Single Particle Emission Research Articles

Cathodoluminescent and Characteristic X-Ray-Emissive Rare-Earth-Doped Core/Shell Protein Labels for Spectromicroscopic Analysis of Cell Surface Receptors.

Understanding the localization and the interactions of biomolecules at the nanoscale and in the cellular context remains challenging. Electron microscopy (EM), unlike light-based microscopy, gives access to the cellular ultrastructure yet results in grey-scale images and averts unambiguous (co-)localization of biomolecules. Multimodal nanoparticle-based protein labels for correlative cathodoluminescence electron microscopy (CCLEM) and energy-dispersive X-ray spectromicroscopy (EDX-SM) are presented. The single-particle STEM-cathodoluminescence (CL) and characteristic X-ray emissivity of sub-20 nm lanthanide-doped nanoparticles are exploited as unique spectral fingerprints for precise label localization and identification. To maximize the nanoparticle brightness, lanthanides are incorporated in a low-phonon host lattice and separated from the environment using a passivating shell. The core/shell nanoparticles are then functionalized with either folic (terbium-doped) or caffeic acid (europium-doped). Their potential for (protein-)labeling is successfully demonstrated using HeLa cells expressing different surface receptors that bind to folic or caffeic acid, respectively. Both particle populations show single-particle CL emission along with a distinctive energy-dispersive X-ray signal, with the latter enabling color-based localization of receptors within swift imaging times well below 2 min per 2 while offering high resolution with a pixel size of 2.78 nm. Taken together, these results open a route to multi-color labeling based on electronspectromicroscopy.

Expanding the Palette of SWIR Emitting Nanoparticles Based on Au Nanoclusters for Single-Particle Tracking Microscopy.

Single-molecule localization microscopy has proved promising to unravel the dynamics and molecular architecture of thin biological samples down to nanoscales. For applications in complex, thick biological tissues shifting single-particle emission wavelengths to the shortwave infrared (SWIR also called NIR II) region between 900 to 2100nm, where biological tissues are more transparent is key. To date, mainly single-walled carbon nanotubes (SWCNTs) enable such applications, but they are inherently 1D objects. Here, 0D ultra-small luminescent gold nanoclusters (AuNCs, <3nm) and ≈25nm AuNC-loaded-polymeric particles that can be detected at the single-particle level in the SWIR are presented. Thanks to high brightness and excellent photostability, it is shown that the dynamics of the spherical polymeric particles can be followed at the single-particle level in solution at video rates for minutes. We compared single particle tracking of AuNC-loaded-polymeric particles with that of SWCNT diffusing in agarose gels demonstrating the specificity and complementarity of diffusion properties of these SWIR-emitting nano-objects when exploring a complex environment. This extends the library of photostable SWIR emitting nanomaterials to 0D nano-objects of variable size for single-molecule localization microscopy in the second biological window, opening unprecedented possibilities for mapping the structure and dynamics of complex biological systems.

A composite electrodynamic mechanism to reconcile spatiotemporally resolved exciton transport in quantum dot superlattices.

Quantum dot (QD) solids are promising optoelectronic materials; further advancing their device functionality requires understanding their energy transport mechanisms. The commonly invoked near-field Förster resonance energy transfer (FRET) theory often underestimates the exciton hopping rate in QD solids, yet no consensus exists on the underlying cause. In response, we use time-resolved ultrafast stimulated emission depletion (STED) microscopy, an ultrafast transformation of STED to spatiotemporally resolve exciton diffusion in tellurium-doped cadmium selenide-core/cadmium sulfide-shell QD superlattices. We measure the concomitant time-resolved exciton energy decay due to excitons sampling a heterogeneous energetic landscape within the superlattice. The heterogeneity is quantified by single-particle emission spectroscopy. This powerful multimodal set of observables provides sufficient constraints on a kinetic Monte Carlo simulation of exciton transport to elucidate a composite transport mechanism that includes both near-field FRET and previously neglected far-field emission/reabsorption contributions. Uncovering this mechanism offers a much-needed unified framework in which to characterize transport in QD solids and additional principles for device design.

