Dynamic Nanocrystal Superlattices with Thermally Triggerable Lubricating Ligands.

The size-dependent and collective physical properties of nanocrystals (NCs) and their self-assembled superlattices (SLs) enable the study of mesoscale phenomena and the design of metamaterials for a broad range of applications. However, the limited mobility of NC building blocks in dried NCSLs often hampers the potential for employing postdeposition methods to produce high-quality NCSLs. In this study, we present tailored promesogenic ligands that exhibit a lubricating property akin to thermotropic liquid crystals. The lubricating ability of ligands is thermally triggerable, allowing the dry solid NC aggregates deposited on the substrates with poor ordering to be transformed into NCSLs with high crystallinity and preferred orientations. The interplay between the dynamic behavior of NCSLs and the molecular structure of the ligands is elucidated through a comprehensive analysis of their lubricating efficacy using both experimental and simulation approaches. Coarse-grained molecular dynamic modeling suggests that a shielding layer from mesogens prevents the interdigitation of ligand tails, facilitating the sliding between outer shells and consequently enhancing the mobility of NC building blocks. The dynamic organization of NCSLs can also be triggered with high spatial resolution by laser illumination. The principles, kinetics, and utility of lubricating ligands could be generalized to unlock stimuli-responsive metamaterials from NCSLs and contribute to the fabrication of NCSLs.

Open and Close-Packed, Shape-Engineered Polygonal Nanoparticle Metamolecules with Tailorable Fano Resonances.

A top-down lithographic patterning and deposition process is reported for producing nanoparticles (NPs) with well-defined sizes, shapes, and compositions that are often not accessible by wet-chemical synthetic methods. These NPs are ligated and harvested from the substrate surface to prepare colloidal NP dispersions. Using a template-assisted assembly technique, fabricated NPs are driven by capillary forces to assemble into size- and shape-engineered templates and organize into open or close-packed multi-NP structures or NP metamolecules. The sizes and shapes of the NPs and of the templates control the NP number, coordination, interparticle gap size, disorder, and location of defects such as voids in the NP metamolecules. The plasmonic resonances of polygonal-shaped Au NPs are exploited to correlate the structure and optical properties of assembled NP metamolecules. Comparing open and close-packed architectures highlights that introduction of a center NP to form close-packed assemblies supports collective interactions, altering magnetic optical modes and multipolar interactions in Fano resonances. Decreasing the distance between NPs strengthens the plasmonic coupling, and the structural symmetries of the NP metamolecules determine the orientation-dependent scattering response.

Three-Dimensionally Complex Phase Behavior and Collective Phenomena in Mixtures of Acoustically Powered Chiral Microspinners.

The process of dynamic self-organization of small building blocks is fundamental to the emergent function of living systems and is characteristic of their out-of-equilibrium homeostasis. The ability to control the interactions of synthetic particles in large groups could lead to the realization of analogous macroscopic robotic systems with microscopic complexity. Rotationally induced self-organization has been observed in biological systems and modeled theoretically, but studies of fast, autonomously moving synthetic rotors remain rare. Here, we report switchable, out-of-equilibrium hydrodynamic assembly and phase separation in suspensions of acoustically powered chiral microspinners. Semiquantitative modeling suggests that three-dimensionally (3D) complex spinners interact through viscous and weakly inertial (streaming) flows. The interactions between spinners were studied over a range of densities to construct a phase diagram, which included gaseous dimer pairing at low density, collective rotation and multiphase separation at intermediate densities, and ultimately jamming at high density. The 3D chirality of the spinners leads to self-organization in parallel planes, forming a three-dimensionally hierarchical system that goes beyond the 2D systems that have so far been modeled computationally. Dense mixtures of spinners and passive tracer particles also show active-passive phase separation. These observations are consistent with recent theoretical predictions of the hydrodynamic coupling between rotlets generated by autonomous spinners and provide an exciting experimental window to the study of colloidal active matter and microrobotic systems.

