Nanomanipulation and controlled self-assembly of metal nanoparticles and nanocrystals for plasmonics.

Localized surface plasmon resonances (LSPRs) associated with metallic nanostructures offer unique possibilities for light concentration beyond the diffraction limit, which can lead to strong field confinement and enhancement in deep subwavelength regions. In recent years, many transformative plasmonic applications have emerged, taking advantage of the spectral and spatial tunability of LSPRs enabled by near-field coupling between constituent metallic nanostructures in a variety of plasmonic metastructures (dimers, metamolecules, metasurfaces, metamaterials, etc.). For example, the "hot spot" formed at the interstitial site (gap) between two coupled metallic nanostructures in a plasmonic dimer can be spectrally tuned via the gap size. Capitalizing on these capabilities, there have been significant advances in plasmon enhanced or enabled applications in light-based science and technology, including ultrahigh-sensitivity spectroscopies, light energy harvesting, photocatalysis, biomedical imaging and theranostics, optical sensing, nonlinear optics, ultrahigh-density data storage, as well as plasmonic metamaterials and metasurfaces exhibiting unusual linear and nonlinear optical properties. In this review, we present two complementary approaches for fabricating plasmonic metastructures. We discuss how meta-atoms can be assembled into unique plasmonic metastructures using a variety of nanomanipulation methods based on single- or multiple-probes in an atomic force microscope (AFM) or a scanning electron microscope (SEM), optical tweezers, and focused electron-beam nanomanipulation. We also provide a few examples of nanoparticle metamolecules with designed properties realized in such well-controlled plasmonic metastructures. For the spatial controllability on the mesoscopic and macroscopic scales, we show that controlled self-assembly is the method of choice to realize scalable two-dimensional, and three-dimensional plasmonic metastructures. In the section of applications, we discuss some key examples of plasmonic applications based on individual hot spots or ensembles of hot spots with high uniformity and improved controllability.

Large-Scale Hot Spot Engineering for Quantitative SERS at the Single-Molecule Scale.

Quantitative surface enhanced Raman spectroscopy (SERS) requires precise control of Raman enhancement factor and detection uniformity across the SERS substrate. Here, we show that alkanethiolate ligand-regulated silver (Ag) nanoparticle films can be used to achieve quantitative SERS measurements down to the single-molecule level. The two-dimensional hexagonal close-packed superlattices of Ag nanoparticles formed in these films allow for SERS detection over a large area with excellent uniformity and high Raman enhancement factor. In particular, the SERS signal from the thiolate ligands on Ag nanoparticle surfaces can be utilized as a stable internal calibration standard for reproducible quantitative measurements. We demonstrate the capability of quantitative SERS by measuring the areal densities of crystal violet molecules embedded in an ultrathin spin-on-glass detection "hot zone", which is a planar and uniformly enhanced region several nanometers above the Ag nanoparticles. The Raman measurement results exhibit a linear response over a wide dynamic range of analyte concentration.

All-color plasmonic nanolasers with ultralow thresholds: autotuning mechanism for single-mode lasing.

We report on the first demonstration of broadband tunable, single-mode plasmonic nanolasers (spasers) emitting in the full visible spectrum. These nanolasers are based on a single metal-oxide-semiconductor nanostructure platform comprising of InGaN/GaN semiconductor nanorods supported on an Al2O3-capped epitaxial Ag film. In particular, all-color lasing in subdiffraction plasmonic resonators is achieved via a novel mechanism based on a property of weak size dependence inherent in spasers. Moreover, we have successfully reduced the continuous-wave (CW) lasing thresholds to ultrasmall values for all three primary colors and have clearly demonstrated the possibility of "thresholdless" lasing for the blue plasmonic nanolaser.

Reversible modulation of superconductivity in thin-film NbSe2 via plasmon coupling.

In recent years, lightwave has stood out as an ultrafast, non-contact control knob for developing compact superconducting circuitry. However, the modulation efficiency is limited by the low photoresponse of superconductors. Plasmons, with the advantages of strong light-matter interaction, present a promising route to overcome the limitations. Here we achieve effective modulation of superconductivity in thin-film NbSe2 via near-field coupling to plasmons in gold nanoparticles. Upon resonant plasmon excitation, the superconductivity of NbSe2 is substantially suppressed. The modulation factor exceeds 40% at a photon flux of 9.36 × 1013 s-1mm-2, and the effect is significantly diminished for thicker NbSe2 samples. Our observations can be theoretically interpreted by invoking the non-equilibrium electron distribution in NbSe2 driven by the plasmon-associated evanescent field. Finally, a reversible plasmon-driven superconducting switch is realized in this system. These findings highlight plasmonic tailoring of quantum states as an innovative strategy for superconducting electronics.

Cholesterol twists the transmembrane Di-Gly region of amyloid-precursor protein.

Nearly 95% of Alzheimer's disease (AD) occurs sporadically without genetic linkage. Aging, hypertension, high cholesterol content, and diabetes are known nongenomic risk factors of AD. Aggregation of Aß peptides is an initial event of AD pathogenesis. Aß peptides are catabolic products of a type I membrane protein called amyloid precursor protein (APP). Aß40 is the major product, whereas the 2-residue-longer version, Aß42, induces amyloid plaque formation in the AD brain. Since cholesterol content is one risk factor for sporadic AD, we aimed to explore whether cholesterol in the membrane affects the structure of the APP transmembrane region, thereby modulating the γ-secretase cutting behavior. Here, we synthesized several peptides containing the APP transmembrane region (sequence 693-726, corresponding to the Aß22-55 sequence) with one or two Cys mutations for spin labeling. We performed three electron spin resonance experiments to examine the structural changes of the peptides in liposomes composed of dioleoyl phosphatidylcholine and different cholesterol content. Our results show that cholesterol increases membrane thickness by 10% and peptide length accordingly. We identified that the di-glycine region of Aß36-40 (sequence VGGVV) exhibits the most profound change in response to cholesterol compared with other segments, explaining how the presence of cholesterol affects the γ-secretase cutting site. This study provides spectroscopic evidence showing how cholesterol modulates the structure of the APP transmembrane region in a lipid bilayer.

