Room-Temperature Fiber-Coupled Single-Photon Sources based on Colloidal Quantum Dots and SiV Centers in Back-Excited Nanoantennas.

We demonstrate an important step toward on-chip integration of single-photon sources at room temperature. Excellent photon directionality is achieved with a hybrid metal-dielectric bullseye antenna, while back-excitation is permitted by placement of the emitter in a subwavelength hole positioned at its center. The unique design enables a direct back-excitation and very efficient front coupling of emission either to a low numerical aperture (NA) optics or directly to an optical fiber. To show the versatility of the concept, we fabricate devices containing either a colloidal quantum dot or a nanodiamond containing silicon-vacancy centers, which are accurately positioned using two different nanopositioning methods. Both of these back-excited devices display front collection efficiencies of ∼70% at NAs as low as 0.5. The combination of back-excitation with forward directionality enables direct coupling of the emitted photons into a proximal optical fiber without any coupling optics, thereby facilitating and simplifying future integration.

Nanoscale imaging of quantum dot dimers using time-resolved super-resolution microscopy combined with scanning electron microscopy.

Time-resolved super-resolution microscopy was used in conjunction with scanning electron microscopy to image individual colloidal CdSe/CdS semiconductor quantum dots (QD) and QD dimers. The photoluminescence (PL) lifetimes, intensities, and structural parameters were acquired with nanometer scale spatial resolution and sub-nanosecond time resolution. The combination of these two techniques was more powerful than either alone, enabling us to resolve the PL properties of individual QDs within QD dimers as they blinked on and off, measure interparticle distances, and identify QDs that may be participating in energy transfer. The localization precision of our optical imaging technique was ∼3 nm, low enough that the emission from individual QDs within the dimers could be spatially resolved. While the majority of QDs within dimers acted as independent emitters, at least one pair of QDs in our study exhibited lifetime and intensity behaviors consistent with resonance energy transfer from a shorter lifetime and lower intensity donor QD to a longer lifetime and higher intensity acceptor QD. For this case, we demonstrate how the combined super-resolution optical imaging and scanning electron microscopy data can be used to characterize the energy transfer rate.

Excited state lifetime modulation in semiconductor nanocrystals for super-resolution imaging.

We report on proof of principle measurements of a concept for a super-resolution imaging method that is based on excitation field density-dependent lifetime modulation of semiconductor nanocrystals. The prerequisite of the technique is access to semiconductor nanocrystals with emission lifetimes that depend on the excitation intensity. Experimentally, the method requires a confocal microscope with fluorescence-lifetime measurement capability that makes it easily accessible to a broad optical imaging community. We demonstrate with single particle imaging that the method allows one to achieve a spatial resolution of the order of several tens of nanometers at moderate fluorescence excitation intensity.

Interplay of Bright Triplet and Dark Excitons Revealed by Magneto-Photoluminescence of Individual PbS/CdS Quantum Dots.

A low-temperature polarization-resolved magneto-photoluminescence experiment is performed on individual PbS/CdS core/shell quantum dots (QDs). The experiment enables a direct measurement of the exciton Landé g factor and the anisotropic zero-field splitting of the lowest emissive bright exciton triplet in PbS/CdS QDs. While anisotropic splittings of individual QDs distribute randomly in 104-325 µeV range, the exciton Landé g factors increase from 0.95 to 2.70 as the emission energy of the QD increases from 1.0 to 1.2 eV. The tight-binding calculations allow to rationalize these trends as a direct consequence of reducing a cubic symmetry of QD via addition/removal of a few (<70) atoms from the surfaces of the PbS core. Furthermore, it is observed that while right (σ  + ) and left (σ  - ) circularly polarized photoluminescence (PL) peaks split linearly with magnetic field as expected for Zeeman effect, the energy splitting between X and Y linearly polarized PL peaks remains nearly unchanged. The theoretical study reveals rich and complex magnetic field-induced interplay of bright triplet and dark exciton states explaining this puzzling behavior. These findings fill the missing gaps in the understanding of lead salt QDs and provide foundation for development of classical and quantum light sources operating at telecommunication wavelengths.

Twist Angle-Dependent Interlayer Exciton Lifetimes in van der Waals Heterostructures.