High-Throughput Characterization of Single-Quantum-Dot Emission Spectra and Spectral Diffusion by Multiparticle Spectroscopy

In recent years, quantum dots (QDs) have emerged as bright, color-tunable light sources for various applications such as light-emitting devices, lasing, and bioimaging. One important next step to advance their applicability is to reduce particle-to-particle variations of the emission properties as well as fluctuations of a single QD’s emission spectrum, also known as spectral diffusion (SD). Characterizing SD is typically inefficient as it requires time-consuming measurements at the single-particle level. Here, however, we demonstrate multiparticle spectroscopy (MPS) as a high-throughput method to acquire statistically relevant information about both fluctuations at the single-particle level and variations at the level of a synthesis batch. In MPS, we simultaneously measure emission spectra of many (20–100) QDs with a high time resolution. We obtain statistics on single-particle emission line broadening for a batch of traditional CdSe-based core–shell QDs and a batch of the less toxic InP-based core–shell QDs. The CdSe-based QDs show significantly narrower homogeneous line widths, less SD, and less inhomogeneous broadening than the InP-based QDs. The time scales of SD are longer in the InP-based QDs than in the CdSe-based QDs. Based on the distributions and correlations in single-particle properties, we discuss the possible origins of line-width broadening of the two types of QDs. Our experiments pave the way to large-scale, high-throughput characterization of single-QD emission properties and will ultimately contribute to facilitating rational design of future QD structures.

Photon correlations in colloidal quantum dot molecules controlled by the neck barrier

<h2>Summary</h2> The charge redistribution upon optical excitation of various necked homodimer colloidal quantum dot molecules (CQDMs) is investigated using single-particle emission spectroscopy. By tuning the hybridization of the electron wavefunctions at a fixed center-to-center distance through controlling the neck girth, we reveal two coupling limits: on one hand, a "connected-but-confined" situation where neighboring CQDs are weakly fused to each other, manifesting a weak-coupling regime, and on the other hand, a "connected-and-delocalized" situation where the neck is filled beyond the facet size, leading to a rod-like architecture manifesting strong coupling. The interplay between the radiative and non-radiative Auger decays of these states turns emitted photons from the CQDMs in the weak-coupling regime highly bunched unlike CQD monomers, while the antibunching is regained at the strong-coupling regime. This work sets an analogy for the artificial molecule CQDMs with regular molecules, where the two distinct regimes of weak and strong coupling correspond to ionic- or covalent-type bonding, respectively.

α−Fe2O3 nanoparticles and hazardous air pollutants release during cooking using cast iron wok in a commercial Chinese restaurant

Long-term exposure to fine particles (PM2.5), ultrafine particles (UFPs), and volatile organic compounds (VOCs) emissions from cooking has been linked to adverse human health effects. Here, we measured the real-time number size distribution of particles emitted when cooking two served food in Chinese restaurants and estimated the emission rate of UFPs and PM2.5. Experiments were conducted under a control hood, and both online measurement and offline analysis of PM2.5 were carried out. The measured emission rates of PM2.5 generated from deep-frying and grilling were 0.68 ± 0.11 mg/min and 1.58 ± 0.25 mg/min, respectively. Moreover, the UFPs emission rate of deep-frying (4.3 × 109 #/min) is three times higher than that of grilling (1.4 × 109 #/min). Additionally, the PM2.5 emission of deep-frying was comprised of a considerable amount of α−Fe2O3 (5.7% of PM2.5 total mass), which is more toxic than other iron oxide species. A total of six carcinogenic HAPs were detected, among which formaldehyde, acrolein, and acetaldehyde were found to exceed the inhalation reference concentration (RfC) for both cooking methods. These findings can contribute to future evaluation of single particle and HAPs emission from cooking to better support toxicity assessment.

Emission of particles from a parametrically driven condensate in a one-dimensional lattice

Motivated by recent experiments, we calculate particle emission from a Bose-Einstein condensate trapped in a single deep well of a one-dimensional lattice when the interaction strength is modulated. In addition to pair emission, which has been widely studied, we observe single-particle emission. Within linear response, we are able to write closed-form expressions for the single-particle emission rates and reduce the pair emission rates to one-dimensional integrals. The full nonlinear theory of single-particle emission is reduced to a single variable integrodifferential equation, which we numerically solve.

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.

