Plasmonic Nanocrystals Research Articles

Visible and near-infrared modulating tungsten suboxide nanorods electrochromic films in acidic aqueous electrolytes

Proton-based aqueous electrolytes can be used to achieve high performance electrochromic nanocrystal thin films due to their small ion size. However, acidic aqueous electrolyte systems have not yet been explored in near-infrared (NIR) absorbing plasmonic tungsten oxide nanocrystal films. Here, we demonstrate tungsten suboxide nanorod films with excellent visible and NIR modulation performance in the H+-based aqueous electrolytes, thanks to their mesoporous structure, nanosized domains, and open tunnel structure. Colloidally synthesized WO2.83 nanorods with an average width of 6 nm and length of 48 nm were converted to WO2.90 nanorod film via annealing in air, while still preserving open tunnels. These films exhibit fast switching speed (tc = 0.9 s, tb = 2.1 s), excellent cycling stability over 2500 cycles, wide optical modulation up to ΔT = 53.8 % in the NIR region, and a high coloration efficiency (CE) of 167 cm2 C⁻1 at 1300 nm. Additionally, introducing a thin spacer (25 μm) reduced intrinsic NIR absorption from water, thereby enhancing the NIR modulation properties. These highly performing aqueous proton-electrolytes-based electrochromic devices open new possibilities for implementing visible and NIR electrochromism.

Tuning emittance in films of plasmonic metal oxide nanocrystals for daytime radiative cooling

Radiative cooling offers a passive, low-cost option for thermal management without expending energy on intensive active cooling mechanisms. Doped metal oxide nanocrystals are a promising option for maintaining high solar transparency while accessing tunable emission in the primary atmospheric transparency window from their localized surface plasmon resonance. Finite element method simulations of nanocrystal films are used to explore impacts of nanocrystal size, doping concentration, and film thickness on film emissivity. We reveal trade-offs between emission intensity and selectivity: Targeting selective emission results in unwanted reflectance from nanocrystal coupling limiting the maximum emissivity, while maximizing emissivity through increasing film thickness causes unwanted solar absorption from broadened emission. The trade-offs result in temperature-dependent design rules for optimizing radiated power. An optimized radiative cooler could provide 20 ° C of cooling, close to the ideal emitter. High emissivity is achievable in real nanocrystals which exhibit extinction peaks close to the best simulated case.

Metallic Degenerately Doped Free-Electron-Confined Plasmonic Nanocrystal and Infrared Extinction Response

In this paper, synthetically scaled-up degenerately n-type doped indium tin oxide (Sn:In2O3) nanocrystals are described as highly transparent conductive materials possessing both optoelectronic and crystalline properties. With tin dopants serving as n-type semiconductor materials, they can generate free-electron carriers. These free electrons, vibrating in resonance with infrared radiation, induce strong localized surface plasmon resonance (LSPR), resulting in efficient infrared absorption. To commercialize products featuring Sn:In2O3 with localized surface plasmon resonance, a scaled-up synthetic process is essential. To reduce the cost of raw materials during synthesis, we aim to proceed with synthesis in a large reactor using industrial raw materials. Sn:In2O3 can be formulated into ink dispersed in solvents. Infrared-absorbing ink formulations can capitalize on their infrared absorption properties to render opaque in the infrared spectrum while remaining transparent in the visible light spectrum. The ink can serve as a security ink material visible only through infrared cameras and as a paint absorbing infrared light. We verified the transparency and infrared absorption properties of the ink produced in this study, demonstrating consistent characteristics in scaled-up synthesis. Due to potential applications requiring infrared absorption properties, it holds significant promise as a robust platform material in various fields.

Observing Metallic Carriers in Highly Faceted Plasmonic Cd2SnO4 Inverse Spinel Nanocrystals

AbstractCorrelating data from optical, structural, and theoretical methods allows the properties of highly faceted Cd2SnO4 (CTO) inverted spinel plasmonic semiconductor nanocrystals (PSNCs) to be fully evaluated. The use of Sn(II) in the colloidal reaction for CTO results in reproducible octahedral PSNCs with an aspect ratio of 1.30. Correlating extinction spectra with magnetic circular dichroism yields a carrier density (n = 5.19 × 1019 cm−3) and carrier effective mass (m* = 0.022me) respectively. 113Cd and 119Sn solid‐state NMR experiments show clear evidence of metallic‐like carriers in CTO NCs based upon the observation of Knight shifts. These data suggest that carrier formation in CTO arises from Sn antisite occupation of octahedral Cd sites (SnCd). From a broader perspective, the results point to wide‐bandgap spinels as being an important but understudied class of plasmonic PSNCs.