In van der Waals (vdW) heterostructures formed by stacking two monolayers of transition metal dichalcogenides, multiple exciton resonances with highly tunable properties are formed and subject to both vertical and lateral confinement. We investigate how a unique control knob, the twist angle between the two monolayers, can be used to control the exciton dynamics. We observe that the interlayer exciton lifetimes in MoSe_{2}/WSe_{2} twisted bilayers (TBLs) change by one order of magnitude when the twist angle is varied from 1° to 3.5°. Using a low-energy continuum model, we theoretically separate two leading mechanisms that influence interlayer exciton radiative lifetimes. The shift to indirect transitions in the momentum space with an increasing twist angle and the energy modulation from the moiré potential both have a significant impact on interlayer exciton lifetimes. We further predict distinct temperature dependence of interlayer exciton lifetimes in TBLs with different twist angles, which is partially validated by experiments. While many recent studies have highlighted how the twist angle in a vdW TBL can be used to engineer the ground states and quantum phases due to many-body interaction, our studies explore its role in controlling the dynamics of optically excited states, thus, expanding the conceptual applications of "twistronics".

Role of shell composition and morphology in achieving single-emitter photostability for green-emitting "giant" quantum dots.

The use of the varied chemical reactivity of precursors to drive the production of a desired nanocrystal architecture has become a common method to grow thick-shell graded alloy quantum dots (QDs) with robust optical properties. Conclusions on their behavior assume the ideal chemical gradation and uniform particle composition. Here, advanced analytical electron microscopy (high-resolution scanning transmission electron microscopy coupled with energy dispersive spectroscopy) is used to confirm the nature and extent of compositional gradation and these data are compared with performance behavior obtained from single-nanocrystal spectroscopy to elucidate structure, chemical-composition, and optical-property correlations. Specifically, the evolution of the chemical structure and single-nanocrystal luminescence was determined for a time-series of graded-alloy "CdZnSSe/ZnS" core/shell QDs prepared in a single-pot reaction. In a separate step, thick (∼6 monolayers) to giant (>14 monolayers) shells of ZnS were added to the alloyed QDs via a successive ionic layer adsorption and reaction (SILAR) process, and the impact of this shell on the optical performance was also assessed. By determining the degree of alloying for each component element on a per-particle basis, we observe that the actual product from the single-pot reaction is less "graded" in Cd and more so in Se than anticipated, with Se extending throughout the structure. The latter suggests much slower Se reaction kinetics than expected or an ability of Se to diffuse away from the initially nucleated core. It was also found that the subsequent growth of thick phase-pure ZnS shells by the SILAR method was required to significantly reduce blinking and photobleaching. However, correlated single-nanocrystal optical characterization and electron microscopy further revealed that these beneficial properties are only achieved if the thick ZnS shell is complete and without large lattice discontinuities. In this way, we identify the necessary structural design features that are required for ideal light emission properties in these green-visible emitting QDs.

Intrinsic Exciton Photophysics of PbS Quantum Dots Revealed by Low-Temperature Single Nanocrystal Spectroscopy.

With a tunable size-dependent photoluminescence (PL) over a wide infrared wavelength range, lead chalcogenide quantum dots (QDs) have attracted significant scientific and technological interest. Nevertheless, the investigation of intrinsic exciton photophysics at the single-QD level has remained a challenge. Herein, we present a comprehensive study of PL properties for the individual core/shell PbS/CdS QDs emissive near 1.0 eV. In contrast to the sub-meV spectral line widths observed for II/VI QDs, PbS/CdS QDs are predicted to possess broad homogeneous line widths. Performing spectroscopy at cryogenic (4 K) temperatures, we provide direct evidence confirming theoretical predictions, showing that intrinsic line widths for PbS/CdS QDs are in the range of 8-25 meV, with an average of 16.4 meV. In addition, low-temperature, single-QD spectroscopy reveals a broad low-energy side emission attributable to optical as well as localized acoustic phonon-assisted transitions. By tracking single QDs from 4 to 250 K, we were able to probe temperature-dependent evolutions of emission energy, line width, and line shape. Finally, polarization-resolved PL imaging showed that PbS/CdS QDs are characterized by a 3D emission dipole, in contrast with the 2D dipole observed for CdSe QDs.

The Role of Liquid Ink Transport in the Direct Placement of Quantum Dot Emitters onto Sub-Micrometer Antennas by Dip-Pen Nanolithography.