Bottom-up assembly of colloidal gold and silver nanostructures for designable plasmonic structures and metamaterials.

We report on bottom-up assembly routes for fabricating plasmonic structures and metamaterials composed of colloidal gold and silver nanostructures, such as nanoparticles ("metatoms") and shape-controlled nanocrystals. Owing to their well-controlled sizes/shapes, facile surface functionalization, and excellent plasmonic properties in the visible and near-infrared regions, these nanoparticles and nanocrystals are excellent building blocks of plasmonic structures and metamaterials for optical applications. Recently, we have utilized two kinds of bottom-up techniques (i.e., multiple-probe-based nanomanipulation and layer-by-layer self-assembly) to fabricate strongly coupled plasmonic dimers, one-dimensional (1D) chains, and large-scale two-dimensional/three-dimensional (2D/3D) nanoparticle supercrystals. These coupled nanoparticle/nanocrystal assemblies exhibit unique and tunable plasmonic properties, depending on the material composition, size/shape, intergap distance, the number of composing nanoparticles/nanocrystals (1D chains), and the nanoparticle layer number in the case of 3D nanoparticle supercrystals. By studying these coupled nanoparticle/nanocrystal assemblies, the fundamental plasmonic metamaterial effects could be investigated in detail under well-prepared and previously unexplored experimental settings.

Plasmon hybridization in individual gold nanocrystal dimers: direct observation of bright and dark modes.

We apply a nanomanipulation technique to assemble pairs of monodispersed octahedral gold nanocrystals (side length, 150 nm) along their major axes with a varying tip-to-tip separation (25-125 nm). These pairs are immobilized onto indium tin oxide coated silica substrates and studied as plasmonic dimers by polarization-selective total internal reflection (TIR) microscopy and spectroscopy. We confirm that the plasmon coupling modes with the scattering polarization along the incident light direction result from the transverse-magnetic-polarized incident light, which induces two near-field-coupled dipole moments oriented normal to the air-substrate interface. In such cases, both in-phase (antibonding) and antiphase (bonding) plasmon coupling modes can be directly observed with the incident light wave vector perpendicular and parallel to the dimer axis, respectively. The observation of antiphase plasmon coupling modes ("dark" plasmons) is made possible by the unique polarization nature of the TIR-generated evanescent field. Furthermore, with decreasing nanocrystal separation, the plasmon coupling modes shift to shorter wavelengths for the incident light perpendicular to the dimer axis, whereas relatively large red shifts of the plasmonic coupling modes are found for the parallel incident light.

Inorganic gyroid with exceptionally low refractive index from block copolymer templating.

Nanoporous polymers with gyroid nanochannels can be fabricated from the self-assembly of degradable block copolymer, polystyrene-b-poly(l-lactide) (PS-PLLA), followed by the hydrolysis of PLLA blocks. A well-defined nanohybrid material with SiO2 gyroid nanostructure in a PS matrix can be obtained using the nanoporous PS as a template for sol-gel reaction. After subsequent UV degradation of the PS matrix, a highly porous inorganic gyroid network remains, yielding a single-component material with an exceptionally low refractive index (as low as 1.1).

Layer-by-layer assembly of three-dimensional colloidal supercrystals with tunable plasmonic properties.

We present a simple and efficient method for synthesizing large-area (>1 cm(2)), three-dimensional (3D) gold and silver nanoparticle supercrystal films. In this approach, Janus nanoparticle (top face solvent-phobic and bottom face solvent-philic) films with an arbitrary number of close-packed nanoparticle monolayers can be formed using layer-by-layer (LbL) assembly from suspensions of thiolate-passivated gold or silver colloids. Furthermore, we demonstrate that these films can act as true 3D plasmonic crystals with strong transverse (intralayer) and longitudinal (interlayer) near-field coupling. In contrast to conventional polyelectrolyte-mediated LbL assembly processes, this approach allows multiple longitudinal coupling modes with a conspicuous spectral dependence on the layer number. We have found a universal scaling relation between the spectral position of the reflectance dips related to the longitudinal modes and the layer number. This relation can be understood in terms of the presence of a plasmonic Fabry-Perot nanocavity along the longitudinal direction that allows the formation of standing plasmon waves under plasmon resonance conditions. The realization of 3D plasmonic coupling enables broadband tuning of the collective plasmon response over a wide spectral range (visible and near-IR) and provides a pathway to designer plasmonic metamaterials.

Tunable plasmonic response from alkanethiolate-stabilized gold nanoparticle superlattices: evidence of near-field coupling.

We report on the self-assembly of large-area, highly ordered 2D superlattices of alkanethiolate-stabilized gold nanoparticles ( approximately 10.5 nm in core diameter) onto quartz substrates with varying lattice constants, which can be controlled by the alkyl chain lengths, ranging from C12 (1-dodecanethiolate), C14 (1-tetradecanethiolate), C16 (1-hexadecanethiolate), to C18 (1-octadecanethiolate). These 2D nanoparticle superlattices exhibit strong collective surface plasmon resonance that is tunable via the near-field coupling of adjacent nanoparticles. The approach presented here provides a unique and viable means of building artificial "plasmonic crystals" with precisely designed optical properties, which can be useful for the emerging fields of plasmonics, such as subwavelength integrated optics.