Self-Assembly of Atomically Aligned Nanoparticle Superlattices from Pt-Fe3O4 Heterodimer Nanoparticles.

Multicomponent nanoparticle superlattices (SLs) promise the integration of nanoparticles (NPs) with remarkable electronic, magnetic, and optical properties into a single structure. Here, we demonstrate that heterodimers consisting of two conjoined NPs can self-assemble into novel multicomponent SLs with a high degree of alignment between the atomic lattices of individual NPs, which has been theorized to lead to a wide variety of remarkable properties. Specifically, by using simulations and experiments, we show that heterodimers composed of larger Fe3O4 domains decorated with a Pt domain at one vertex can self-assemble into an SL with long-range atomic alignment between the Fe3O4 domains of different NPs across the SL. The SLs show an unanticipated decreased coercivity relative to nonassembled NPs. In situ scattering of the self-assembly reveals a two-stage mechanism of self-assembly: translational ordering between NPs develops before atomic alignment. Our experiments and simulation indicate that atomic alignment requires selective epitaxial growth of the smaller domain during heterodimer synthesis and specific size ratios of the heterodimer domains as opposed to specific chemical composition. This composition independence makes the self-assembly principles elucidated here applicable to the future preparation of multicomponent materials with fine structural control.

Deterministic Quantum Light Arrays from Giant Silica-Shelled Quantum Dots.

Colloidal quantum dots (QDs) are promising candidates for single-photon sources with applications in photonic quantum information technologies. Developing practical photonic quantum devices with colloidal materials, however, requires scalable deterministic placement of stable single QD emitters. In this work, we describe a method to exploit QD size to facilitate deterministic positioning of single QDs into large arrays while maintaining their photostability and single-photon emission properties. CdSe/CdS core/shell QDs were encapsulated in silica to both increase their physical size without perturbing their quantum-confined emission and enhance their photostability. These giant QDs were then precisely positioned into ordered arrays using template-assisted self-assembly with a 75% yield for single QDs. We show that the QDs before and after assembly exhibit antibunching behavior at room temperature and their optical properties are retained after an extended period of time. Together, this bottom-up synthetic approach via silica shelling and the robust template-assisted self-assembly offer a unique strategy to produce scalable quantum photonics platforms using colloidal QDs as single-photon emitters.

Chemical and Physical Properties of Photonic Noble-Metal Nanomaterials.

Colloidal noble metal nanoparticles (NPs) are composed of metal cores and organic or inorganic ligand shells. These NPs support size- and shape-dependent plasmonic resonances. They can be assembled from dispersions into artificial metamolecules which have collective plasmonic resonances originating from coupled bright and dark optical electric and magnetic modes that form depending on the size and shape of the constituent NPs and their number, arrangement, and interparticle distance. NPs can also be assembled into extended 2D and 3D metamaterials that are glassy thin films or ordered thin films or crystals, also known as superlattices and supercrystals. The metamaterials have tunable optical properties that depend on the size, shape, and composition of the NPs, and on the number of NP layers and their interparticle distance. Interestingly, strong light-matter interactions in superlattices form plasmon polaritons. Tunable interparticle distances allow designer materials with dielectric functions tailorable from that characteristic of an insulator to that of a metal, and serve as strong optical absorbers or scatterers, respectively. In combination with lithography techniques, these extended assemblies can be patterned to create subwavelength NP superstructures and form large-area 2D and 3D metamaterials that manipulate the amplitude, phase, and polarization of transmitted or reflected light.

Single-Particle Insights into Plasmonic Hot Carrier Separation Augmenting Photoelectrochemical Ethanol Oxidation with Photocatalytically Synthesized Pd-Au Bimetallic Nanorods.

