Observation of Room-Temperature Exciton-Polariton Emission from Wide-Ranging 2D Semiconductors Coupled with a Broadband Mie Resonator.

Two-dimensional exciton-polaritons in monolayer transition metal dichalcogenides (TMDs) exhibit practical advantages in valley coherence, optical nonlinearities, and even bosonic condensation owing to their light-emission capability. To achieve robust exciton-polariton emission, strong photon-exciton couplings are required at the TMD monolayer, which is challenging due to its atomic thickness. High-quality (Q) factor optical cavities with narrowband resonances are an effective approach but typically limited to a specific excitonic state of a certain TMD material. Herein, we achieve on-demand exciton-polariton emission from a wide range of TMDs at room temperature by hybridizing excitons with broadband Mie resonances spanning the whole visible spectrum. By confining broadband light at the TMD monolayer, our one type of Mie resonator on different TMDs enables enhanced light-matter interactions with multiple excitonic states simultaneously. We demonstrate multi-Rabi splittings and robust polaritonic photoluminescence in monolayer WSe2, WS2, and MoS2. The hybrid system also shows the potential to approach the ultrastrong coupling regime.

Cesium Methylammonium Lead Iodide (Csx MA1-x PbI3 ) Nanocrystals with Wide Range Cation Composition Tuning and Enhanced Thermal Stability of the Perovskite Phase.

Cesium methylammonium lead iodide (Csx MA1-x PbI3 ) nanocrystals were obtained with a wide range of A-site Cs-MA compositions by post-synthetic, room temperature cation exchange between CsPbI3 nanocrystals and MAPbI3 nanocrystals. The alloyed Csx MA1-x PbI3 nanocrystals retain their photoactive perovskite phase with incorporated Cs content, x, as high as 0.74 and the expected composition-tunable photoluminescence (PL). Excess methylammonium oleate from the reaction mixture in the MAPbI3 nanocrystal dispersions was necessary to obtain fast Cs-MA cation exchange. The phase transformation and degradation kinetics of films of Csx MA1-x PbI3 nanocrystals were measured and modeled using an Avrami expression. The transformation kinetics were significantly slower than those of the parent CsPbI3 and MAPbI3 nanocrystals, with Avrami rate constants, k, at least an order of magnitude smaller. These results affirm that A-site cation alloying is a promising strategy for stabilizing iodide-based perovskites.

Synthetic Control of Intrinsic Defect Formation in Metal Oxide Nanocrystals Using Dissociated Spectator Metal Salts.

Crystallographic defects are essential to the functional properties of semiconductors, controlling everything from conductivity to optical properties and catalytic activity. In nanocrystals, too, defect engineering with extrinsic dopants has been fruitful. Although intrinsic defects like vacancies can be equally useful, synthetic strategies for controlling their generation are comparatively underdeveloped. Here, we show that intrinsic defect concentration can be tuned during the synthesis of colloidal metal oxide nanocrystals by the addition of metal salts. Although not incorporated in the nanocrystals, the metal salts dissociate at high temperatures, promoting the dissociation of carboxylate ligands from metal precursors, leading to the introduction of oxygen vacancies. For example, the concentration of oxygen vacancies can be controlled up to 9% in indium oxide nanocrystals. This method is broadly applicable as we demonstrate by generating intrinsic defects in metal oxide nanocrystals of various morphologies and compositions.

Tunable Chiral Optics in All-Solid-Phase Reconfigurable Dielectric Nanostructures.

Subwavelength nanostructures with tunable compositions and geometries show favorable optical functionalities for the implementation of nanophotonic systems. Precise and versatile control of structural configurations on solid substrates is essential for their applications in on-chip devices. Here, we report all-solid-phase reconfigurable chiral nanostructures with silicon nanoparticles and nanowires as the building blocks in which the configuration and chiroptical response can be tailored on-demand by dynamic manipulation of the silicon nanoparticle. We reveal that the optical chirality originates from the handedness-dependent coupling between optical resonances of the silicon nanoparticle and the silicon nanowire via numerical simulations and coupled-mode theory analysis. Furthermore, the coexisting electric and magnetic resonances support strong enhancement of optical near-field chirality, which enables label-free enantiodiscrimination of biomolecules in single nanostructures. Our results not only provide insight into the design of functional high-index materials but also bring new strategies to develop adaptive devices for photonic and electronic applications.

Broadband Forward Light Scattering by Architectural Design of Core-Shell Silicon Particles.