Space-time structure of the pion emission in central Au+Au collisions at RHIC energies

The spatial and temporal properties of pion emission in 0%–5% central Au+Au collisions at , 14.5 GeV, and 19.6 GeV were investigated using the UrQMD model. The three-dimensional femtoscopic radii, R out , R side , and R long , were extracted for several regions of pair transverse momentum. Times of maximum emission, , were extracted from the fit to R long with the assumptions of the absence and presence of the transverse flow and compared to each other. In addition, the was estimated directly from the single-particle emission function at kinetic freeze-out. The two methods provide consistent results at the considered energies.

Single and bi-excitonic characteristics of ligand-modified silicon nanoparticles as demonstrated via single particle photon statistics and plasmonic effects.

Silicon nanoparticles (Si NPs) are of great interest to researchers due to their fluorescence properties, low toxicity, and the low cost of the Si precursor. Recent studies have shown that Si NPs surface-modified with secondary aryl amine ligands emit light at wavelengths ranging from cyan to yellow and with quantum yields of up to 90%. The predominant emitting state in these species has been assigned to a charge-transfer (CT) transition from the ligand to the Si particle as the emission wavelength is determined by the dipolar properties of the ligand rather than the size of the Si core. This contribution focuses on the single-molecule emission properties of Si NPs functionalized with a 1,2,3,4-tetrahydrocarbazole-4-one ligand (Te-On) which have a peak emission wavelength of 550 nm and a quantum yield of 90%. In single-particle dispersed emission spectra, a weak long-wavelength sideband is seen in addition to the dominant yellow emission derived from the CT state. The photon statistical behavior of single Si NPs in the red emission region is consistent with that of a state having collective or bi-excitonic character. In contrast, the yellow emission exhibits predominantly CT character. Deposition of the sample onto a thin gold film causes the CT emission to be quenched whereas that attributed to a bi-exciton state of the Si core is enhanced. These results provide new insights into the mechanism of single-molecule intensity fluctuation in these surface-modified silicon nanoparticles that will benefit proposed applications in biological labeling and as single-photon sources.

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.

Dual-Mode Superresolution Imaging Using Charge Transfer Dynamics in Semiconducting Polymer Dots.

In a conjugated polymer-based single-particle heterojunction, stochastic fluctuations of the photogenerated hole population lead to spontaneous fluorescence switching. We found that 405 nm irradiation can induce charge recombination and activate the single-particle emission. Based on these phenomena, we developed a novel class of semiconducting polymer dots that can operate in two superresolution imaging modes. The spontaneous switching mode offers efficient imaging of large areas, with <10 nm localization precision, while the photoactivation/deactivation mode offers slower imaging, with further improved localization precision (ca. 1 nm), showing advantages in resolving small structures that require high spatial resolution. Superresolution imaging of microtubules and clathrin-coated pits was demonstrated, under both modes. The excellent localization precision and versatile imaging options provided by these nanoparticles offer clear advantages for imaging of various biological systems.

Minimal excitation single-particle emitters: Comparison of charge-transport and energy-transport properties

We investigate different types of time-dependently driven single-particle sources whose common feature is that they produce pulses of integer charge and minimally excite the Fermi sea. These sources are: a slowly driven mesoscopic capacitor, a Lorentzian-shaped time-dependent bias voltage, and a local gate-voltage modulation of a quantum Hall edge state. They differ by their specific driving protocols, e.g., they have a pure ac driving or a driving with a dc component. In addition, only in the first of these setups, strong confinement leading to a discrete energy spectrum of the conductor, is exploited for the single-particle emission. Here, we study if and how these basic differences impact transport properties. Specifically, we address time- and energy-resolved charge and energy currents, as well as their zero-frequency correlators (charge-, energy- and mixed noise), as they are frequently used to characterize experiments in quantum optics with electrons. Beyond disparities due to a different number and polarity of particles emitted per period, we in particular identify differences in the impact, which temperature has on the observables for sources with and without energy-dependent scattering properties. We trace back these characteristics to a small set of relevant parameter ratios.

Single Nanocrystal Spectroscopy of Shortwave Infrared Emitters.

