Plasmon Shift Research Articles

Large-scale plasmonic-SERS templates by successive growth steps

This work presents the fabrication of large-scale tunable-plasmonic surface-enhanced Raman scattering (SERS) templates and investigates their Raman enhancement. Substrates for SERS were prepared by deposition of gold nanoparticles on a glass slide followed by their growth. A plasmon shift was observed upon growing due to the formation of elongated nanoparticles and their mutual coupling. The changes in particle size, shape and interparticle distances were indicated by SEM measurements. Surface-enhanced Raman spectra of Nile blue A at a very low concentration on top of a blocking layer were measured. The overall Raman enhancement is correlated with the number of growth steps. For excitation at 532 nm four growth steps lead to maximum enhancement. Better overlap of excitation laser and the plasmon resonances upon growing increased the enhancement until four steps while further growing decreased the enhancement. At longer wavelengths excitation (633 and 785 nm) the enhancement further increased beyond the fourth growth step. This enhancement is caused by the plasmon excitation of narrower gap sizes. The proposed procedure for the SERS substrates is simple, allows covering large surface areas and plasmon band tuning from 530 nm to the near infrared in order to increase overall Raman enhancement.

Silver/gold core-shell nanoprism-based plasmonic nanoprobes for highly sensitive and selective detection of hydrogen sulfide.

A simple and highly sensitive and selective hydrogen sulfide assay utilizing plasmonic nanoprobes is presented in this report. The assay employs the etching of silver in the Ag/Au core-shell nanoprisms, accompanied by surface plasmon resonance (SPR) signal depression and shift. Briefly, thin layers of gold are first coated onto silver nanoprisms. The thin gold layer not only guarantees the high stability of the plasmonic nanoprobes but also ensures the high selectivity toward hydrogen sulfide. Once hydrogen sulfide is introduced, the silver core is converted to Ag2S mainly from its lateral walls. Moreover, the SPR peak is located in the NIR region that makes these plasmonic nanoprobes more appealing for the detection of hydrogen sulfide in real-world samples and in in vivo applications.

Size-Dependent Shifts of Plasmon Resonance in Silver Nanoparticle Films Using Controlled Dissolution: Monitoring the Onset of Surface Screening Effects

A study of the size dependent blue- and red-shift of the plasmon band of silver nanoparticle films in aqueous solution is reported. A detection scheme, where the particle size is continuously decreased by means of controlled dissolution, while measuring the plasmon band position by UV–vis absorption spectroscopy is used. Both blue- and red-shifts of the peak position are observed, depending on the presence of electron donors and/or acceptors in the solution, respectively. A great increase in plasmon shifts for smaller particle sizes (R 10 nm) is demonstrated, which we ascribe to a transition from an extrinsic regime for the larger particles, where shifts of the plasmon frequency are related to changes in the dielectric environment, while the dielectric function of the metal is constant, to an intrinsic regime for the smaller particles. For this intrinsic regime, operative for small particles, nonlocality of the dielectric constant has to be considered. The experimental data are fitted with a...

Optical refractive nanosensor with planar resonators metamaterial

We numerically investigated the optical properties of planar resonators metamaterial that exhibits two narrow transmitted dips with quality factors of 23 and 50 in the optical regions. The results show that, both of the two resonances reveal a distinct plasmon shift with respect to a small fluctuation in the refractive index of the surrounding medium, and calculated average refractive index sensitivities are 900nm/RIU and 493nm/RIU, and corresponding figure of merits of two modes are 16 and 32 in vacuum, respectively. The sensing performance can be improved by changing the geometric parameters of planar metamaterial due to the plasmon modes coupling effect, which offer an excellent potential for optical nanosensing applications.

Tuning the plasmon band number of aluminum nanorod within the ultraviolet-visible region by gold coating

The localized surface plasmon (LSP) properties of Al nanorod with Au coating have been investigated by using the quasi-static calculation. Because of the anisotropic plasmon splitting and the plasmon coupling between the Al and Au surfaces, the band number of LSP in the Al-Au core-shell nanorod could be tuned from 2 to 4 continuously in the ultraviolet-visible region. Due to the non-spherical symmetry and the dielectric polarization-induced plasmon energy fading, the Au coating-dependent plasmon shift and split are further affected by the aspect ratio and the dielectric surrounding. When the aspect ratio or the surrounding dielectric constant has a small value, the band number of LSP could only be tuned from 2 to 3. However, the band number of LSP could only be tuned from 3 to 4 when the aspect ratio or the surrounding dielectric constant has a large value. This tunable band number of LSP in the Au-coated Al nanorod provides potential application for multichannel plasmonic nanosensors.

