Design considerations for enhancing absorption in semiconductors on metals through surface plasmon polaritons.

Surface plasmon polaritons have attracted attention for energy applications such as photovoltaic and photoelectrochemical cells because of their ability to improve optical absorption in thin films. We show that surface plasmon polaritons enhance absorption most significantly in materials with small positive real permittivity and large positive imaginary permittivity, e.g. organics or CdTe. Additional losses, accounting for dissipation in the metal and the existence of a cutoff frequency above which polaritons are no longer bound, are incorporated into efficiency calculations. Owing to these losses, devices with optical absorption based solely on SPPs will necessarily always have a lower efficiency than that predicted by the Shockley-Queisser limit. Calculations are presented for specific materials, including crystalline and amorphous Si, GaAs, CdTe, a P3HT:PCBM blend, α-Fe2O3 and rutile TiO2, as well as for general materials of arbitrary permittivity. Guidelines for selecting absorber materials and determining whether specific materials are good candidates for improving optical absorption with SPPs are presented.

Multi-resonant plasmonic nanodome arrays for label-free biosensing applications.

The characteristics and utility of plasmonic nanodome arrays capable of supporting multiple resonance modes are described. A low-cost, large-area replica molding process is used to produce, on flexible plastic substrates, two-dimensional periodic arrays of cylinders that are subsequently coated with SiO2 and Ag thin films to form dome-shaped structures, with 14 nm spacing between the features, in a precise and reproducible fashion. Three distinct optical resonance modes, a grating diffraction mode and two localized surface plasmon resonance (LSPR) modes, are observed experimentally and confirmed by finite-difference-time-domain (FDTD) modeling which is used to calculate the electromagnetic field distribution of each resonance around the nanodome array structure. Each optical mode is characterized by measuring sensitivity to bulk refractive index changes and to surface effects, which are examined using stacked polyelectrolyte layers. The utility of the plasmonic nanodome array as a functional interface for biosensing applications is demonstrated by performing a bioassay to measure the binding affinity constant between protein A and human immunoglobulin G (IgG) as a model system. The nanoreplica molding process presented in this work allows for simple, inexpensive, high-throughput fabrication of nanoscale plasmonic structures over a large surface area (120 × 120 mm(2)) without the requirement for high resolution lithography or additional processes such as etching or liftoff. The availability of multiple resonant modes, each with different optical properties, allows the nanodome array surface to address a wide range of biosensing problems with various target analytes of different sizes and configurations.

Effect of interdome spacing on the resonance properties of plasmonic nanodome arrays for label-free optical sensing.

In this paper, we report on experimental and theoretical studies that investigate how the structural properties of plasmonic nanodome array devices determine their optical properties and sensing performance. We examined the effect of the interdome gap spacing within the plasmonic array structures on the performance for detection of change in local refractive index environment for label-free capture affinity biosensing applications. Optical sensing properties were characterized for nanodome array devices with interdome spacings of 14 nm, 40 nm, and 79 nm, as well as for a device where adjacent domes are in contact. For each interdome spacing, the extinction spectrum was measured using a broadband reflection instrumentation, and finite-difference-time-domain (FDTD) simulation was used to model the local electric field distribution associated with the resonances. Based on these studies, we predict that nanodome array devices with gap between 14 nm to 20 nm provide optimal label-free capture affinity biosensing performances, where the dipole resonance mode exhibits the highest overall surface sensitivity, as well as the lowest limit of detection.

Plasmonic nanogap-enhanced Raman scattering using a resonant nanodome array.

The optical properties and surface-enhanced Raman scattering (SERS) of plasmonic nanodome array (PNA) substrates in air and aqueous solution are investigated. PNA substrates are inexpensively and uniformly fabricated with a hot spot density of 6.25 × 10(6) mm(-2) using a large-area nanoreplica moulding technique on a flexible plastic substrate. Both experimental measurement and numerical simulation results show that PNAs exhibit a radiative localized surface plasmon resonance (LSPR) due to dipolar coupling between neighboring nanodomes and a non-radiative surface plasmon resonance (SPR) resulting from the periodic array structure. The high spatial localization of electromagnetic field within the ∼10 nm nanogap together with the spectral alignment between the LSPR and excited and scattered light results in a reliable and reproducible spatially averaged SERS enhancement factor (EF) of 8.51 × 10(7) for Au-coated PNAs. The SERS enhancement is sufficient for a wide variety of biological and chemical sensing applications, including detection of common metabolites at physiologically relevant concentrations.

Biochemical sensor tubing for point-of-care monitoring of intravenous drugs and metabolites.

In medical facilities, there is strong motivation to develop detection systems that can provide continuous analysis of fluids in medical tubing used to either deliver or remove fluids from a patient's body. Possible applications include systems that increase the safety of intravenous (IV) drug injection and point-of-care health monitoring. In this work, we incorporated a surface-enhanced Raman scattering (SERS) sensor comprised of an array of closely spaced metal nanodomes into flexible tubing commonly used for IV drug delivery and urinary catheters. The nanodome sensor was fabricated by a low-cost, large-area process that enables single use disposable operation. As exemplary demonstrations, the sensor was used to kinetically detect promethazine (pain medication) and urea (urinary metabolite) within their clinically relevant concentration ranges. Distinct SERS peaks for each analyte were used to demonstrate separate detection and co-detection of the analytes.