A goal in the field of nanoscale optics is the fabrication of nanostructures with strong directional light scattering at visible frequencies. Here, the synthesis of Mie-resonant core-shell particles with overlapping electric and magnetic dipole resonances in the visible spectrum is demonstrated. The core consists of silicon surrounded by a lower index silicon oxynitride (SiOxNy) shell of an adjustable thickness. Optical spectroscopies coupled to Mie theory calculations give the first experimental evidence that the relative position and intensity of the magnetic and electric dipole resonances are tuned by changing the core-shell architecture. Specifically, coating a high-index particle with a low-index shell coalesces the dipoles, while maintaining a high scattering efficiency, thus generating broadband forward scattering. This synthetic strategy opens a route toward metamaterial fabrication with unprecedented control over visible light manipulation.

Enhanced Coloration Efficiency of Electrochromic Tungsten Oxide Nanorods by Site Selective Occupation of Sodium Ions.

Coloration efficiency is an important figure of merit in electrochromic windows. Though it is thought to be an intrinsic material property, we tune optical modulation by effective utilization of ion intercalation sites. Specifically, we enhance the coloration efficiency of m-WO2.72 nanocrystal films by selectively intercalating sodium ions into optically active hexagonal sites. To accurately measure coloration efficiencies, significant degradation during cycling is mitigated by introducing atomic-layer-deposited Al2O3 layers. Galvanostatic spectroscopic measurement shows that the site-selective intercalation of sodium ions in hexagonal tunnels enhances the coloration efficiency compared to a nonselective lithium ion-based electrolyte. Electrochemical rate analysis shows insertion of sodium ions to be capacitive-like, another indication of occupying hexagonal sites. Our results emphasize the importance of different site occupation on spectroelectrochemical properties, which can be used for designing materials and selecting electrolytes for enhanced electrochromic performance. In this context, we suggest sodium ion-based electrolytes hold unrealized potential for tungsten oxide electrochromic applications.

Spectrally tunable infrared plasmonic F,Sn:In2O3 nanocrystal cubes.

A synthetic challenge in faceted metal oxide nanocrystals (NCs) is realizing tunable localized surface plasmon resonance (LSPR) near-field response in the infrared (IR). Cube-shaped nanoparticles of noble metals exhibit LSPR spectral tunability limited to visible spectral range. Here, we describe the colloidal synthesis of fluorine, tin codoped indium oxide (F,Sn:In2O3) NC cubes with tunable IR range LSPR for around 10 nm particle sizes. Free carrier concentration is tuned through controlled Sn dopant incorporation, where Sn is an aliovalent n-type dopant in the In2O3 lattice. F shapes the NC morphology into cubes by functioning as a surfactant on the {100} crystallographic facets. Cube shaped F,Sn:In2O3 NCs exhibit narrow, shape-dependent multimodal LSPR due to corner, edge, and face centered modes. Monolayer NC arrays are fabricated through a liquid-air interface assembly, further demonstrating tunable LSPR response as NC film nanocavities that can heighten near-field enhancement (NFE). The tunable F,Sn:In2O3 NC near-field is coupled with PbS quantum dots, via the Purcell effect. The detuning frequency between the nanocavity and exciton is varied, resulting in IR near-field dependent enhanced exciton lifetime decay. LSPR near-field tunability is directly visualized through IR range scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS). STEM-EELS mapping of the spatially confined near-field in the F,Sn:In2O3 NC array interparticle gap demonstrates elevated NFE tunability in the arrays.

All-optical reconfigurable chiral meta-molecules.

Chirality is a ubiquitous phenomenon in the natural world. Many biomolecules without inversion symmetry such as amino acids and sugars are chiral molecules. Measuring and controlling molecular chirality at a high precision down to the atomic scale are highly desired in physics, chemistry, biology, and medicine, however, have remained challenging. Herein, we achieve all-optical reconfigurable chiral meta-molecules experimentally using metallic and dielectric colloidal particles as artificial atoms or building blocks to serve at least two purposes. One is that the on-demand meta-molecules with strongly enhanced optical chirality are well-suited as substrates for surface-enhanced chiroptical spectroscopy of chiral molecules and as active components in optofluidic and nanophotonic devices. The other is that the bottom-up-assembled colloidal meta-molecules provide microscopic models to better understand the origin of chirality in the actual atomic and molecular systems.

Deliquescent Chromism of Nickel(II) Iodide Thin Films.

Color-changing materials have a variety of applications, ranging from smart windows to sensors. Here, we report deliquescent chromism of thin, color neutral films of nickel(II) iodide (NiI2) that are less than 10 µm thick. This behavior does not occur in the bulk material. Dark brown thin films of crystalline NiI2 turn clear when exposed to humidity and can be switched back to the dark state when mildly heated (>35 °C). This optical transition between dark and clear states of an NiI2 thin film is reversible with thermal cycling.

