental data.     

Nanoarray-based biomolecular detection using individual Au nanoparticles with minimized localized surface plasmon resonance variations

Here, we present a mean to expand the use of individual metallic nanoparticles to two-dimensional plasmonic nanoarrays. An optical detection platform to track down localized surface plasmon resonance (LSPR) signals of individual nanoparticles on substrates was built for the application of plasmonic nanoarrays. A pseudoimage of nanoparticles on a substrate was reconstructed from their scattering spectra obtained by scanning a user-defined area. The spectral and spatial resolutions of the system were also discussed in detail. Most importantly, we present a method to normalize the localized surface plasmon resonance from geometrically different nanoparticles. After normalization, plasmonic responses from different particles become highly consistent, creating well-fitted dose-response curves of both surrounding refractive index changes and receptor-analyte binding to the surface of individual nanoparticles. Finally, the proof-of-concept system for plasmonic nanoarray detection is demonstrated by the measurement of the aptamer-thrombin binding event.     

Tunable plasmonic properties of silver nanorods for nanosensing applications

Localized surface plasmon resonance (LSPR) sensitivity to the surrounding medium refractive index has been studied for silver nanorods using Gans theory including the effect of retardation and surface scattering. The simulation results show the refractive index sensitivity (eV/RIU) maxima positions at width of 9, 6, and 4 nm for aspect ratios of 2, 3, and 4, respectively. Based on the sensing figure of merit (FOM), 9 nm is found to be a significant nanorod width, where the FOM dependence on width with respect to aspect ratio inverts. However, the optimal nanorod width for both the FOM and the modified figure of merit (MFOM) is about 6 nm for aspect ratios of 2, 3, and 4. A comparison with gold shows that silver nanorods exhibit relatively higher FOM and MFOM and thus, making them potential candidates for biochemical nanosensing applications.     

Solid-phase synthesis and photochromic switching of a polymeric photochromic layer on a gold surface

The preparation of a novel carboxymethylated dextran photochromic polymer on a gold surface is presented here. Ethylester-dihydroindolizine is attached by amine coupling to a carboxymethylated dextran polymer on the gold surface of a Surface Plasmon Resonance (SPR) sensor. The photoinduced switch between the two isomers of the ethylester-dihydroindolizine photochromic polymer was investigated by fiber optics based surface plasmon resonance. The different solvent effect on the SPR shift is also reported. A larger absolute shift was obtained in solvents with low relative dielectric constants, than in solvents with a larger relative dielectric constant. A blue shift was observed with organic solvents and a red shift for the aqueous solvent. Moreover, by changing the solvent, the refractive index of the surrounding media in contact with the gold surface also changes and the wavelength used to excite the surface plasmon can be shifted outside the excitation/relaxation range of the photochromic system.     

Simulation on wavelength-dependent complex refractive index of liquids obtained by phase retrieval from reflectance dip due to surface plasmon resonance

A method for the calculation of the wavelength-dependent complex refractive index of absorbing liquid from reflectance in the vicinity of surface plasmon resonance (SPR) is presented. The calculation is based on the maximum entropy method (MEM). As an example, phase retrieval from a simulated SPR reflectance of a red colored liquid solution is carried out. It is proposed that MEM can be applied to wavelength-dependent complex refractive index assessment from reflectance of absorbing liquids in SPR measurement in wavelength scanning mode.     

Optical detection of single non-absorbing molecules using the surface plasmon resonance of a gold nanorod

Existing methods for the optical detection of single molecules require the molecules to absorb light to produce fluorescence or direct absorption signals. This limits the range of species that can be detected, because most molecules are purely refractive. Metal nanoparticles or dielectric resonators can be used to detect non-absorbing molecules because local changes in the refractive index produce a resonance shift. However, current approaches only detect single molecules when the resonance shift is amplified by a highly polarizable label or by a localized precipitation reaction on the surface of a nanoparticle. Without such amplification, single-molecule events can only be identified in a statistical way. Here, we report the plasmonic detection of single molecules in real time without the need for labelling or amplification. Our sensor consists of a single gold nanorod coated with biotin receptors, and the binding of single proteins is detected by monitoring the plasmon resonance of the nanorod with a sensitive photothermal assay. The sensitivity of our device is ～700 times higher than state-of-the-art plasmon sensors and is intrinsically limited by spectral diffusion of the surface plasmon resonance.     

Localized surface plasmon resonance biosensor using silver nanostructures fabricated by glancing angle deposition

Glancing angle deposition was used to produce approximately 150-nm-thick silver nanoparticle films, which were evaluated as localized surface plasmon resonance (LSPR) biosensors. The films have a strong extinction peak around 368 nm in air due to LSPR. As the refractive index of the surrounding environment is increased, the extinction peak red-shifts with a linear dependence. The films were functionalized with 11-amino-1-undecanethiol and rabbit immunoglobulin G (rIgG) to allow for the detection of anti-rIgG binding. Binding of biomolecules to the nanoparticle surface increases the local refractive index and results in a red-shifting of the extinction peak. The wavelength shift at varying concentrations of anti-rIgG was measured and fit to the Langmuir isotherm. This yielded approximate values for the saturation response, Delta lambda max = 29.4 +/- 0.7 nm, and the surface confined binding constant, Ka = (2.7 +/- 0.3) x 10(6) M(-1). The response to nonspecific binding was also investigated.