Plasmonic Nanotweezers and Nanosensors for Point-of-Care Applications.

The capabilities of manipulating and analyzing biological cells, bacteria, viruses, DNAs, and proteins at high resolution are significant in understanding biology and enabling early disease diagnosis. We discuss progress in developments and applications of plasmonic nanotweezers and nanosensors where the plasmon-enhanced light-matter interactions at the nanoscale improve the optical manipulation and analysis of biological objects. Selected examples are presented to illustrate their design and working principles. In the context of plasmofluidics, which merges plasmonics and fluidics, the integration of plasmonic nanotweezers and nanosensors with microfluidic systems for point-of-care (POC) applications is envisioned. We provide our perspectives on the challenges and opportunities in further developing and applying the plasmofluidic POC devices.

Plasmon-trion and plasmon-exciton resonance energy transfer from a single plasmonic nanoparticle to monolayer MoS2.

Resonance energy transfer (RET) from plasmonic metal nanoparticles (NPs) to two-dimensional (2D) materials enhances the performance of 2D optoelectronic devices and sensors. Herein, single-NP scattering spectroscopy is employed to investigate plasmon-trion and plasmon-exciton RET from single Au nanotriangles (AuNTs) to monolayer MoS2, at room temperature. The large quantum confinement and reduced dielectric screening in monolayer MoS2 facilitates efficient RET between single plasmonic metal NPs and the monolayer. Because of the large exciton binding energy of monolayer MoS2, charged excitons (i.e., trions) are observed at room temperature, which enable us to study the plasmon-trion interactions under ambient conditions. Tuning of plasmon-trion and plasmon-exciton RET is further achieved by controlling the dielectric constant of the medium surrounding the AuNT-MoS2 hybrids. Our observation of switchable plasmon-trion and plasmon-exciton RET inspires new applications of the hybrids of 2D materials and metal nanoparticles.

Controlling Plasmon-Enhanced Fluorescence via Intersystem Crossing in Photoswitchable Molecules.

By harnessing photoswitchable intersystem crossing (ISC) in spiropyran (SP) molecules, active control of plasmon-enhanced fluorescence in the hybrid systems of SP molecules and plasmonic nanostructures is achieved. Specifically, SP-derived merocyanine (MC) molecules formed by photochemical ring-opening reaction display efficient ISC due to their zwitterionic character. In contrast, ISC in quinoidal MC molecules formed by thermal ring-opening reaction is negligible. The high ISC rate can improve fluorescence quantum yield of the plasmon-modified spontaneous emission, only when the plasmonic electromagnetic field enhancement is sufficiently high. Along this line, extensive photomodulation of fluorescence is demonstrated by switching the ISC in MC molecules at Au nanoparticle aggregates, where strongly enhanced plasmonic hot spots exist. The ISC-mediated plasmon-enhanced fluorescence represents a new approach toward controlling the spontaneous emission of fluorophores near plasmonic nanostructures, which expands the applications of active molecular plasmonics in information processing, biosensing, and bioimaging.

Patterning and fluorescence tuning of quantum dots with haptic-interfaced bubble printing.

Semiconductor quantum dots (QDs) are attractive for a wide range of applications such as displays, light-emitting devices, and sensors due to their properties such as tunable fluorescence wavelength, high brightness, and narrow bandwidth. Most of the applications require precise patterning of QDs with targeted properties on solid-state substrates. Herein, we have developed a haptic-interfaced bubble printing (HIBP) technique to enable high-resolution (510 nm) high-throughput (>104 µm s-1) patterning of QDs with strong emission tunability and to significantly enhance the accessibility of the technique via a smartphone device. The scalability and versatility of the HIBP are demonstrated in our arbitrary patterning of QDs on plasmonic substrates. A detailed study of plasmonic and photothermal interactions is performed via programmed stage movements to realize tunability of the emission wavelength and lifetime. Finally, the influence of the hand movement on the properties of the printed QDs in terms of emission wavelength tuning from yellow to blue is established. This work provides a single-step macroscale platform to manipulate nanoscale properties at high resolution and high throughput.

Dual-band moiré metasurface patches for multifunctional biomedical applications.

There has been strong interest in developing multi-band plasmonic metasurfaces for multiple optical functions on single platforms. Herein, we developed Au moiré metasurface patches (AMMP), which leverage the tunable multi-band responses of Au moiré metasurfaces and the additional field enhancements of the metal-insulator-metal configuration to achieve dual-band plasmon resonance modes in near-infrared and mid-infrared regimes with high field enhancement. Furthermore, we demonstrate the multifunctional applications of AMMP, including surface-enhanced infrared spectroscopy, optical capture and patterning of bacteria, and photothermal denaturation of proteins. With their multiple functions of high performance, in combination with cost-effective fabrication using moiré nanosphere lithography, the AMMP will enable the development of highly integrated biophotonic platforms for a wide range of applications in disease theranostics, sterilization, and the study of microbiomes.

Plasmon-enhanced nanoporous BiVO4 photoanodes for efficient photoelectrochemical water oxidation.

Conversion of solar irradiation into chemical fuels such as hydrogen with the use of a photoelectrochemical (PEC) cell is an attractive strategy for green energy. The promising technique of incorporating metal nanoparticles (NPs) in the photoelectrodes is being explored to enhance the performance of the photoelectrodes. In this work, we developed Au-NPs-functionalized nanoporous BiVO4 photoanodes, and utilized the plasmonic effects of Au NPs to enhance the photoresponse. The plasmonic enhancement leads to an AM 1.5 photocurrent of 5.1 ± 0.1 mA cm(-2) at 1.23 V versus a reverse hydrogen electrode. We observed an enhancement of five times with respect to pristine BiVO4 in the photocurrent with long-term stability and high energy-conversion efficiency. The overall performance enhancement is attributed to the synergy between the nanoporous architecture of BiVO4 and the plasmonic effects of Au NPs. Our further study reveals that the commendable photoactivity arises from the different plasmonic effects and co-catalyst effects of Au NPs.