An All-Inorganic Colloidal Nanocrystal Flexible Polarizer.

Inorganic single crystals with anisotropic structures usually suffer from high brittleness and stiffness. Flexible polymers are used to replace inorganic crystals, but the hot-stretching-induced orientation process is tedious, and oriented molecular chains tend to revert to random coils during aging. To overcome these obstacles and using the similarities between sub-1 nm nanowires (NWs) and linear polymers, we successfully fabricated anisotropic, transparent, flexible, and stable (ATFS) NW films with great potential for optical applications through a wet-spinning method. The NW films show birefringence, and their birefractive index is higher than that of many polymers. They also showed polarized absorption of UV light and anisotropic scattering of visible light. The integrated films composed of NWs and quantum dots showed good fluorescence polarization. The tedious synthesis of quantum rods and fabrication of oriented polymer films can thus be avoided.

Efficient Carrier Multiplication in Colloidal Silicon Nanorods.

Auger recombination lifetimes, absorption cross sections, and the quantum yields of carrier multiplication (CM), or multiexciton generation (MEG), were determined for solvent-dispersed silicon (Si) nanorods using transient absorption spectroscopy (TAS). Nanorods with an average diameter of 7.5 nm and aspect ratios of 6.1, 19.3, and 33.2 were examined. Colloidal Si nanocrystals of similar diameters were also studied for comparison. The nanocrystals and nanorods were passivated with organic ligands by hydrosilylation to prevent surface oxidation and limit the effects of surface trapping of photoexcited carriers. All samples used in the study exhibited relatively efficient photoluminescence. The Auger lifetimes increased with nanorod length, and the nanorods exhibited higher CM quantum yield and efficiency than the nanocrystals with a similar band gap energy Eg. Beyond a critical length, the CM quantum yield decreases. Nanorods with the aspect ratio of 19.3 had the highest CM quantum yield of 1.6 ± 0.2 at 2.9Eg, which corresponded to a multiexciton yield that was twice as high as observed for the spherical nanocrystals.

Silicon-Based Dielectric Metamaterials: Focus on the Current Synthetic Challenges.

Metamaterials have optical properties that are unprecedented in nature. They have opened new horizons in light manipulation, with the ability to bend, focus, completely reflect, transmit, or absorb an incident wave front. Optically active metamaterials in particular could be used for applications ranging from 3D information storage to photovoltaic cells. Silicon (Si) particles are some of the most promising building blocks for optically active metamaterials, with high scattering efficiency coupled to low light absorption for visible frequencies. However, to date ideal Si building blocks cannot be produced by bulk synthesis techniques. The key is to find a synthetic route to produce Si building blocks between 75-200 nm in diameter of uniform size and shape, that are crystalline, have few impurities, and little to no porosity. This Review provides a theoretical background on Si optical properties for metamaterials, an overview of current synthetic methods and gives direction towards the most promising routes to ideal Si particles for metamaterials.

Highly Fluorescent Silicon Nanocrystals Stabilized in Water Using Quatsomes.

Fluorescent silicon (Si) nanocrystals (2.8 nm diameter) were incorporated into surfactant assemblies of cetyltrimethylammonium bromide (CTAB) and cholesterol, called quatsomes. In water, the quatsome-Si nanocrystal assemblies remain fluorescent and well-dispersed for weeks. In contrast to Si nanocrystals, alkanethiol-capped gold (Au) nanocrystals do not form stable dispersions in water with quatsomes. Cryogenic transmission electron microscopy (cryo-TEM) confirmed that the Si nanocrystal-quatsome structures do not change over the course of several weeks. The long-term stability of the Si nanocrystal-quatsome assemblies, their fluorescence, and biocompatibility makes them attractive candidates for medical applications.

Silicon Nanocrystal Superlattice Nucleation and Growth.

Colloidal dodecene-passivated silicon (Si) nanocrystals were dispersed in hexane or chloroform and deposited onto substrates as face-centered cubic superlattices by slowly evaporating the solvent. The uniformity of the nanocrystals enables extended order; however, the solvent and the evaporation protocol significantly influence the self-assembly process, determining the morphology of the films, the extent of order, and the superlattice orientation on the substrate. Chloroform yielded superlattices with step-flow growth morphologies and (111)SL, (100)SL, and (110)SL orientations. Hexane led to mostly island morphologies when evaporated at room temperature with exclusively (111)SL orientations. Higher evaporation temperatures led to more extensive step-flow deposition. A model for the surface diffusion of nanocrystals adsorbed on the superlattice surface is developed.

Orientationally Ordered Silicon Nanocrystal Cuboctahedra in Superlattices.

