A Single-Step Bottom-up Approach for Synthesis of Highly Uniform Mie-Resonant Crystalline Semiconductor Particles at Visible Wavelengths.

Optically Mie-resonant crystalline silicon nanoparticles have long attracted interest for their unique scattering behaviors. Here, we report a bottom-up nonthermal plasma process that produces highly monodisperse particles, with diameters controllable between 60 and 214 nm, by temporarily electrostatically trapping nanoparticles inside a continuous-flow plasma reactor. The particle size is tuned by adjusting the gas residence time in the reactor. By dispersing the nanoparticles in water, optical extinction measurements indicate colloidal solutions of a particle-based metafluid in which particles support both strong magnetic and electric dipole resonances at visible wavelengths. The spectral overlap of the electric and magnetic resonances gives rise to directional Kerker scattering. The extinction measurements show excellent agreement with Mie theory, supporting the idea that the fabrication process enables particles with narrow distributions in size, shape, and composition. This single-step gas-phase process can also produce Mie-resonant nanoparticles of dielectric materials other than silicon and directly deposit them on the desired substrates.

Capacitively coupled nonthermal plasma synthesis of aluminum nanocrystals for enhanced yield and size control.

Uniform-size, non-native oxide-passivated metallic aluminum nanoparticles (Al NPs) have desirable properties for fuel applications, battery components, plasmonics, and hydrogen catalysis. Nonthermal plasma-assisted synthesis of Al NPs was previously achieved with an inductively coupled plasma (ICP) reactor, but the low production rate and limited tunability of particle size were key barriers to the applications of this material. This work focuses on the application of capacitively coupled plasma (CCP) to achieve improved control over Al NP size and a ten-fold increase in yield. In contrast with many other materials, where NP size is controlled via the gas residence time in the reactor, the Al NP size appeared to depend on the power input to the CCP system. The results indicate that the CCP reactor assembly, with a hydrogen-rich argon/hydrogen plasma, was able to produce Al NPs with diameters that were tunable between 8 and 21 nm at a rate up ∼ 100 mg h-1. X-ray diffraction indicates that a hydrogen-rich environment results in crystalline metal Al particles. The improved synthesis control of the CCP system compared to the ICP system is interpreted in terms of the CCP's lower plasma density, as determined by double Langmuir probe measurements, leading to reduced NP heating in the CCP that is more amenable to NP nucleation and growth.

Distance-dependent resonance energy transfer in alkyl-terminated Si nanocrystal solids.

Understanding and controlling the energy transfer between silicon nanocrystals is of significant importance for the design of efficient optoelectronic devices. However, previous studies on silicon nanocrystal energy transfer were limited because of the strict requirements to precisely control the inter-dot distance and to perform all measurements in air-free environments to preclude the effect of ambient oxygen. Here, we systematically investigate the distance-dependent resonance energy transfer in alkyl-terminated silicon nanocrystals for the first time. Silicon nanocrystal solids with inter-dot distances varying from 3 to 5 nm are fabricated by varying the length and surface coverage of alkyl ligands in solution-phase and gas-phase functionalized silicon nanocrystals. The inter-dot energy transfer rates are extracted from steady-state and time-resolved photoluminescence measurements, enabling a direct comparison to theoretical predictions. Our results reveal that the distance-dependent energy transfer rates in Si NCs decay faster than predicted by the Förster mechanism, suggesting higher-order multipole interactions.

Inductively coupled nonthermal plasma synthesis of aluminum nanoparticles.

Metallic nanoparticles of aluminum (Al), a nontoxic and earth-abundant element, are relevant to plasmonic and energetic applications. However, monodisperse Al nanoparticles are difficult to synthesize using all gas-phase approaches, especially in the 10 to 20 nm size range; yet, many applications require particles of this size due to their enhanced properties. Here, an inductive nonthermal plasma reactor fed with aluminum trichloride (AlCl3) and Ar is used to synthesize single-crystal aluminum nanoparticles. The particles can be produced with or without hydrogen. Several reactor conditions such as AlCl3vapor concentration, flow rates, and power are found to strongly influence particle properties such as the oxide shell thickness, particle mono-dispersity, and particle size. Significant quantities of Ar relative to AlCl3, short residence times of 10 s of ms, and pressures in excess of 4.7 Torr are required to form Al particles with geometric mean sizes of 10-20 nm and geometric standard deviations as low as 1.3. While the Al nanoparticles are covered with 2-4 nm thick oxide shells, the best synthesis conditions yield particle sizes determined by electron microscopy that are comparable to crystallite sizes determined from x-ray diffraction.