Fast characterization of gold nanorods ensemble by correlating its structure with optical extinction spectral features

Owing to unique size- and shape- dependent localized surface plasmon resonance (LSPR) of noble metal nanoparticles (NPs), the optical extinction spectroscopy method (OES) has received much attention to characterize the geometry of metal NPs by fitting experimental UV-vis-NIR spectra. In this work, we aimed to develop a more convenient and accurate OES method to characterize the structural parameters and concentration of the gold nanorods (GNRs) ensemble. The main difference between our approach and previous OES methods is that we solve this inverse spectra problem by establishing the LSPR relation equations of GNRs ensemble so that there is no need of UV-vis-NIR spectra fitting process. The aspect ratio (AR) and AR distribution can be directly retrieved from two of UV-vis-NIR spectral parameters (peak position and full width at half maximum) using the obtained relation equations. Furthermore, the relation equations are modified for applying to the more general GNRs samples by considering the plasmon shift due to the near distance dielectric sensitivity. Finally, instead of inductively coupled plasma mass spectrometry (ICP-MS) measurement, we provide a more facile measure of the mass-volume concentration which can be determined from the extinction value at 400 nm. By comparing with the experimental results, it shows that the retrieved results by the relation equations are reliable.

Ultrasensitive Plasmonic Response of Bimetallic Au/Pd Nanostructures to Hydrogen

Hydrogen detection is crucial for the safety of all hydrogen‐related applications. Compared to electrical hydrogen sensors, which usually suffer from possible electric sparks, optical hydrogen sensors offer advantages of remote and contact‐free readout and therefore the avoidance of spark generation. Herein, bimetallic Au/Pd nanostructure monolayers that exhibit ultrasensitive plasmonic response to hydrogen are reported. Bimetallic Au/Pd nanostructures with continuous and discontinuous Pd shells are prepared. The plasmonic response to hydrogen is monitored by measuring the extinction spectra of the ensemble Au/Pd nanostructures deposited on glass slides. Introduction of hydrogen induces red plasmon shifts, which become larger for the nanostructures with thicker Pd shells. For the nanostructures with continuous Pd shell, the plasmon shift can reach 56 nm at the hydrogen volume concentration below the explosion limit. The plasmon resonance wavelength displays an excellent linear dependence on the hydrogen volume concentration below 1%. The detection limit in the experiments reaches 0.2%. The nanostructures with discontinuous Pd shell show smaller plasmon shifts than those with continuous Pd shell. The extinction measurements on the ensemble nanostructures supported on transparent substrates and the unprecedentedly large plasmon shifts and sensitivity make the results very promising for the development of practical optical hydrogen sensors.

Further reduction of efficiency droop effect by adding a lower-index dielectric interlayer in a surface plasmon coupled blue light-emitting diode with surface metal nanoparticles

Further reduction of the efficiency droop effect and further enhancements of internal quantum efficiency (IQE) and output intensity of a surface plasmon coupled, blue-emitting light-emitting diode (LED) by inserting a dielectric interlayer (DI) of a lower refractive index between p-GaN and surface Ag nanoparticles are demonstrated. The insertion of a DI leads to a blue shift of the localized surface plasmon (LSP) resonance spectrum and increases the LSP coupling strength at the quantum well emitting wavelength in the blue range. With SiO2 as the DI, a thinner DI leads to a stronger LSP coupling effect, when compared with the case of a thicker DI. By using GaZnO, which is a dielectric in the optical range and a good conductor under direct-current operation, as the DI, the LSP coupling results in the highest IQE, highest LED output intensity, and weakest droop effect.

(Gold core)@(ceria shell) nanostructures for plasmon-enhanced catalytic reactions under visible light.