Uniform silicon nanocrystals were synthesized with cuboctahedral shape and passivated with 1-dodecene capping ligands. Transmission electron microscopy, electron diffraction, and grazing incidence wide-angle and small-angle X-ray scattering show that these soft cuboctahedra assemble into face-centered cubic superlattices with orientational order. The preferred nanocrystal orientation was found to depend on the orientation of the superlattices on the substrate, indicating that the interactions with the substrate and assembly kinetics can influence the orientation of faceted nanocrystals in superlattices.

Zero-bias photocurrents in highly-disordered networks of Ge and Si nanowires.

Semiconducting nanowire (NW) devices have garnered attention in self-powered electronic and optoelectronic applications. This work explores and exhibits, for the first time for visible light, clear evidence of the zero-biased optoelectronic switching in randomly dispersed Ge and Si NW networks. The test bench, on which the NWs were dispersed for optoelectronic characterization, was fabricated using a standard CMOS fabrication process, and utilized metal contacts with dissimilar work functions-Al and Ni. The randomly dispersed NWs respond to light by exhibiting substantial photocurrents and, most remarkably, demonstrate zero-bias photo-switching. The magnitude of the photocurrent is dependent on the NW material, as well as the channel length. The photocurrent in randomly dispersed GeNWs was found to be higher by orders of magnitude compared to SiNWs. In both of these material systems, when the length of the NWs was comparable to the channel length, the currents in sparse NW networks were found to be higher than those in dense NW networks, which can be explained by considering various possible arrangements of NWs in these devices.

Controlled Styrene Monolayer Capping of Silicon Nanocrystals by Room Temperature Hydrosilylation.

Undecanoic acid facilitates attachment of styrene to hydride-terminated Si nanocrystals at room temperature, avoiding polymerization of styrene, yielding free-standing styrene-terminated Si nanocrystals. The nanocrystals have diamond cubic crystal structure, with photophysical properties similar to typical alkene-capped Si nanocrystals, such as bright photoluminescence with relatively long radiative lifetimes. We propose a reaction mechanism for room temperature styrene addition in which the resonance form of undecanoic acid coordinates to surface Si-H and facilitates H(-) attack at terminal C═C of styrene.

Synthesis and Ligand Exchange of Thiol-Capped Silicon Nanocrystals.

Hydride-terminated silicon (Si) nanocrystals were capped with dodecanethiol by a thermally promoted thiolation reaction. Under an inert atmosphere, the thiol-capped nanocrystals exhibit photoluminescence (PL) properties similar to those of alkene-capped Si nanocrystals, including size-tunable emission wavelength, relatively high quantum yields (>10%), and long radiative lifetimes (26-280 µs). X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy confirmed that the ligands attach to the nanocrystal surface via covalent Si-S bonds. The thiol-capping layer, however, readily undergoes hydrolysis and severe degradation in the presence of moisture. Dodecanethiol could be exchanged with dodecene by hydrosilylation for enhanced stability.

Role of Halides in the Ordered Structure Transitions of Heated Gold Nanocrystal Superlattices.

Dodecanethiol-capped gold (Au) nanocrystal superlattices can undergo a surprisingly diverse series of ordered structure transitions when heated (Goodfellow, B. W.; Rasch, M. R.; Hessel, C. M.; Patel, R. N.; Smilgies, D.-M.; Korgel, B. A. Nano Lett. 2013, 13, 5710-5714). These are the result of highly uniform changes in nanocrystal size, which subsequently force a spontaneous rearrangement of superlattice structure. Here, we show that halide-containing surfactants play an essential role in these transitions. In the absence of any halide-containing surfactant, superlattices of dodecanethiol-capped (1.9-nm-diameter) Au nanocrystals do not change size until reaching about 190-205 °C, at which point the gold cores coalesce. In the presence of halide-containing surfactant, such as tetraoctylphosphonium bromide (TOPB) or tetraoctylammounium bromide (TOAB), the nanocrystals ripen at much lower temperature and superlattices undergo various ordered structure transitions upon heating. Chloride- and iodide-containing surfactants induce similar behavior, destabilizing the Au-thiol bond and reducing the thermal stability of the nanocrystals.

Light-harvesting antennae based on photoactive silicon nanocrystals functionalized with porphyrin chromophores.

Silicon nanocrystals functionalized with tetraphenylporphyrin Zn(II) chromophores at the periphery perform as light harvesting antennae: excitation of the porphyrin units in the visible spectral region yields sensitized emission of the silicon nanocrystal core in the near infrared with a long lifetime (λ(max) = 905 nm, τ = 130 µs). This result demonstrates that this hybrid material has a potential application as a luminescent probe for bioimaging.