Probing Dopant Locations in Silicon Nanocrystals via High Energy X-ray Diffraction and Reverse Monte Carlo Simulation.

Understanding the locations of dopant atoms in ensembles of nanocrystals is crucial to controlling the dopants' function. While electron microscopy and atom probe tomography methods allow investigation of dopant location for small numbers of nanocrystals, assessing large ensembles has remained a challenge. Here, we are using high energy X-ray diffraction (HE-XRD) and structure reconstruction via reverse Monte Carlo simulation to characterize nanocrystal structure and dopant locations in ensembles of highly boron and phosphorus doped silicon nanocrystals (Si NCs). These plasma-synthesized NCs are a particularly intriguing test system for such an investigation, as elemental analysis suggests that Si NCs can be "hyperdoped" beyond the thermodynamic solubility limit in bulk silicon. Yet, free carrier densities derived from local surface plasmon resonances suggest that only a fraction of dopants are active. We demonstrate that the structural characteristics garnered from HE-XRD and structure reconstruction elucidate dopant location and doping efficacy for doped Si NCs from an atomic-scale perspective.

Synthesis of PEG-grafted boron doped Si nanocrystals.

Silicon nanocrystals are intriguing materials for biomedical imaging applications because of their unique optical properties and biological compatibility. We report a new surface functionalization route to synthesize biological buffer soluble and colloidally stable silicon nanocrystals, which is enabled by surface boron doping. Harnessing the distinctive Lewis acidic boron surface sites, postsynthetic modifications of plasma synthesized boron doped nanocrystals were carried out with polyethylene glycol (PEG-OH) ligands in dimethyl sulfoxide under photochemical conditions. The influence of PEG concentration, PEG molecular weight, and boron doping percentage on the nanocrystal solubility in a biological buffer has been investigated. The boron doping facilitates the surface functionalization via two probable pathways, by providing excellent initial dispersiblity in polar solvents and providing available acidic boron surface sites for bonding. These boron doped silicon nanocrystals have nearly identical absorption features as intrinsic silicon nanocrystals, indicating that they are promising candidates for biological imaging applications.

Thermodynamic Driving Force in the Spontaneous Formation of Inorganic Nanoparticle Solutions.

Nanoparticles are the bridge between the molecular and the macroscopic worlds. The growing number of commercial applications for nanoparticles spans from consumer products to new frontiers of medicine and next-generation optoelectronic technology. They are most commonly deployed in the form of a colloid, or "ink", which are formulated with solvents, surfactants, and electrolytes to kinetically prevent the solid particulate phase from reaching the thermodynamically favored state of separate solid and liquid phases. In this work, we theoretically determine the thermodynamic requirements for forming a single-phase solution of spherical particles and engineer a model system to experimentally demonstrate the spontaneous formation of solutions composed of only solvent and bare inorganic nanoparticles. We show molecular interactions at the nanoparticle interface are the driving force in high-concentration nanoparticle solutions. The work establishes a regime where inorganic nanoparticles behave as molecular solutes as opposed to kinetically stable colloids, which has far-reaching implications for the future design and deployment of nanomaterial technologies.

Tuning Nanocrystal Surface Depletion by Controlling Dopant Distribution as a Route Toward Enhanced Film Conductivity.

Electron conduction through bare metal oxide nanocrystal (NC) films is hindered by surface depletion regions resulting from the presence of surface states. We control the radial dopant distribution in tin-doped indium oxide (ITO) NCs as a means to manipulate the NC depletion width. We find in films of ITO NCs of equal overall dopant concentration that those with dopant-enriched surfaces show decreased depletion width and increased conductivity. Variable temperature conductivity data show electron localization length increases and associated depletion width decreases monotonically with increased density of dopants near the NC surface. We calculate band profiles for NCs of differing radial dopant distributions and in agreement with variable temperature conductivity fits find NCs with dopant-enriched surfaces have narrower depletion widths and longer localization lengths than those with dopant-enriched cores. Following amelioration of NC surface depletion by atomic layer deposition of alumina, all films of equal overall dopant concentration have similar conductivity. Variable temperature conductivity measurements on alumina-capped films indicate all films behave as granular metals. Herein, we conclude that dopant-enriched surfaces decrease the near-surface depletion region, which directly increases the electron localization length and conductivity of NC films.