Short-wave infrared (SWIR) emitters are at the center of ground-breaking applications in biomedical imaging, next-generation optoelectronic devices, and optical communications. Colloidal nanocrystals based on indium arsenide are some of the most promising SWIR emitters to date. However, the lack of single-particle spectroscopic methods accessible in the SWIR has prevented advances in both nanocrystal synthesis and fundamental characterization of emitters. Here, we demonstrate an implementation of a solution photon correlation Fourier spectroscopy (s-PCFS) experiment utilizing the SWIR sensitivity and time resolution of superconducting nanowire single-photon detectors to extract single-particle emission linewidths from colloidal indium arsenide/cadmium selenide (InAs/CdSe) core/shell nanocrystals emissive from 1.2 to 1.6 μm. We show that the average single InAs/CdSe nanocrystal fluorescence linewidth is, remarkably, as narrow as 52 meV, similar to what has been observed in some of the most narrowband nanostructured emitters in the visible region. Additionally, the single nanocrystal fluorescence linewidth increases with increasing shell thickness, suggesting exciton-phonon coupling as the dominant emission line-broadening mechanism in this system. The development of the SWIR s-PCFS technique has enabled measurements of spectral linewidths of colloidal SWIR-emissive NCs in solution and provides a platform to study the single NC spectral characteristics of SWIR emitters.

Chemical Structure, Ensemble and Single-Particle Spectroscopy of Thick-Shell InP-ZnSe Quantum Dots.

Thick-shell (>5 nm) InP-ZnSe colloidal quantum dots (QDs) grown by a continuous-injection shell growth process are reported. The growth of a thick crystalline shell is attributed to the high temperature of the growth process and the relatively low lattice mismatch between the InP core and ZnSe shell. In addition to a narrow ensemble photoluminescence (PL) line-width (∼40 nm), ensemble and single-particle emission dynamics measurements indicate that blinking and Auger recombination are reduced in these heterostructures. More specifically, high single-dot ON-times (>95%) were obtained for the core-shell QDs, and measured ensemble biexciton lifetimes, τ2x ∼ 540 ps, represent a 7-fold increase compared to InP-ZnS QDs. Further, high-resolution energy dispersive X-ray (EDX) chemical maps directly show for the first time significant incorporation of indium into the shell of the InP-ZnSe QDs. Examination of the atomic structure of the thick-shell QDs by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) reveals structural defects in subpopulations of particles that may mitigate PL efficiencies (∼40% in ensemble), providing insight toward further synthetic refinement. These InP-ZnSe heterostructures represent progress toward fully cadmium-free QDs with superior photophysical properties important in biological labeling and other emission-based technologies.

Single-particle emission at finite temperatures

The state of particles injected onto the surface of the Fermi sea depends essentially on the temperature. The pure state injected at zero temperature becomes a mixed state if injected at finite temperature. Moreover the electron source injecting a single-particle state at zero temperature may excite a multi-particle state if the Fermi sea is at finite temperature. Here I unveil a symmetry of the scattering amplitude of a source, which is sufficient to preserve a single-particle emission regime at finite temperatures if such a regime is achieved at zero temperature. I give an example and analyze the effect of temperature on time-dependent electrical and heat currents carried by a single-particle excitation.

Thick-Shell CuInS2/ZnS Quantum Dots with Suppressed "Blinking" and Narrow Single-Particle Emission Line Widths.

Quantum dots (QDs) of ternary I-III-VI2 compounds such as CuInS2 and CuInSe2 have been actively investigated as heavy-metal-free alternatives to cadmium- and lead-containing semiconductor nanomaterials. One serious limitation of these nanostructures, however, is a large photoluminescence (PL) line width (typically >300 meV), the origin of which is still not fully understood. It remains even unclear whether the observed broadening results from considerable sample heterogeneities (due, e.g., to size polydispersity) or is an unavoidable intrinsic property of individual QDs. Here, we answer this question by conducting single-particle measurements on a new type of CuInS2 (CIS) QDs with an especially thick ZnS shell. These QDs show a greatly enhanced photostability compared to core-only or thin-shell samples and, importantly, exhibit a strongly suppressed PL blinking at the single-dot level. Spectrally resolved measurements reveal that the single-dot, room-temperature PL line width is much narrower (down to ∼60 meV) than that of the ensemble samples. To explain this distinction, we invoke a model wherein PL from CIS QDs arises from radiative recombination of a delocalized band-edge electron and a localized hole residing on a Cu-related defect and also account for the effects of electron-hole Coulomb coupling. We show that random positioning of the emitting center in the QD can lead to more than 300 meV variation in the PL energy, which represents at least one of the reasons for large PL broadening of the ensemble samples. These results suggest that in addition to narrowing size dispersion, future efforts on tightening the emission spectra of these QDs might also attempt decreasing the "positional" heterogeneity of the emitting centers.