Bubble-Pen Lithography.

Current lithography techniques, which employ photon, electron, or ion beams to induce chemical or physical reactions for micro/nano-fabrication, have remained challenging in patterning chemically synthesized colloidal particles, which are emerging as building blocks for functional devices. Herein, we develop a new technique - bubble-pen lithography (BPL) - to pattern colloidal particles on substrates using optically controlled microbubbles. Briefly, a single laser beam generates a microbubble at the interface of colloidal suspension and a plasmonic substrate via plasmon-enhanced photothermal effects. The microbubble captures and immobilizes the colloidal particles on the substrate through coordinated actions of Marangoni convection, surface tension, gas pressure, and substrate adhesion. Through directing the laser beam to move the microbubble, we create arbitrary single-particle patterns and particle assemblies with different resolutions and architectures. Furthermore, we have applied BPL to pattern CdSe/ZnS quantum dots on plasmonic substrates and polystyrene (PS) microparticles on two-dimensional (2D) atomic-layer materials. With the low-power operation, arbitrary patterning and applicability to general colloidal particles, BPL will find a wide range of applications in microelectronics, nanophotonics, and nanomedicine.

Molecular-Fluorescence Enhancement via Blue-Shifted Plasmon-Induced Resonance Energy Transfer.

We report molecular-fluorescence enhancement via the blue-shifted plasmon-induced resonance energy transfer (PIRET) from single Au nanorods (AuNRs) to merocyanine (MC) dye molecules. The blue-shifted PIRET occurs when there is a proper spectral overlap between the scattering of AuNRs and the absorption of MC molecules. Along with the quenching of scattering from AuNRs, the blue-shifted PIRET enhances the fluorescence of nearby molecules. On the basis of the fluorescence enhancement, we conclude that AuNRs can be used as donors with clear advantages to excite the fluorescence of molecules as acceptors in AuNR-molecule hybrids. On the one hand, compared to conventional molecular donors in Förster resonance energy transfer (FRET), AuNRs have much larger absorption cross sections at the plasmon resonance frequencies. On the other hand, energy-transfer efficiency of PIRET decreases at a lower rate than that of FRET when the donor-acceptor distance is increased. Besides, the blue-shifted PIRET allows excitation with incident light of lower energy than the acceptor's absorption, which is difficult to achieve in FRET because of the Stokes shift. With the capability of enhancing molecular fluorescence with excitation light of low intensity and long wavelength, the blue-shifted PIRET will expand the applications of nanoparticle- molecule hybrids in biosensing and bioimaging by increasing signal-to-noise ratio and by reducing photodamage to biological cells and organelles at the targeted areas.

Thermodynamic synthesis of solution processable ladder polymers.

The synthesis of a carbazole-derived, well-defined ladder polymer was achieved under thermodynamic control by employing reversible ring-closing olefin metathesis. This unique approach featured mild conditions and excellent efficiency, affording the ladder polymer backbone with minimum levels of unreacted defects. Rigorous NMR analysis on a 13C isotope-enriched product revealed that the main-chain contained less than 1% of unreacted precursory vinyl groups. The rigid conformation of the ladder-type backbone was confirmed by photophysical analysis, while the extended rod-like structure was visualized under scanning tunneling microscope. Excellent solubility of this polymer in common organic solvents allowed for feasible processing of thin films using solution-casting techniques. Atomic force microscopy and grazing incident X-ray scattering revealed a uniform and amorphous morphology of these films, in sharp contrast to the polycrystalline thin films of its small molecular counterpart.

Moiré Nanosphere Lithography.

We have developed moiré nanosphere lithography (M-NSL), which incorporates in-plane rotation between neighboring monolayers, to extend the patterning capability of conventional nanosphere lithography (NSL). NSL, which uses self-assembled layers of monodisperse micro/nanospheres as masks, is a low-cost, scalable nanofabrication technique and has been widely employed to fabricate various nanoparticle arrays. Combination with dry etching and/or angled deposition has greatly enriched the family of nanoparticles NSL can yield. In this work, we introduce a variant of this technique, which uses sequential stacking of polystyrene nanosphere monolayers to form a bilayer crystal instead of conventional spontaneous self-assembly. Sequential stacking leads to the formation of moiré patterns other than the usually observed thermodynamically stable configurations. Subsequent O2 plasma etching results in a variety of complex nanostructures. Using the etched moiré patterns as masks, we have fabricated complementary gold nanostructures and studied their optical properties. We believe this facile technique provides a strategy to fabricate complex nanostructures or metasurfaces.

Regioselective Localization and Tracking of Biomolecules on Single Gold Nanoparticles.

Selective localization of biomolecules at the hot spots of a plasmonic nanoparticle is an attractive strategy to exploit the light-matter interaction due to the high field concentration. Current approaches for hot spot targeting are time-consuming and involve prior knowledge of the hot spots. Multiphoton plasmonic lithography is employed to rapidly immobilize bovine serum albumin (BSA) hydrogel at the hot spot tips of a single gold nanotriangle (AuNT). Regioselectivity and quantity control by manipulating the polarization and intensity of the incident laser are also established. Single AuNTs are tracked using dark-field scattering spectroscopy and scanning electron microscopy to characterize the regioselective process. Fluorescence lifetime measurements further confirm BSA immobilization on the AuNTs. Here, the AuNT-BSA hydrogel complexes, in conjunction with single-particle optical monitoring, can act as a framework for understanding light-molecule interactions at the subnanoparticle level and has potential applications in biophotonics, nanomedicine, and life sciences.