Variable range hopping conduction in ZnO nanocrystal thin films.

Zinc oxide (ZnO) nanocrystal films are of interest for new applications in thin film transistors and as transparent conductive oxides. Previous work has concentrated on achieving highly conductive, metallic films. This work focusses on the less explored insulating to semi-insulating regime, which enables obtaining deeper insights into the roles of surface states and defect states trapped at the nanocrystal interfaces. We examine the effects of various post-deposition treatments including controlled dosing with ultraviolet light, filling the voids between nanocrystals with a matrix material deposited by atomic layer deposition, and thermal annealing of the nanocrystal films. Both Mott and Efros-Shklovskii variable range hopping are observed depending on the carrier concentration in the nanocrystals. Using the above post-treatments to transition the films between the two conduction mechanisms enables determining the Fermi level density of states and the electron localization length. To interpret our results, we propose a model based on the assumption of nanocrystals consisting of quasi-neutral cores surrounded by shells depleted by surface OH trap states. The model suggests that the primary source of the increased conductivity in ZnO nanocrystal films based on post-treatments is an increase in the ability to tunnel between nanocrystals due to a reduction of the distance between the quasi-neutral nanocrystal cores.

Nonthermal Plasma Synthesis of Nanocrystals: Fundamental Principles, Materials, and Applications.

Nonthermal plasmas have emerged as a viable synthesis technique for nanocrystal materials. Inherently solvent and ligand-free, nonthermal plasmas offer the ability to synthesize high purity nanocrystals of materials that require high synthesis temperatures. The nonequilibrium environment in nonthermal plasmas has a number of attractive attributes: energetic surface reactions selectively heat the nanoparticles to temperatures that can strongly exceed the gas temperature; charging of nanoparticles through plasma electrons reduces or eliminates nanoparticle agglomeration; and the large difference between the chemical potentials of the gaseous growth species and the species bound to the nanoparticle surfaces facilitates nanocrystal doping. This paper reviews the state of the art in nonthermal plasma synthesis of nanocrystals. It discusses the fundamentals of nanocrystal formation in plasmas, reviews practical implementations of plasma reactors, surveys the materials that have been produced with nonthermal plasmas and surface chemistries that have been developed, and provides an overview of applications of plasma-synthesized nanocrystals.

Ultrafast Silicon Photonics with Visible to Mid-Infrared Pumping of Silicon Nanocrystals.

Dynamic optical control of infrared (IR) transparency and refractive index is achieved using boron-doped silicon nanocrystals excited with mid-IR optical pulses. Unlike previous silicon-based optical switches, large changes in transmittance are achieved without a fabricated structure by exploiting strong light coupling of the localized surface plasmon resonance (LSPR) produced from free holes of p-type silicon nanocrystals. The choice of optical excitation wavelength allows for selectivity between hole heating and carrier generation through intraband or interband photoexcitation, respectively. Mid-IR optical pumping heats the free holes of p-Si nanocrystals to effective temperatures greater than 3500 K. Increases of the hole effective mass at high effective hole temperatures lead to a subpicosecond change of the dielectric function, resulting in a redshift of the LSPR, modulating mid-IR transmission by as much as 27%, and increasing the index of refraction by more than 0.1 in the mid-IR. Low hole heat capacity dictates subpicosecond hole cooling, substantially faster than carrier recombination, and negligible heating of the Si lattice, permitting mid-IR optical switching at terahertz repetition frequencies. Further, the energetic distribution of holes at high effective temperatures partially reverses the Burstein-Moss effect, permitting the modulation of transmittance at telecommunications wavelengths. The results presented here show that doped silicon, particularly in micro- or nanostructures, is a promising dynamic metamaterial for ultrafast IR photonics.

ZnO Nanocrystal Networks Near the Insulator-Metal Transition: Tuning Contact Radius and Electron Density with Intense Pulsed Light.