Driving catalytic reactions with sunlight is an excellent example of sustainable chemistry. A prerequisite of solar-driven catalytic reactions is the development of photocatalysts with high solar-harvesting efficiencies and catalytic activities. Herein, we describe a general approach for uniformly coating ceria on monometallic and bimetallic nanocrystals through heterogeneous nucleation and growth. The method allows for control of the shape, size, and type of the metal core as well as the thickness of the ceria shell. The plasmon shifts of the Au@CeO2 nanostructures resulting from the switching between Ce(IV) and Ce(III) are observed. The selective oxidation of benzyl alcohol to benzaldehyde, one of the fundamental reactions for organic synthesis, performed under both broad-band and monochromatic light, demonstrates the visible-light-driven catalytic activity and reveals the synergistic effect on the enhanced catalysis of the Au@CeO2 nanostructures.

Plasmonic response of DNA-assembled gold nanorods: Effect of DNA linker length, temperature and linker/nanoparticles ratio

Optical properties of gold nanorod (AuNR) particles self-assembled with DNA are systematically investigated. The particles assembly is driven by specific base-pair recognition between single strand (ss) DNA linker and DNA anchored to AuNRs, and it results in the distance- and morphology-dependent plasmonic coupling of AuNRs. The longitudinal plasmon band is distinctly affected by tuning the length of DNA linker, the temperature and linker/AuNRs ratio. We observed that the increase of temperature enhances the interparticle interactions and leads to clear distinguishable plasmonic signals between linker lengths up to 100 bases. Both absorbance decrease and shift of the longitudinal plasmon allow for use of AuNR for the DNA sensing applications.

Electrically tunable plasmonic behavior of nanocube-polymer nanomaterials induced by a redox-active electrochromic polymer.

We present a plasmon-active hybrid nanomaterial design with electrochemical tunability of the localized surface plasmon resonances. The plasmonic-active nanostructures are composed of silver nanocube aggregates embedded into an electrochromic polymer coating on an indium tin oxide electrode with the nanocube aggregation controlled by the surface pressure. Such polymer-nanocube hybrid nanomaterials demonstrated unique tunable plasmonic behavior under an applied electrochemical potential. A significant reversible experimental peak shift of 22 nm at an electrical potential of 200 mV has been achieved in these measurements. Finite-difference time-domain (FDTD) simulations show that, under full oxidation potential, a maximal spectral shift of ca. 80 nm can be potentially achieved, which corresponds to a high sensitivity of 178 nm per refractive index unit. Furthermore, FDTD modeling suggests that the electrochemically controlled tunability of plasmonic peaks is caused by reversible changes in the refractive index of the electrochromic polymer coating caused by oxidation or reduction reactions under external electrical potential. Consequently, we define the orthogonal plasmonic resonance shift as a shift that is orthogonal to the redox process responsible for the refractive index change. On the basis of these results, we suggest that the combination of anisotropic nanostructures and electrochromic matrix has the potential to reversibly electrically tune plasmonic resonances over the full visible spectrum.

Spatial extent of plasmonic enhancement of vibrational signals in the infrared.

Infrared vibrations of molecular species can be enhanced by several orders of magnitude with plasmonic nanoantennas. Based on the confined electromagnetic near-fields of resonantly excited metal nanoparticles, this antenna-assisted surface-enhanced infrared spectroscopy enables the detection of minute amounts of analytes localized in the nanometer-scale vicinity of the structure. Among other important parameters, the distance of the vibrational oscillator of the analyte to the nanoantenna surface determines the signal enhancement. For sensing applications, this is a particularly important issue since the vibrating dipoles of interest may be located far away from the antenna surface because of functional layers and the large size of biomolecules, proteins, or bacteria. The relation between distance and signal enhancement is thus of paramount importance and measured here with in situ infrared spectroscopy during the growth of a probe layer. Our results indicate a diminishing signal enhancement and the effective saturation of the plasmonic resonance shift beyond 100 nm. The experiments carried out under ultra-high-vacuum conditions are supported by numerical calculations.