Cholesteric Liquid Crystal‐Mediated Chiral Plasmonic Films with Strong Chiroptical Response, Dynamic Tunability, and Reversible Thermal Reconfigurability

AbstractChiral assemblies of plasmonic nanocrystals (NCs) are of immense interest due to their distinctive physicochemical characteristics and promising potential in future optoelectronic applications. Despite recent advances in the construction of chiral NC assemblies, most approaches have led to the formation of static irreversible structures with modest optical responses and limited configurational tunability. Herein, a way to prepare a thermally reconfigurable helical assembly of Au nanorods (AuNRs) with a strong chiroptical response is introduced by employing cholesteric liquid crystals (CLCs) as a chiral template. Circular dichroism (CD) spectroscopy and polarized optical microscopy are used to verify the strong chiroptical activity and dynamic optical tunability of chiral plasmonic film of AuNR–CLC composites and to unveil the interactions between constituents. For the system, chiral dopants are employed to induce strong helical procession along the hierarchical structure of the CLC template, resulting in a strong CD response, which can further be enhanced by increasing the amount of AuNRs. Furthermore, the thermotropic nature of the CLC template leads to the reversible on/off switching of the chiroptical responses of the system at a moderate temperature window with almost complete recovery of the original response, suggesting its feasibility as a promising material for chiral optoelectronic devices.

Statistical and Correlative Characterization of Individual Nanoparticle in Gap Plasmon Resonator Sensors

AbstractPlasmonic nanocavities are receving increased attention from the nanophotonics, nanoelectronics, and quantum optics community due to their ability to confine light in extremely small volumes. Coupling colloidal plasmonic nanocrystals to metal films is an inexpensive approach to fabricate virtually unlimited individual resonators that can be tuned by adjusting nanoparticle size, gap thickness, and refractive index. The focus is on silver nanocubes separated from a gold mirror by thin amorphous dielectric layers (Al2O3, TiO2). The optical response is measured and correlative electron microscopy is performed on a large number (>800) of individual resonators to unveil the statistical distribution of gap plasmon modes and assess systematically their sensitivity. A sensitivity as large as 8 nm/nm to nanocube size variation, 50 nm/nm to Al2O3 thickness variation, and 130 nm/RIU for index change of the spacer layer is found. With the help of numerical simulations, this approach enables to infer a quantitative statistical distribution of molecular coatings present on the nanocubes surface, such as polyvinylpyrrolidone, which can affect the performance of nanoelectronic devices and assess the strategy to remove it. Finally, polarization‐resolved measurements enable to unveil a birefringent behavior when nanocubes are supported on annealed TiO2 layers (2–4 nm).

Plasmon-Induced Hot Electrons in Nanostructured Materials: Generation, Collection, and Application to Photochemistry.

Plasmon refers to the coherent oscillation of all conduction-band electrons in a nanostructure made of a metal or a heavily doped semiconductor. Upon excitation, the plasmon can decay through different channels, including nonradiative Landau damping for the generation of plasmon-induced energetic carriers, the so-called hot electrons and holes. The energetic carriers can be collected by transferring to a functional material situated next to the plasmonic component in a hybrid configuration to facilitate a range of photochemical processes for energy or chemical conversion. This article centers on the recent advancement in generating and utilizing plasmon-induced hot electrons in a rich variety of hybrid nanostructures. After a brief introduction to the fundamentals of hot-electron generation and decay in plasmonic nanocrystals, we extensively discuss how to collect the hot electrons with various types of functional materials. With a focus on plasmonic nanocrystals made of metals, we also briefly examine those based upon heavily doped semiconductors. Finally, we illustrate how site-selected growth can be leveraged for the rational fabrication of different types of hybrid nanostructures, with an emphasis on the parameters that can be experimentally controlled to tailor the properties for various applications.

Direct Determination of Carrier Parameters in Indium Tin Oxide Nanocrystals.