Surface-enhanced Raman nanodomes.

We demonstrate a surface-enhanced Raman scattering (SERS) substrate consisting of a closely spaced metal nanodome array fabricated on flexible plastic film. We used a low-cost, large-area replica molding process to produce a two-dimensional periodic array of cylinders that is subsequently overcoated with SiO(2) and silver thin films to form dome-shaped structures. Finite element modeling was used to investigate the electromagnetic field distribution of the nanodome array structure and the effect of the nanodome separation distance on the electromagnetic field enhancement. The SERS enhancement from the nanodome array substrates was experimentally verified using rhodamine 6G as the analyte. With a separation distance of 17 nm achieved between adjacent domes using a process that is precisely controlled during thin film deposition, a reproducible SERS enhancement factor of 1.37 × 10(8) was demonstrated. The nanoreplica molding process presented in this work allows for simple, low-cost, high-throughput fabrication of uniform nanoscale SERS substrates over large surface areas without the requirement for high resolution lithography or defect-free deposition of spherical microparticle monolayer templates.

Comparison of label-free biosensing in microplate, microfluidic, and spot-based affinity capture assays.

Using both experimental assays and fluid-dynamic finite element simulation models, we directly compared the achievable performance limits of four distinct assay configurations for label-free detection of an analyte from a test sample on a biosensor surface. The assay configurations studied in this work included a biosensor incorporated into the bottom surface of a microplate well and a microfluidic channel. For each configuration, we compared assay performance for the scenario in which the entire bottom surface of the fluid-handling vessel is coated with capture ligands with assay performance for the scenario in which the capture ligands are applied in the form of localized spots. As a model system, we used detection of the protein biomarker tumor necrosis factor-alpha (TNF-alpha) using immobilized TNF-alpha capture antibody. Results show that the microfluidic assay format dramatically reduces the time required to establish a stable equilibrium. Spot-based assays are advantageous for microplate-based detection for reducing the time required for equilibrium sensor response. The results derived are generally applicable to any label-free biosensor technology and any ligand-analyte system with adjustable variables that include sensor mass density sensitivity, analyte-ligand adsorption/desorption rate constants, immobilized ligand density, flow channel geometry, flow rate, and spot size.

Microfluidic chip for combinatorial mixing and screening of assays.

This paper reports the design, fabrication and validation of a microfluidic well plate for combinatorial screening applications. Each well within the array is comprised of two 200 picoliter compartments that each contain a photonic crystal biosensor to enable the on-chip, in situ detection of (bio-) molecular binding events. This microfluidic chip utilizes arrays of Actuate-to-Open valves to isolate all compartments, which allows the chip to be decoupled from pneumatic control lines and thus to be transported freely between filling, sensing and characterization platforms. A proof-of-principle 4 x 4 protein/antibody binding assay was performed to demonstrate the discrete mixing and on-chip sensing capabilities.

A 96-well microplate incorporating a replica molded microfluidic network integrated with photonic crystal biosensors for high throughput kinetic biomolecular interaction analysis.

A nanoreplica molding process has been used to produce polymer microfluidic channels, with integrated label-free photonic crystal biosensors as the bottom surface of the channels. Multiple flow channels are gathered in parallel so that an imaging detection instrument may simultaneously monitor the binding kinetics of many biomolecular interactions. In this work, the flow channel pattern has been adapted to a 96-well microplate format in which, for each 12-element row of the microplate, a single well serves as a common access port for 11 flow channels that are connected to separate microplate wells. Application of pneumatic pressure or suction to the common well serves to drive forward or backward flow to the channels. The system is demonstrated by measuring the kinetic binding interaction of protein A with IgG molecules of high, medium, and low affinity. The approach offers a means for minimizing the volume of reagent required to functionalize the biosensor surface, while retaining compatibility with the microplate assay fluid-handling methods that are most commonly used in biological research.

Single-step fabrication and characterization of photonic crystal biosensors with polymer microfluidic channels.

A method for simultaneously integrating label-free photonic crystal biosensor technology into microfluidic channels by a single-step replica molding process is presented. By fabricating both the sub-micron features of the photonic crystal sensor structure and the >10 microm features of a flow channel network in one step at room temperature on a plastic substrate, the sensors are automatically self-aligned with the flow channels, and patterns of arbitrary shape may be produced. By measuring changes in the resonant peak reflected wavelength from the photonic crystal structure induced by changes in dielectric permittivity within an evanescent field region near its surface, detection of bulk refractive index changes in the fluid channel or adsorption of biological material to the sensor surface is demonstrated. An imaging detection instrument is used to characterize the spatial distribution of the photonic crystal resonant wavelength, gathering thousands of independent sensor readings within a single fluid channel.