Networks of ligand-free semiconductor nanocrystals (NCs) offer a valuable combination of high carrier mobility and optoelectronic properties tunable via quantum confinement. In principle, maximizing carrier mobility entails crossing the insulator-metal transition (IMT), where carriers become delocalized. A recent theoretical study predicted that this transition occurs at nρ3 ≈ 0.3, where n is the carrier density and ρ is the interparticle contact radius. In this work, we satisfy this criterion in networks of plasma-synthesized ZnO NCs by using intense pulsed light (IPL) annealing to tune n and ρ independently. IPL applied to as-deposited NCs increases ρ by inducing sintering, and IPL applied after the NCs are coated with Al2O3 by atomic layer deposition increases n by removing electron-trapping surface hydroxyls. This procedure does not substantially alter NC size or composition and is potentially applicable to a wide variety of nanomaterials. As we increase nρ3 to at least twice the predicted critical value, we observe conductivity scaling consistent with arrival at the critical region of a continuous quantum phase transition. This allows us to determine the critical behavior of the dielectric constant and electron localization length at the IMT. However, our samples remain on the insulating side of the critical region, which suggests that the critical value of nρ3 may in fact be significantly higher than 0.3.

Metal-insulator transition in films of doped semiconductor nanocrystals.

To fully deploy the potential of semiconductor nanocrystal films as low-cost electronic materials, a better understanding of the amount of dopants required to make their conductivity metallic is needed. In bulk semiconductors, the critical concentration of electrons at the metal-insulator transition is described by the Mott criterion. Here, we theoretically derive the critical concentration nc for films of heavily doped nanocrystals devoid of ligands at their surface and in direct contact with each other. In the accompanying experiments, we investigate the conduction mechanism in films of phosphorus-doped, ligand-free silicon nanocrystals. At the largest electron concentration achieved in our samples, which is half the predicted nc, we find that the localization length of hopping electrons is close to three times the nanocrystals diameter, indicating that the film approaches the metal-insulator transition.

Broadband Absorbing Exciton-Plasmon Metafluids with Narrow Transparency Windows.

Optical metafluids that consist of colloidal solutions of plasmonic and/or excitonic nanomaterials may play important roles as functional working fluids or as means for producing solid metamaterial coatings. The concept of a metafluid employed here is based on the picture that a single ballistic photon, propagating through the metafluid, interacts with a large collection of specifically designed optically active nanocrystals. We demonstrate water-based metafluids that act as broadband electromagnetic absorbers in a spectral range of 200-3300 nm and feature a tunable narrow (∼100 nm) transparency window in the visible-to-near-infrared region. To define this transparency window, we employ plasmonic gold nanorods. We utilize excitonic boron-doped silicon nanocrystals as opaque optical absorbers ("optical wall") in the UV and blue-green range of the spectrum. Water itself acts as an opaque "wall" in the near-infrared to infrared. We explore the limits of the concept of a "simple" metafluid by computationally testing and validating the effective medium approach based on the Beer-Lambert law. According to our simulations and experiments, particle aggregation and the associated decay of the window effect are one example of the failure of the simple metafluid concept due to strong interparticle interactions.

Influence of the surface termination on the light emission of crystalline silicon nanoparticles.

The light emission properties of silicon crystalline nanoparticles (SiNPs) have been investigated using steady-state and time-resolved photoluminescence measurements carried out at 12 K and at room temperature. To enable a comparative study of the role of surface terminal groups on the optical properties, we investigated SiNPs-H ensembles with the same mean NP diameter but differing on the surface termination, namely organic-functionalized with 1-dodecene (SiNPs-C12) and H-terminated (SiNPs-H). We show that although the spectral dependence of the light emission is rather unaffected by surface termination, characterized by a single broad band peaking at ∼1.64 eV, both the exciton recombination lifetimes and quantum yields display a pronounced dependence on the surface termination. Exciton lifetimes and quantum yields are found to be significantly lower in SiNPs-H compared SiNPs-C12. This difference is due to distinct non-radiative recombination probabilities resulting from inter-NP exciton migration, which in SiNPs-C12 is inhibited by the energy barriers imposed by the bulky surface groups. The surface groups of organic-terminated SiPs are responsible for the inhibition of inter-NP exciton transfer, yielding a higher quantum yield compared to SiNPs-H. The surface oxidation of SiNPs-C12 leads to the appearance of a phenomenon of an exciton transference from to the Si core to oxide-related states that contribute to light emission. These excitons recombine radiatively, explaining why the emission quantum of the organic-terminated SiNPs is the same after surface oxidation of SiNPs-C12.