Quantification of cardiac biomarkers using label-free and multiplexed gold nanorod bioprobes for myocardial infarction diagnosis

Gold nanorod (GNR) is an attractive optical transducer for label-free biosensing owing to the localized surface plasmon resonance (LSPR) which is highly sensitive to the dielectric constant of the surrounding medium modulated by biological bindings. By adjusting the nanorod aspect ratio (length to width ratio), desired absorption wavelength can be continuously tuned from 600 to 1100nm. Here we demonstrated a linear relationship between the aspect ratio and the LSPR peak wavelength. Taking advantage of this tunability feature, we developed a multiplexed GNR sensor by combining nanorods with distinct LSPR wavelengths. Specifically, GNRs of AR 2.1 and 4.2 exhibiting longitudinal plasmonic band of 640 and 830nm, respectively, were functionalized with specific antibody. Concentrations of multiple analytes were measured by correlating to the spectral shift at the distinct plasmon band maxima upon specific binding. The practical use of this mixed bioprobes for simultaneous quantification of cardiac biomarkers (myoglobin and cardiac troponin I) in the clinically significant sensing range was described. The LSPR red shift magnitude is linearly proportional to the increase in the target analyte concentration (R2=0.98). The calibration curve can clearly differentiate varying biomarker amounts with a high specificity. For multiplexed biosensing, the plasmon shift at the dedicated peak wavelength can be specifically correlated with spiked biomarker for simultaneous detection in the sample mixture. This technology can be further transformed onto miniaturized biochips based on the nanosized optical transducer to allow point-of-care blood testing for risk stratifications of cardiac patients in clinical settings.

Cholesterol aided etching of tomatine gold nanoparticles: A non-enzymatic blood cholesterol monitor

Colloidal gold is extensively used for molecular sensing because of the wide flexibilities it offers in terms of modifications of the gold nanoparticles (GNPs) surface with a variety of functional groups. We describe a simple, enzyme free assay for the detection of cholesterol, and demonstrate its applicability by estimating cholesterol in human serum samples. To enable cholesterol detection, we functionalized GNPs with tomatine, a glycoalkaloid found in the leaves and stem of tomato plants. The binding of cholesterol onto tomatine functionalized gold nanoparticles (TGNPs) was characterized by a blue shift in the plasmon absorption spectra (SPR) followed by reduction in the particle size. The TGNPs have been core etched with increasing concentration of cholesterol and with 800ng/mL of cholesterol particles in the size range of 10–12nm have been obtained. This behavior was attributed to the enhanced hydrophobicity of the surface acquired by cholesterol binding resulting in the folding or shrinkage of molecule in turn leading to core etching. The method was successfully applied for the detection of cholesterol in real samples and agrees well with values obtained from the conventional method. Because of its significant plasmonic shift and simplicity, this biosensor could be used for cholesterol detection as it does not demand either any hazardous and costly chemicals or any complex synthetic routes.

Effect of surface roughness on self-assembled monolayer plasmonic ruler in nonlocal regime.

Recently, self-assembled monolayers (SAMs) have been used for plasmonic rulers to measure the nonlocal influence on the Au nanoparticle - metal film resonance wavelength shift and probe the ultimate field enhancement. Here we examine the influence of surface roughness on this plasmonic ruler in the nonlocal regime by comparing plasmonic resonance shifts for as-deposited and for ultra-flat Au films. It is shown that the resonance shift is larger for ultra-flat films, suggesting that there is not the saturation from nonlocal effects previously reported for the spacer range from 0.7 nm to 1.6 nm. We attribute the previously reported saturation to the planarization of the as-deposited films by thinner SAMs, as measured here by atomic-force microscopy. This work is of interest both in probing the ultimate limits of plasmonic enhancement with SAMs for applications in Raman and nonlinear optics, but also in the study of SAMs planarization as a function surface roughness.

Colorimetric Stress Memory Sensor Based on Disassembly of Gold Nanoparticle Chains

We report the development of a stress-responsive colorimetric film that can memorize the stress it has experienced. The system is designed by taking advantage of the plasmonic shift associated with the disassembly of one-dimensional gold nanoparticle chains driven by the plastic deformation of the surrounding polymer matrix. By modifying the plasticity of the polymer, we demonstrate that the plasmonic shift and colorimetric change respond to a large range of stresses. This novel pressure indicating film can be used to capture and record the pressure distribution and magnitude between two contacting or impacting surfaces by outputting color information.