Dip-pen nanolithography (DPN) is used to precisely position core/thick-shell ("giant") quantum dots (gQDs; ≥10 nm in diameter) exclusively on top of silicon nanodisk antennas (≈500 nm diameter pillars with a height of ≈200 nm), resulting in periodic arrays of hybrid nanostructures and demonstrating a facile integration strategy toward next-generation quantum light sources. A three-step reading-inking-writing approach is employed, where atomic force microscopy (AFM) images of the pre-patterned substrate topography are used as maps to direct accurate placement of nanocrystals. The DPN "ink" comprises gQDs suspended in a non-aqueous carrier solvent, o-dichlorobenzene. Systematic analyses of factors influencing deposition rate for this non-conventional DPN ink are described for flat substrates and used to establish the conditions required to achieve small (sub-500 nm) feature sizes, namely: dwell time, ink-substrate contact angle and ink volume. Finally, it is shown that the rate of solvent transport controls the feature size in which gQDs are found on the substrate, but also that the number and consistency of nanocrystals deposited depends on the stability of the gQD suspension. Overall, the results lay the groundwork for expanded use of nanocrystal liquid inks and DPN for fabrication of multi-component nanostructures that are challenging to create using traditional lithographic techniques.

Giant PbSe/CdSe/CdSe Quantum Dots: Crystal-Structure-Defined Ultrastable Near-Infrared Photoluminescence from Single Nanocrystals.

Toward a truly photostable PbSe quantum dot (QD), we apply the thick-shell or "giant" QD structural motif to this notoriously environmentally sensitive nanocrystal system. Namely, using a sequential application of two shell-growth techniques-partial-cation exchange and successive ionic layer adsorption and reaction (SILAR)-we are able to overcoat the PbSe QDs with sufficiently thick CdSe shells to impart new single-QD-level photostability, as evidenced by suppression of both photobleaching and blinking behavior. We further reveal that the crystal structure of the CdSe shell (cubic zinc-blende or hexagonal wurtzite) plays a key role in determining the photoluminescence properties of these giant QDs, with only cubic nanocrystals sufficiently bright and stable to be observed as single emitters. Moreover, we demonstrate that crystal structure and particle shape (cubic, spherical, or tetrapodal) and, thereby, emission properties can be synthetically tuned by either withholding or including the coordinating ligand, trioctylphosphine, in the SILAR component of the shell-growth process.

Photoluminescence Enhancement of CuInS2 Quantum Dots in Solution Coupled to Plasmonic Gold Nanocup Array.

A strong plasmonic enhancement of photoluminescence (PL) decay rate in quantum dots (QDs) coupled to an array of gold-coated nanocups is demonstrated. CuInS2 QDs that emit at a wavelength that overlaps with the extraordinary optical transmission (EOT) of the gold nanocup array are placed in the cups as solutions. Time-resolved PL reveals that the decay rate of the QDs in the plasmonically coupled system can be enhanced by more than an order of magnitude. Using finite-difference time-domain (FDTD) simulations, it is shown that this enhancement in PL decay rate results from an enhancement factor of ≈100 in electric field intensity provided by the plasmonic mode of the nanocup array, which is also responsible for the EOT. The simulated Purcell factor approaches 86 at the bottom of the nanocup and is ≈3-15 averaged over the nanocup cavity height, agreeing with the experimental enhancement result. This demonstration of solution-based coupling between QDs and gold nanocups opens up new possibilities for applications that would benefit from a solution environment such as biosensing.

Two types of luminescence blinking revealed by spectroelectrochemistry of single quantum dots.

Photoluminescence blinking--random switching between states of high (ON) and low (OFF) emissivities--is a universal property of molecular emitters found in dyes, polymers, biological molecules and artificial nanostructures such as nanocrystal quantum dots, carbon nanotubes and nanowires. For the past 15 years, colloidal nanocrystals have been used as a model system to study this phenomenon. The occurrence of OFF periods in nanocrystal emission has been commonly attributed to the presence of an additional charge, which leads to photoluminescence quenching by non-radiative recombination (the Auger mechanism). However, this 'charging' model was recently challenged in several reports. Here we report time-resolved photoluminescence studies of individual nanocrystal quantum dots performed while electrochemically controlling the degree of their charging, with the goal of clarifying the role of charging in blinking. We find that two distinct types of blinking are possible: conventional (A-type) blinking due to charging and discharging of the nanocrystal core, in which lower photoluminescence intensities correlate with shorter photoluminescence lifetimes; and a second sort (B-type), in which large changes in the emission intensity are not accompanied by significant changes in emission dynamics. We attribute B-type blinking to charge fluctuations in the electron-accepting surface sites. When unoccupied, these sites intercept 'hot' electrons before they relax into emitting core states. Both blinking mechanisms can be electrochemically controlled and completely suppressed by application of an appropriate potential.