Plasmonic Properties of Silicon Nanocrystals Doped with Boron and Phosphorus.

Degenerately doped silicon nanocrystals are appealing plasmonic materials due to silicon's low cost and low toxicity. While surface plasmonic resonances of boron-doped and phosphorus-doped silicon nanocrystals were recently observed, there currently is poor understanding of the effect of surface conditions on their plasmonic behavior. Here, we demonstrate that phosphorus-doped silicon nanocrystals exhibit a plasmon resonance immediately after their synthesis but may lose their plasmonic response with oxidation. In contrast, boron-doped nanocrystals initially do not exhibit plasmonic response but become plasmonically active through postsynthesis oxidation or annealing. We interpret these results in terms of substitutional doping being the dominant doping mechanism for phosphorus-doped silicon nanocrystals, with oxidation-induced defects trapping free electrons. The behavior of boron-doped silicon nanocrystals is more consistent with a strong contribution of surface doping. Importantly, boron-doped silicon nanocrystals exhibit air-stable plasmonic behavior over periods of more than a year.

Nonequilibrium-Plasma-Synthesized ZnO Nanocrystals with Plasmon Resonance Tunable via Al Doping and Quantum Confinement.

Metal oxide semiconductor nanocrystals (NCs) exhibit localized surface plasmon resonances (LSPRs) tunable within the infrared (IR) region of the electromagnetic spectrum by vacancy or impurity doping. Although a variety of these NCs have been produced using colloidal synthesis methods, incorporation and activation of dopants in the liquid phase has often been challenging. Herein, using Al-doped ZnO (AZO) NCs as an example, we demonstrate the potential of nonthermal plasma synthesis as an alternative strategy for the production of doped metal oxide NCs. Exploiting unique, thoroughly nonequilibrium synthesis conditions, we obtain NCs in which dopants are not segregated to the NC surfaces and local doping levels are high near the NC centers. Thus, we achieve overall doping levels as high as 2 × 10(20) cm(-3) in NCs with diameters ranging from 12.6 to 3.6 nm, and for the first time experimentally demonstrate a clear quantum confinement blue shift of the LSPR energy in vacancy- and impurity-doped semiconductor NCs. We propose that doping of central cores and heavy doping of small NCs are achievable via nonthermal plasma synthesis, because chemical potential differences between dopant and host atoms-which hinder dopant incorporation in colloidal synthesis-are irrelevant when NC nucleation and growth proceed via irreversible interactions among highly reactive gas-phase ions and radicals and ligand-free NC surfaces. We explore how the distinctive nucleation and growth kinetics occurring in the plasma influences dopant distribution and activation, defect structure, and impurity phase formation.

Phase separation and the 'coffee-ring' effect in polymer-nanocrystal mixtures.

The coupling between the 'coffee-ring' effect and liquid-liquid phase separation is examined for ternary mixtures of solvent, polymer and semiconductor nanocrystal. Specifically, we study mixtures of toluene, polystyrene (PS) and colloidal silicon nanocrystals (SiNCs) using real-space imaging and spectroscopic techniques to resolve the kinetic morphology of the drying front for varied molecular weight of the PS. Our results demonstrate that the size of the polymer has a significant impact on both phase-separation and drying, and we relate these observations to simulations, measured and predicted binodal curves, and the observed shape of the flow field at the contact line. The results inform a deposition process that reduces the influence of drying instabilities for low-molecular-weight polymers while paving the way for more detailed and generic computational descriptions of drying instabilities in complex fluids.

Phosphorus-doped silicon nanocrystals exhibiting mid-infrared localized surface plasmon resonance.

Localized surface plasmon resonances (LSPRs) enable tailoring of the optical response of nanomaterials through their free carrier concentration, morphology, and dielectric environment. Recent efforts to expand the spectral range of usable LSPR frequencies into the infrared successfully demonstrated LSPRs in doped semiconductor nanocrystals. Despite silicon's importance for electronic and photonic applications, no LSPRs have been reported for doped silicon nanocrystals. Here we demonstrate doped silicon nanocrystals synthesized via a nonthermal plasma technique that exhibits tunable LSPRs in the energy range of 0.07-0.3 eV or mid-infrared wavenumbers of 600-2500 cm(-1).