Low-power all-optical tunable plasmonic-mode coupling in nonlinear metamaterials

All-optical tunable plasmonic-mode coupling is realized in a nonlinear photonic metamaterial consisting of periodic arrays of gold asymmetrically split ring resonators, covered with a poly[(methyl methacrylate)-co-(disperse red 13 acrylate)] azobenzene polymer layer. The third-order optical nonlinearity of the azobenzene polymer is enormously enhanced by using resonant excitation. Under excitation with a 17-kW/cm2, 532-nm pump light, plasmonic modes shift by 51 nm and the mode interval is enlarged by 30 nm. Compared with previous reports, the threshold pump intensity is reduced by five orders of magnitude, while extremely large tunability is maintained.

Detection of Dissolved CO2 Based on the Aggregation of Gold Nanoparticles

A sensitive colorimetric assay of dissolved CO2 (dCO2) was developed based on the plasmon shift of gold nanoparticles (AuNPs). A water-soluble random copolymer poly(dimethyl acrylamide-co-(N-amidino)ethyl acrylamide), or P(DMA-co-NAEAA), containing amidine groups was synthesized. In the presence of dCO2, the amidine groups in the NAEAA block protonate and convert the polymer from a neutral to a positive-charged state, hence triggering the negative-charged AuNPs to aggregate by the electrostatic interaction. The degree of AuNP aggregation is dependent on the charge density of polymer, which is related to dCO2 concentration. The aggregation of AuNPs results in a red shift of the AuNP plasmonic spectrum, or a color change from red to blue. In addition, dCO2 concentration can be quantitatively measured by the UV absorbance change of the AuNP solution. A linear relationship between 0.264 and 6.336 hPa of dCO2 with a limit of detection (LOD) of 0.04 hPa can be acquired. This is the first report to detect dCO2 using the optical properties of nanoparticles.

Using the Plasmon Linewidth To Calculate the Time and Efficiency of Electron Transfer between Gold Nanorods and Graphene

We present a quantitative analysis of the electron transfer between single gold nanorods and monolayer graphene under no electrical bias. Using single-particle dark-field scattering and photoluminescence spectroscopy to access the homogeneous linewidth, we observe broadening of the surface plasmon resonance for gold nanorods on graphene compared to nanorods on a quartz substrate. Because of the absence of spectral plasmon shifts, dielectric interactions between the gold nanorods and graphene are not important and we instead assign the plasmon damping to charge transfer between plasmon-generated hot electrons and the graphene that acts as an efficient acceptor. Analysis of the plasmon linewidth yields an average electron transfer time of 160 ± 30 fs, which is otherwise difficult to measure directly in the time domain with single-particle sensitivity. In comparison to intrinsic hot electron decay and radiative relaxation, we furthermore calculate from the plasmon linewidth that charge transfer between the gold nanorods and the graphene support occurs with an efficiency of ∼10%. Our results are important for future applications of light harvesting with metal nanoparticle plasmons and efficient hot electron acceptors as well as for understanding hot electron transfer in plasmon-assisted chemical reactions.

Large-Area Low-Cost Flexible Plastic Nanohole Arrays for Integrated Bio-Chemical Sensing

Detection of plasmonic resonance peak shifts of nano-structured metamaterials is a promising method for sensing bio-chemical binding events. Although the concept is widely demonstrated in the laboratory environment using surface nano-structures machined at low-throughput and high-costs, practical solutions for high-volume production of an integrated sensing device are very limited. We present a concept of an integrated architecture that combines a thin layer of plasmonic nanohole sensing arrays, organic light-emitting diode illumination source, and microfluidic chip, for point-of-care, field, or lab applications. We discuss the fabrication of the sensor components. In particular, we present the improved fabrication of master nano-structure replication stamps, and demonstrate outstanding results for producing singular sheets or scale up to roll-to-roll embossing of nanohole arrays on a 2000 ft production roll. We further demonstrate that nanohole arrays embossed on flexible polyethylene terephthalate plastic sheets, when coated with 100 nm thin Au metal film, are capable of generating average plasmonic resonance shifts of 180 nm refractive index unit. Hence, we report the extraordinary transmission and plasmonic resonance shifts of nanohole arrays fabricated on roll-to-roll plastic sheets for the very first time. Our results show that the embossed nano-structures on plastic are suitable as sensor elements in our proposed integrated sensor architecture, and a promising technology for low-cost disposable applications.