Understanding the nature of hot carrier pathways following surface plasmon excitation of heterometallic nanostructures and their mechanistic prevalence during photoelectrochemical oxidation of complex hydrocarbons, such as ethanol, remains challenging. This work studies the fate of carriers from Au nanorods before and after the presence of reductively photodeposited Pd at the single-particle level using scattering and emission spectroscopy, along with ensemble photoelectrochemical methods. A sub-2 nm epitaxial Pd0 shell was reductively grown onto colloidal Au nanorods via hot carriers generated from surface plasmon resonance excitation in the presence of [PdCl4]2-. These bimetallic Pd-Au nanorod architectures exhibited 14% quenched emission quantum yields and 9% augmented plasmon damping determined from their scattering spectra compared to the bare Au nanorods, consistent with injection/separation of intraband hot carriers into the Pd. Absorbed photon-to-current efficiency in photoelectrochemical ethanol oxidation was enhanced 50× from 0.00034% to 0.017% due to the photodeposited Pd. Photocurrent during ethanol oxidation improved 13× under solar-simulated AM1.5G and 40× for surface plasmon resonance-targeted irradiation conditions after photodepositing Pd, consistent with enhanced participation of intraband-excited sp-band holes and desorption of ethanol oxidation reaction intermediates owing to photothermal effects.

Light emission from plasmonic nanostructures.

The mechanism of light emission from metallic nanoparticles has been a subject of debate in recent years. Photoluminescence and electronic Raman scattering mechanisms have both been proposed to explain the observed emission from plasmonic nanostructures. Recent results from Stokes and anti-Stokes emission spectroscopy of single gold nanorods using continuous wave laser excitation carried out in our laboratory are summarized here. We show that varying excitation wavelength and power change the energy distribution of hot carriers and impact the emission spectral lineshape. We then examine the role of interband and intraband transitions in the emission lineshape by varying the particle size. We establish a relationship between the single particle emission quantum yield and its corresponding plasmonic resonance quality factor, which we also tune through nanorod crystallinity. Finally, based on anti-Stokes emission, we extract electron temperatures that further suggest a hot carrier based mechanism. The central role of hot carriers in our systematic study on gold nanorods as a model system supports a Purcell effect enhanced hot carrier photoluminescence mechanism. We end with a discussion on the impact of understanding the light emission mechanism on fields utilizing hot carrier distributions, such as photocatalysis and nanothermometry.

Plasmon Energy Transfer in Hybrid Nanoantennas.

Plasmonic metal nanoparticles exhibit large dipole moments upon photoexcitation and have the potential to induce electronic transitions in nearby materials, but fast internal relaxation has to date limited the spatial range and efficiency of plasmonic mediated processes. In this work, we use photo-electrochemistry to synthesize hybrid nanoantennas comprised of plasmonic nanoparticles with photoconductive polymer coatings. We demonstrate that the formation of the conductive polymer is selective to the nanoparticles and that polymerization is enhanced by photoexcitation. In situ spectroscopy and simulations support a mechanism in which up to 50% efficiency of nonradiative energy transfer is achieved. These hybrid nanoantennas combine the unmatched light-harvesting properties of a plasmonic antenna with the similarly unmatched device processability of a polymer shell.

Increased Intraband Transitions in Smaller Gold Nanorods Enhance Light Emission.

Photoinduced light emission from plasmonic nanoparticles has attracted considerable interest within the scientific community because of its potential applications in sensing, imaging, and nanothermometry. One of the suggested mechanisms for the light emission from plasmonic nanoparticles is the plasmon-enhanced radiative recombination of hot carriers through inter- and intraband transitions. Here, we investigate the nanoparticle size dependence on the photoluminescence through a systematic analysis of gold nanorods with similar aspect ratios. Using single-particle emission and scattering spectroscopy along with correlated scanning electron microscopy and electromagnetic simulations, we calculate the emission quantum yields and Purcell enhancement factors for individual gold nanorods. Our results show strong size-dependent quantum yields in gold nanorods, with higher quantum yields for smaller gold nanorods. Furthermore, by determining the relative contributions to the photoluminescence from inter- and intraband transitions, we deduce that the observed size dependence predominantly originates from the size dependence of intraband transitions. Specifically, within the framework of Fermi's golden rule for radiative recombination of excited charge carriers, we demonstrate that the Purcell factor enhancement alone cannot explain the emission size dependence and that changes in the transition matrix elements must also occur. Those changes are due to electric field confinement enhancing intraband transitions. These results provide vital insight into the intraband relaxation in metallic nanoconfined systems and therefore are of direct importance to the rapidly developing field of plasmonic photocatalysis.