We develop here a comprehensive experimental approach to independently determine charge carrier parameters, namely, carrier density and mass, in plasmonic indium tin oxide nanocrystals. Typically, in plasmonic nanocrystals, only the ratio between these two parameters is accessible through optical absorption experiments. The multitechnique methodology proposed here combines single particle and ensemble optical and magneto-optical spectroscopies, also using 119Sn solid-state nuclear magnetic resonance spectroscopy to probe the surface depletion layer. Our methodology overcomes the limitations of standard fitting approaches based on absorption spectroscopy and ultimately gives access to carrier effective mass directly on the NCs, discarding the use of literature value based on bulk or thin film materials. We found that mass values depart appreciably from those measured on thin films; consequently, we found carrier density values that are different from reported literature values for similar systems. The effective mass was found to deviate from the parabolic approximation at a high carrier density. Finally, the dopant activation and defect diagram for ITO NCs for tin doping between 2.5 and 15% are determined. This approach can be generalized to other plasmonic heavily doped semiconductor nanostructures and represents, to the best of our knowledge, the only method to date to characterize the full Drude parameter space of 0-D nanosystems.

Open-Nanogap-Induced Strong Electromagnetic Enhancement in Au/AgAu Monolayer as a Stable and Uniform SERS Substrate for Ultrasensitive Detection.

Nanogap-based plasmonic metal nanocrystals have been applied in surface-enhanced Raman scattering detection, while the closed and insufficient electromagnetic fields as well as the nonreproducible Raman signal of the substrate greatly restrict the actual application. Herein, a highly uniform Au/AgAu monolayer with abundant nanogaps and huge electromagnetic enhancement is prepared, which shows ultrasensitive and reproducible SERS detection. Au/AgAu with an inner nanogap is first prepared based on Au nanotriangles, and the nanogap is opened from the three tips via a subsequent etching process. The open-gap Au/AgAu displays much higher SERS efficiency than Au and Au/AgAu with an inner nanogap on detecting crystal violet due to the open-gap induced electromagnetic enhancement and improved molecular absorption. Furthermore, the open-gap Au/AgAu monolayer is prepared via interfacial self-assembly, which shows further improved SERS due to the dense and strong hotspots in the nanocavities induced by the electromagnetic coupling between adjacent open gaps. The monolayer possesses excellent signal stability, uniformity, and reproducibility. The analytic enhancement factor and relative standard deviation reach to 2.12 × 108 and 4.65% on detecting crystal violet, respectively. Moreover, the monolayer achieves efficient detection of thiram in apple juice, biphenyl-4-thiol, 4-mercaptobenzoic, melamine, and a mixed solution of four different molecules, showing great promise in practical detection.

Circular Differential Photocurrent Mapping of Hot Electron Response from Individual Plasmonic Nanohelicoids.

Chiral plasmonic nanocrystals have recently attracted increasing attention in circular polarization-dependent photocatalysis driven by hot carriers. While being concealed in traditional ensemble measurements, the individual chiral photocatalytic activity of nanocrystals can exclusively be revealed by directly correlating the circular differential photocurrent response to helical morphologies using single-particle techniques. Herein, we develop a method named circular differential photocurrent mapping (CDPM) and demonstrate that CDPM can be used to characterize the circular differential hot electron (CDHE) response from individual Au nanohelicoids (AuNHs) on a TiO2 photoanode in a photoelectrochemical cell. The single-particle circular differential scattering and CDHE measurements were interpreted with calculations performed on a model in direct correlation to the helical morphologies of the nanocrystal. While CDHE response was found inactive at a dipolar resonance of 750 nm, helicity-convoluted sites of HE generation were identified on the AuNH at a specific higher-order mode of 550 nm, resulting in a significant response of CDHE in association with the handedness of the AuNH. Details of circular differential contributions were further resolved by examining the efficiencies of individual AuNHs in terms of g-factors. Our study provides a powerful microscopic method at the single-particle level for the photocatalytic characterization of chiral nanocrystals, gaining fundamental insights into the photocatalysis of chirality, especially toward plasmon-induced asymmetrical photochemistry or photoelectrochemistry.

Tuning the Chiral Growth of Plasmonic Bipyramids via the Wavelength and Polarization of Light.

Circularly polarized light (CPL) is a versatile tool to prepare chiral nanostructures, but the mechanism for inducing enantioselectivity is not well understood. This work shows that the energy and polarization of visible photons can initiate photodeposition at different sites on plasmonic nanocrystals. Here, CPL on achiral gold bipyramids (AuBPs) creates hot holes that oxidatively deposit PbO2 asymmetrically. We show for the first time that the location of PbO2 photodeposition and hence optical dissymmetry depends on the CPL wavelength. Specifically, 488 and 532 nm CPL induce PbO2 growth in the middle of AuBPs, whereas 660 nm CPL induces PbO2 growth at the tips. Our observations show that wavelength-dependent plasmonic field distributions are more important than surface lightning rod effects in localizing plasmon-mediated photochemistry. The largest optical dissymmetry occurs at excitation wavelengths between the transverse and longitudinal resonances of the AuBPs because higher-order modes are required to induce chiral electric fields.