Colloidal lead halide perovskite nanocrystals: synthesis, optical properties and applications

Lead halide perovskite nanocrystals (NCs) are receiving a lot of attention nowadays, due to their exceptionally high photoluminescence quantum yields reaching almost 100% and tunability of their optical band gap over the entire visible spectral range by modifying composition or dimensionality/size. We review recent developments in the direct synthesis and ion exchange-based reactions, leading to hybrid organic–inorganic (CH3NH3PbX3) and all-inorganic (CsPbX3) lead halide (X=Cl, Br, I) perovskite NCs, and consider their optical properties related to quantum confinement effects, single emission spectroscopy and lasing. We summarize recent developments on perovskite NCs employed as an active material in several applications such as light-emitting devices, solar cells and photodetectors, and provide a critical outlook into the existing and future challenges. Although research into perovskite nanocrystals is still in its infancy, they are expected to be major players in future nanoscience. Lead halide perovskite nanocrystals are attracting much interest because their quantum yields for photoluminescence are approaching 100% and their optical band gap can be tuned over the entire visible wavelength region – properties that make them promising for use in lasers, light-emitting diodes (LEDs) and solar cells. Andrey Rogach of City University of Hong Kong and co-workers review the latest developments in the synthesis (of both hybrid organic-inorganic and all-inorganic nanocrystals), optical properties (quantum confinement effects, single particle emission and lasing studies) and applications (LEDs, solar cells and photodiodes) of these materials. They outline some of the many remaining challenges, but state their confidence that these should soon be overcome. This review summarizes recent developments in the direct synthesis and ion exchange-based reactions leading to hybrid organic–inorganic and all-inorganic lead halide perovskite nanocrystals. Optical properties related to quantum confinement effects, single emission spectroscopy and lasing are considered. Perovskite nanocrystals have been employed as an active material in several applications such as light-emitting devices, solar cells and photodetectors.

Single Particle and PET-based Platform for Identifying Optimal Plasmonic Nano-Heaters for Photothermal Cancer Therapy.

Plasmonic nanoparticle-based photothermal cancer therapy is a promising new tool to inflict localized and irreversible damage to tumor tissue by hyperthermia, without harming surrounding healthy tissue. We developed a single particle and positron emission tomography (PET)-based platform to quantitatively correlate the heat generation of plasmonic nanoparticles with their potential as cancer killing agents. In vitro, the heat generation and absorption cross-section of single irradiated nanoparticles were quantified using a temperature sensitive lipid-based assay and compared to their theoretically predicted photo-absorption. In vivo, the heat generation of irradiated nanoparticles was evaluated in human tumor xenografts in mice using 2-deoxy-2-[F-18]fluoro-D-glucose (18F-FDG) PET imaging. To validate the use of this platform, we quantified the photothermal efficiency of near infrared resonant silica-gold nanoshells (AuNSs) and benchmarked this against the heating of colloidal spherical, solid gold nanoparticles (AuNPs). As expected, both in vitro and in vivo the heat generation of the resonant AuNSs performed superior compared to the non-resonant AuNPs. Furthermore, the results showed that PET imaging could be reliably used to monitor early treatment response of photothermal treatment. This multidisciplinary approach provides a much needed platform to benchmark the emerging plethora of novel plasmonic nanoparticles for their potential for photothermal cancer therapy.

Deblurring Poisson noisy images by total variation with overlapping group sparsity

Deblurring Poisson noisy images has recently been subject of an increasingly amount of works in various applications such as astronomical imaging, fluorescent confocal microscopy imaging, single particle emission computed tomography (SPECT) and positron emission tomography (PET). Many works promote the introduction of an explicit prior on the solution to regularize the ill-posed inverse problem for improving the quality of the images. In this paper, we consider using the total variation with overlapping group sparsity as a prior information. The proposed method can avoid staircase effect and preserve edges in the restored images. After converting the proposed model to a constrained problem by variable splitting, we solve the corresponding problem with the alternating direction method of multipliers (ADMM). Numerical examples for deblurring Poisson noisy images are given to show that the proposed method outperforms some existing methods in terms of the signal-to-noise ratio, relative error and structural similarity index.