Kunli Xiong

Plasmon Enhanced Internal Photoemission in Antenna-Spacer-Mirror Based Au/TiO2 Nanostructures

Emission of photoexcited hot electrons from plasmonic metal nanostructures to semiconductors is key to a number of proposed nanophotonics technologies for solar harvesting, water splitting, photocatalysis, and a variety of optical sensing and photodetector applications. Favorable materials and catalytic properties make systems based on gold and TiO2 particularly interesting, but the internal photoemission efficiency for visible light is low because of the wide bandgap of the semiconductor. We investigated the incident photon-to-electron conversion efficiency of thin TiO2 films decorated with Au nanodisk antennas in an electrochemical circuit and found that incorporation of a Au mirror beneath the semiconductor amplified the photoresponse for light with wavelength λ = 500-950 nm by a factor 2-10 compared to identical structures lacking the mirror component. Classical electrodynamics simulations showed that the enhancement effect is caused by a favorable interplay between localized surface plasmon excitations and cavity modes that together amplify the light absorption in the Au/TiO2 interface. The experimentally determined internal quantum efficiency for hot electron transfer decreases monotonically with wavelength, similar to the probability for interband excitations with energy higher than the Schottky barrier obtained from a density functional theory band structure simulation of a thin Au/TiO2 slab.

A Thermal Plasmonic Sensor Platform: Resistive Heating of Nanohole Arrays

We have created a simple and efficient thermal plasmonic sensor platform by letting a DC current heat plasmonic nanohole arrays. The sensor can be used to determine thermodynamic parameters in addition to monitoring molecular reactions in real-time. As an application example, we use the thermal sensor to determine the kinetics and activation energy for desorption of thiol monolayers on gold. Further, the temperature of the metal can be measured optically by the spectral shift of the bonding surface plasmon mode (0.015 nm/K). We show that this resonance shift is caused by thermal lattice expansion, which reduces the plasma frequency of the metal. The sensor is also used to determine the thin film thermal expansion coefficient through a theoretical model for the expected resonance shift.

Plasmonic Metasurfaces with Conjugated Polymers for Flexible Electronic Paper in Color

A flexible electronic paper in full color is realized by plasmonic metasurfaces with conjugated polymers. An ultrathin large-area electrochromic material is presented which provides high polarization-independent reflection, strong contrast, fast response time, and long-term stability. This technology opens up for new electronic readers and posters with ultralow power consumption.

Biosensing using plasmonic nanohole arrays with small, homogenous and tunable aperture diameters

Plasmonic nanohole arrays are widely used for optical label-free molecular detection. An important factor for many applications is the diameter of the apertures. So far nanohole arrays with controllable diameters below 100 nm have not been demonstrated and it has not been systematically investigated how the diameter influences the optical properties. In this work we fine-tune the diameter in short range ordered nanohole arrays down to 50 nm. The experimental far field spectra show how the wavelength of maximum extinction remains unaffected while the transmission maximum blue shifts with smaller diameters. The near field is visualized by numerical simulations, showing a homogenous enhancement throughout the cylindrical void at the transmission maximum for diameters between 50 and 100 nm. For diameters below 50 nm plasmon excitation is no longer possible experimentally or by simulations. Further, we investigate the refractive index sensing capabilities of the smaller holes. As the diameter was reduced, the sensitivity in terms of resonance shift with bulk liquid refractive index was found to be unaltered. However, for the transmission maximum the sensitivity becomes more strongly localized to the hole interior. By directing molecular binding to the bottom of the holes we demonstrate how smaller holes enhance the sensitivity in terms of signal per molecule. A real-time detection limit well below one protein per nanohole is demonstrated. The smaller plasmonic nanoholes should be suitable for studies of molecules confined in small volumes and as mimics of biological nanopores.

Switchable Plasmonic Metasurfaces with High Chromaticity Containing Only Abundant Metals

Plasmonic color generation offers several advantages but is also limited by the cost and availability of noble metals like gold. In this work, we present color-tunable metasurfaces with high chromaticity and reflectivity consisting of an aluminum mirror, a dielectric spacer, and a plasmonic nanohole array in copper. Copper is shown to be an excellent alternative to gold when properly protected from oxidation and makes it possible to generate a wide RGB gamut covering 27% of the standard RGB. By patterning the metasurfaces into microscale pixel triplets, color photos can be well reproduced with high resolution over wafer-sized areas. Further, we demonstrate active modulation of the reflected intensity using an electrochromic conductive polymer deposited on top of the nanostructures by screen printing. This technology opens up for ultrathin and flexible reflective displays in full color, that is, plasmonic electronic paper, compatible with large-scale sustainable production.