Dynamic Behavior of Platinum Atoms and Clusters in the Native Oxide Layer of Aluminum Nanocrystals.

Strong metal-support interactions (SMSIs) are well-known in the field of heterogeneous catalysis to induce the encapsulation of platinum (Pt) group metals by oxide supports through high temperature H2 reduction. However, demonstrations of SMSI overlayers have largely been limited to reducible oxides, such as TiO2 and Nb2O5. Here, we show that the amorphous native surface oxide of plasmonic aluminum nanocrystals (AlNCs) exhibits SMSI-induced encapsulation of Pt following reduction in H2 in a Pt structure dependent manner. Reductive treatment in H2 at 300 °C induces the formation of an AlOx SMSI overlayer on Pt clusters, leaving Pt single-atom sites (Ptiso) exposed available for catalysis. The remaining exposed Ptiso species possess a more uniform local coordination environment than has been observed on other forms of Al2O3, suggesting that the AlOx native oxide of AlNCs presents well-defined anchoring sites for individual Pt atoms. This observation extends our understanding of SMSIs by providing evidence that H2-induced encapsulation can occur for a wider variety of materials and should stimulate expanded studies of this effect to include nonreducible oxides with oxygen defects and the presence of disorder. It also suggests that the single-atom sites created in this manner, when combined with the plasmonic properties of the Al nanocrystal core, may allow for site-specific single-atom plasmonic photocatalysis, providing dynamic control over the light-driven reactivity in these systems.

Metal dimer nanojunction-magnetic material composites for magnetic field sensing.

Noble metal nanocrystals are used as high sensitivity optoelectronic sensors, such as surface-enhanced Raman scattering, SERS. The sensing performance of metal nanocrystals can be further improved by forming dimer nanojunctions with strong "plasmonic coupling". Since the strength of "plasmonic coupling" is highly sensitive to the sub-nanoscale spacing between plasmonic nanocrystals in nanojunctions, nanojunctions can be used to detect external stimuli that can change the spacing of nanocrystals in the nanojunction and thus change the sensitivity of the Raman scattering spectrum. Here, we utilize this principle to detect the direction and strength of an external magnetic field (MF) using dimer nanojunctions surrounded by magnetic materials as a sensing platform. The results reveal that the changes in nanocrystal spacing in the nanojunction are caused by the rearrangement of the magnetic material under an external MF, which strongly depends on the interaction between the magnetic material and the ligands on the nanocrystal surface and the steric repulsion generated by the ligand configuration on the nanocrystal surface. Compared with the Raman spectrum without an external MF, the enhancement factors of the Raman scattering spectrum under an external MF can reach up to ∼900%, which makes dimer nanojunctions with magnetic materials suitable for "magnetic field" sensing applications.

Towards photoelectrochromic modulation of NIR absorption in plasmonic ITO using pentacene films

Pentacene molecules are deposited onto plasmonic ITO nanocrystals as hybrid organic–inorganic bilayers, holding promise as prospective NIR-modulating electrochromic systems being self-powered by VIS-light-driven photocharging.

Single-crystal and pentatwinned nanorods reverse the handedness of chiral plasmonic nanocrystals: An electron tomography study

Single-crystal and pentatwinned nanorods reverse the handedness of chiral plasmonic nanocrystals: An electron tomography study

Wavelength Tunable Infrared Perfect Absorption in Plasmonic Nanocrystal Monolayers.

The ability to efficiently absorb light in ultrathin (subwavelength) layers is essential for modern electro-optic devices, including detectors, sensors, and nonlinear modulators. Tailoring these ultrathin films' spectral, spatial, and polarimetric properties is highly desirable for many, if not all, of the above applications. Doing so, however, often requires costly lithographic techniques or exotic materials, limiting scalability. Here we propose, demonstrate, and analyze a mid-infrared absorber architecture leveraging monolayer films of nanoplasmonic colloidal tin-doped indium oxide nanocrystals (ITO NCs). We fabricate a series of ITO NC monolayer films using the liquid-air interface method; by synthetically varying the Sn dopant concentration in the NCs, we achieve spectrally selective perfect absorption tunable between wavelengths of two and five micrometers. We achieve monolayer thickness-controlled coupling strength tuning by varying NC size, allowing access to different coupling regimes. Furthermore, we synthesize a bilayer film that enables broadband absorption covering the entire midwave IR region (λ = 3-5 μm). We demonstrate a scalable platform, with perfect absorption in monolayer films only hundredths of a wavelength in thickness, enabling strong light-matter interaction, with potential applications for molecular detection and ultrafast nonlinear optical applications.