Anti-Stokes Emission from Hot Carriers in Gold Nanorods.

The origin of light emission from plasmonic nanoparticles has been strongly debated lately. It is present as the background of surface-enhanced Raman scattering and, despite the low yield, has been used for novel sensing and imaging applications because of its photostability. Although the role of surface plasmons as an enhancing antenna is widely accepted, the main controversy regarding the mechanism of the emission is its assignment to either radiative recombination of hot carriers (photoluminescence) or electronic Raman scattering (inelastic light scattering). We have previously interpreted the Stokes-shifted emission from gold nanorods as the Purcell effect enhanced radiative recombination of hot carriers. Here we specifically focused on the anti-Stokes emission from single gold nanorods of varying aspect ratios with excitation wavelengths below and above the interband transition threshold while still employing continuous wave lasers. Analysis of the intensity ratios between Stokes and anti-Stokes emission yields temperatures that can only be interpreted as originating from the excited electron distribution and not a thermally equilibrated phonon population despite not using pulsed laser excitation. Consistent with this result as well as previous emission studies using ultrafast lasers, the power-dependence of the upconverted emission is nonlinear and gives the average number of participating photons as a function of emission wavelength. Our findings thus show that hot carriers and photoluminescence play a major role in the upconverted emission.

Polycrystallinity of Lithographically Fabricated Plasmonic Nanostructures Dominates Their Acoustic Vibrational Damping.

The study of acoustic vibrations in nanoparticles provides unique and unparalleled insight into their mechanical properties. Electron-beam lithography of nanostructures allows precise manipulation of their acoustic vibration frequencies through control of nanoscale morphology. However, the dissipation of acoustic vibrations in this important class of nanostructures has not yet been examined. Here we report, using single-particle ultrafast transient extinction spectroscopy, the intrinsic damping dynamics in lithographically fabricated plasmonic nanostructures. We find that in stark contrast to chemically synthesized, monocrystalline nanoparticles, acoustic energy dissipation in lithographically fabricated nanostructures is solely dominated by intrinsic damping. A quality factor of Q = 11.3 ± 2.5 is observed for all 147 nanostructures, regardless of size, geometry, frequency, surface adhesion, and mode. This result indicates that the complex Young's modulus of this material is independent of frequency with its imaginary component being approximately 11 times smaller than its real part. Substrate-mediated acoustic vibration damping is strongly suppressed, despite strong binding between the glass substrate and Au nanostructures. We anticipate that these results, characterizing the optomechanical properties of lithographically fabricated metal nanostructures, will help inform their design for applications such as photoacoustic imaging agents, high-frequency resonators, and ultrafast optical switches.

Photoluminescence of Gold Nanorods: Purcell Effect Enhanced Emission from Hot Carriers.

We demonstrate, experimentally and theoretically, that the photon emission from gold nanorods can be viewed as a Purcell effect enhanced radiative recombination of hot carriers. By correlating the single-particle photoluminescence spectra and quantum yields of gold nanorods measured for five different excitation wavelengths and varied excitation powers, we illustrate the effects of hot carrier distributions evolving through interband and intraband transitions and the photonic density of states on the nanorod photoluminescence. Our model, using only one fixed input parameter, describes quantitatively both emission from interband recombination and the main photoluminescence peak coinciding with the longitudinal surface plasmon resonance.