Polymer brushes in solid-state nanopores form an impenetrable entropic barrier for proteins

Polymer brushes are widely used to prevent the adsorption of proteins, but the mechanisms by which they operate have remained heavily debated for many decades. We show conclusive evidence that a polymer brush can be a remarkably strong kinetic barrier towards proteins by using poly(ethylene glycol) grafted to the sidewalls of pores in 30 nm thin gold films. Despite consisting of about 90% water, the free coils seal apertures up to 100 nm entirely with respect to serum protein translocation, as monitored label-free through the plasmonic activity of the nanopores. The conclusions are further supported by atomic force microscopy and fluorescence microscopy. A theoretical model indicates that the brush undergoes a morphology transition to a sealing state when the ratio between the extension and the radius of curvature is approximately 0.8. The brush-sealed pores represent a new type of ultrathin filter with potential applications in bioanalytical systems.

Fabrication and Characterization of Plasmonic Nanopores with Cavities in the Solid Support

Plasmonic nanostructures are widely used for various sensing applications by monitoring changes in refractive index through optical spectroscopy or as substrates for surface enhanced Raman spectroscopy. However, in most practical situations conventional surface plasmon resonance is preferred for biomolecular interaction analysis because of its high resolution in surface coverage and the simple single-material planar interface. Still, plasmonic nanostructures may find unique sensing applications, for instance when the nanoscale geometry itself is of interest. This calls for new methods to prepare nanoscale particles and cavities with controllable dimensions and curvature. In this work, we present two types of plasmonic nanopores where the solid support underneath a nanohole array has been etched, thereby creating cavities denoted as ‘nanowells’ or ‘nanocaves’ depending on the degree of anisotropy (dry or wet etch). The refractometric sensitivity is shown to be enhanced upon removing the solid support because of an increased probing volume and a shift of the asymmetric plasmonic field towards the liquid side of the finite gold film. Furthermore, the structures exhibit different spectral changes upon binding inside the cavities compared to the gold surface, which means that the structures can be used for location-specific detection. Other sensing applications are also suggested.

Nanoplasmonic Sensing Architectures for Decoding Membrane Curvature-Dependent Biomacromolecular Interactions

Nanoplasmonic sensors have emerged as a promising measurement approach to track biomacromolecular interactions involving lipid membrane interfaces. By taking advantage of nanoscale fabrication capabilities, it is possible to design sensing platforms with various architectural configurations. Such capabilities open the door to fabricating lipid membrane-coated nanoplasmonic sensors with varying degrees of membrane curvature in order to understand how biomacromolecular interaction processes are influenced by membrane curvature. Herein, we employed an indirect nanoplasmonic sensing approach to characterize the fabrication of supported lipid bilayers (SLBs) on silica-coated nanowell and nanodisk sensing platforms and to investigate how membrane curvature influences membrane-peptide interactions by evaluating the corresponding measurement responses from different spectral signatures that are sensitive to specific regions of the sensor geometries. SLBs were prepared by the vesicle fusion method, as monitored in real-time by nanoplasmonic sensing measurements and further characterized by fluorescence recovery after photobleaching (FRAP) experiments. By resolving different spectral signatures in the nanoplasmonic sensing measurements, it was determined that peptide binding induces membrane disruption at positively curved membrane regions, while peptide binding without subsequent disruption was observed at planar and negatively curved regions. These findings are consistent with the peptides known preference to selectively form pores in positively curved membranes, providing validation to the nanoplasmonic sensing approach and highlighting how the integration of nanoplasmonic sensors with different nanoscale architectures can be utilized to study the influence of membrane curvature on biomacromolecular interaction processes.

Gating Protein Transport in Solid State Nanopores by Single Molecule Recognition

Control of molecular translocation through nanoscale apertures is of great interest for DNA sequencing, biomolecular filters, and new platforms for single molecule analysis. However, methods for controlling the permeability of nanopores are very limited. Here, we show how nanopores functionalized with poly(ethylene glycol) brushes, which fully prevent protein translocation, can be reversibly gated to an “open” state by binding of single IgG antibodies that disrupt the macromolecular barrier. On the basis of surface plasmon resonance data we propose a two-state model describing the antibody–polymer interaction kinetics. Reversibly (weakly) bound antibodies decrease the protein exclusion height while irreversibly (strongly) bound antibodies do not. Our results are further supported by fluorescence readout from pore arrays and high-speed atomic force microscopy on single pores. This type of dynamic barrier control on the nanoscale provides new possibilities for biomolecular separation and analysis.