Dipolar Ligands Tune Plasmonic Properties of Tin-Doped Indium Oxide Nanocrystals.

Surface functionalization with dipolar molecules is known to tune the electronic band alignment in semiconductor films and colloidal quantum dots. Yet, the influence of surface modification on plasmonic nanocrystals and their properties remains little explored. Here, we functionalize tin-doped indium oxide nanocrystals (ITO NCs) via ligand exchange with a series of cinnamic acids with different electron-withdrawing and -donating dipolar characters. Consistent with previous reports on semiconductors, we find that withdrawing (donating) ligands increase (decrease) the work function caused by an electrostatic potential shift across the molecular layer. Quantitative analyses of the plasmonic extinction spectra reveal that varying the ligand molecular dipole affects the near-surface depletion layer, with an anticorrelated trend between the electron concentration and electronic volume fraction, factors that are positively correlated in as-synthesized NCs. Electronic structure engineering through surface modification provides access to distinctive combinations of plasmonic properties that could enable optoelectronic applications, sensing, and hot electron-driven processes.

Hierarchically Doped Plasmonic Nanocrystal Metamaterials.

Assembling plasmonic nanocrystals in regular superlattices can produce effective optical properties not found in homogeneous materials. However, the range of these metamaterial properties is limited when a single nanocrystal composition is selected for the constituent meta-atoms. Here, we show how continuously varying doping at two length scales, the atomic and nanocrystal scales, enables tuning of both the frequency and bandwidth of the collective plasmon resonance in nanocrystal-based metasurfaces, while these features are inextricably linked in single-component superlattices. Varying the mixing ratio of indium tin oxide nanocrystals with different dopant concentrations, we use large-scale simulations to predict the emergence of a broad infrared spectral region with near-zero permittivity. Experimentally, tunable reflectance and absorption bands are observed, owing to in- and out-of-plane collective resonances. These spectral features and the predicted strong near-field enhancement establish this multiscale doping strategy as a powerful new approach to designing metamaterials for optical applications.

High-Yield Gold Nanohydrangeas on Three-Dimensional Carbon Nanotube Foams for Surface-Enhanced Raman Scattering Sensors.

Recently, carbon nanomaterial-supported plasmonic nanocrystals used as high-performance surface-enhanced Raman scattering (SERS) substrates have attracted increasing attention due to their ultra-high sensitivity of detection. However, most of the work focuses on the design of 2-D planar substrates with traditional plasmonic structures, such as nanoparticles, nanorods, nanowires, and so forth. Here, we report a novel strategy for the preparation of high-yield Au nanohydrangeas on three-dimensional porous polydopamine (PDA)/polyvinyl alcohol (PVA)/carbon nanotube (CNT) foams. The structures and growth mechanisms of these specific Au nanocrystals are systematically investigated. PDA plays the role of both a reducing agent as well as an anchoring site for Au nanohydrangeas' growth. We also show that the ratio of surfactant KBr to the gold precursor (HAuCl4) is key to obtain these structures in a manner of high production. Moreover, the substrate of the CNT foam-Au nanohydrangea hybrid can be employed as SERS sensors and can detect the analytes down to 10-9 M.

Passively Q-switched ytterbium doped fiber laser based on a weak-photothermal saturable absorber

Recently, plasmonic nanocrystals (NCs) have attracted much attention due to their wide applications in bioimaging, photothermal therapy and photonics devices. Compared to other metal NCs, copper NCs show a weak photo-thermal effect, which shows that the copper NCs are a good candidate for nonlinear optical materials. In this paper, we demonstrated a Q-switched fiber laser at 1 μm wavelength by using Cu1.8S NCs as a saturable absorber (SA). By incorporating the Cu1.8S SA into an ytterbium doped fiber laser cavity pumped by a 980 nm laser diode, stable passive Q-switching at 1038 nm was obtained for a threshold pump power of 63 mW. On gradually increasing the pump power from 64 mW to 160 mW, the repetition rate of a Q-switched laser increases from 25.7 kHz to 54.5 kHz and the pulse duration decreases from 6.7 μs to 2.33 μs. Our results showed that Cu1.8S NCs is an effective SA for constructing pulsed lasers with a broadband operating wavelength.