Optimization of Spectral and Spatial Conditions to Improve Super-Resolution Imaging of Plasmonic Nanoparticles.

Interactions between fluorophores and plasmonic nanoparticles modify the fluorescence intensity, shape, and position of the observed emission pattern, thus inhibiting efforts to optically super-resolve plasmonic nanoparticles. Herein, we investigate the accuracy of localizing dye fluorescence as a function of the spectral and spatial separations between fluorophores (Alexa 647) and gold nanorods (NRs). The distance at which Alexa 647 interacts with NRs is varied by layer-by-layer polyelectrolyte deposition while the spectral separation is tuned by using NRs with varying localized surface plasmon resonance (LSPR) maxima. For resonantly coupled Alexa 647 and NRs, emission to the far field through the NR plasmon is highly prominent, resulting in underestimation of NR sizes. However, we demonstrate that it is possible to improve the accuracy of the emission localization when both the spectral and spatial separations between Alexa 647 and the LSPR are optimized.

Single-particle absorption spectroscopy by photothermal contrast.

Removing effects of sample heterogeneity through single-molecule and single-particle techniques has advanced many fields. While background free luminescence and scattering spectroscopy is widely used, recording the absorption spectrum only is rather difficult. Here we present an approach capable of recording pure absorption spectra of individual nanostructures. We demonstrate the implementation of single-particle absorption spectroscopy on strongly scattering plasmonic nanoparticles by combining photothermal microscopy with a supercontinuum laser and an innovative calibration procedure that accounts for chromatic aberrations and wavelength-dependent excitation powers. Comparison of the absorption spectra to the scattering spectra of the same individual gold nanoparticles reveals the blueshift of the absorption spectra, as predicted by Mie theory but previously not detectable in extinction measurements that measure the sum of absorption and scattering. By covering a wavelength range of 300 nm, we are furthermore able to record absorption spectra of single gold nanorods with different aspect ratios. We find that the spectral shift between absorption and scattering for the longitudinal plasmon resonance decreases as a function of nanorod aspect ratio, which is in agreement with simulations.

Photochemically engineering the metal-semiconductor interface for room-temperature transfer hydrogenation of nitroarenes with formic acid.

A mild photochemical approach was applied to construct highly coupled metal-semiconductor dyads, which were found to efficiently facilitate the hydrogenation of nitrobenzene. Aniline was produced in excellent yield (>99 %, TOF: 1183) using formic acid as hydrogen source and water as solvent at room temperature. This general and green catalytic process is applicable to a wide range of nitroarenes without the involvement of high-pressure gases or sacrificial additives.

The crystallinity effect of mesocrystalline BaZrO3 hollow nanospheres on charge separation for photocatalysis.

Highly crystalline mesocrystalline BaZrO3 hollow nanospheres offered higher photocatalytic activities. It is found that the highly crystalline sample can function as a "highway" for electron transport with less grain boundaries, resulting in better charge separation and thus photocatalytic performance.

Synergistic effect of Brønsted acid and platinum on purification of automobile exhaust gases.

The catalytic purification of automobile exhaust gases (CO, NOx and hydrocarbons) is one of the most practiced conversion processes used to lower the emissions and to reduce the air pollution. Nevertheless, the good performance of exhaust gas purification catalysts often requires the high consumption of noble metals such as platinum. Here we report that the Brønsted acid sites on the external surface of a microporous silicoaluminophosphate (SAPO) act as a promoter for exhaust gas purification, effectively cutting the loading amount of platinum in the catalyst without sacrifice of performance. It is revealed that in the Pt-loaded SAPO-CHA catalyst, there exists a remarkable synergistic effect between the Brønsted acid sites and the Pt nanoparticles, the former helping to adsorb and activate the hydrocarbon molecules for NO reduction during the catalytic process. The thermal stability of SAPO-CHA also makes the composite catalyst stable and reusable without activity decay.