Quantifying engineered nanomaterial toxicity: comparison of common cytotoxicity and gene expression measurements.

BACKGROUND: When evaluating the toxicity of engineered nanomaterials (ENMS) it is important to use multiple bioassays based on different mechanisms of action. In this regard we evaluated the use of gene expression and common cytotoxicity measurements using as test materials, two selected nanoparticles with known differences in toxicity, 5 nm mercaptoundecanoic acid (MUA)-capped InP and CdSe quantum dots (QDs). We tested the effects of these QDs at concentrations ranging from 0.5 to 160 µg/mL on cultured normal human bronchial epithelial (NHBE) cells using four common cytotoxicity assays: the dichlorofluorescein assay for reactive oxygen species (ROS), the lactate dehydrogenase assay for membrane viability (LDH), the mitochondrial dehydrogenase assay for mitochondrial function, and the Comet assay for DNA strand breaks. RESULTS: The cytotoxicity assays showed similar trends when exposed to nanoparticles for 24 h at 80 µg/mL with a threefold increase in ROS with exposure to CdSe QDs compared to an insignificant change in ROS levels after exposure to InP QDs, a twofold increase in the LDH necrosis assay in NHBE cells with exposure to CdSe QDs compared to a 50% decrease for InP QDs, a 60% decrease in the mitochondrial function assay upon exposure to CdSe QDs compared to a minimal increase in the case of InP and significant DNA strand breaks after exposure to CdSe QDs compared to no significant DNA strand breaks with InP. High-throughput quantitative real-time polymerase chain reaction (qRT-PCR) data for cells exposed for 6 h at a concentration of 80 µg/mL were consistent with the cytotoxicity assays showing major differences in DNA damage, DNA repair and mitochondrial function gene regulatory responses to the CdSe and InP QDs. The BRCA2, CYP1A1, CYP1B1, CDK1, SFN and VEGFA genes were observed to be upregulated specifically from increased CdSe exposure and suggests their possible utility as biomarkers for toxicity. CONCLUSIONS: This study can serve as a model for comparing traditional cytotoxicity assays and gene expression measurements and to determine candidate biomarkers for assessing the biocompatibility of ENMs.

Competing Interactions between Various Entropic Forces toward Assembly of Pt3Ni Octahedra into a Body-Centered Cubic Superlattice.

Anisotropic nanocrystal assembled supercrystals with open superlattices (SLs) manifest novel and unique properties, but poor understanding of the nucleation/growth mechanisms limits their design and fabrication for practical applications. Using highly anisotropic Pt3Ni octahedral nanocrystals, we have grown large single supercrystals with an open body-centered cubic (bcc) superlattice that has a low filling factor of 26.8%. Synchrotron-based X-ray structural reconstruction fully revealed the coherence of translational and orientational orderings and determined that the constituent octahedra arrange themselves with the vertex-to-vertex and face-to-face configurations along the SL[100] and SL[111] directions, respectively. The large face-to-face separation and flexible vertex-to-vertex elastic contact provided the rattle space and supporting axis for local rotations of Pt3Ni octahedra within the bcc superlattice. Development of orientational disordering along with robust preservation of translational ordering during the heating process of a supercrystal in the oleic acid wetting environment confirmed the dominance of rotational entropy of hard octahedra in the formation of the open bcc superlattice. Ultimate achievement of dynamic equilibrium between the vertex-oriented elastic repulsions and the face-oriented attractions of surface-coating ligands governs the structural and mechanical stability of the supercrystal. This discovery provides significant insights into the design and control of geometrical shapes for the fabrication of highly anisotropic nanocrystals into desired open superlattices with tailored optical and electronic properties.

An Obtuse Rhombohedral Superlattice Assembled by Pt Nanocubes.

We grew large single three-dimensional supercrystals from colloidal Pt nanocubes (NCs) suspended in hexane. A synchrotron-based two circle diffractometer was used to obtain an unprecedented level of detail from full sets of small/wide-angle X-ray scattering (SAXS/WAXS) patterns. Automatic indexing and simulations of X-ray patterns enabled detailed reconstruction of NC translation and shape orientation within the supercrystals from atomic to mesometric levels. The supercrystal has an obtuse rhombohedral (Rh) superlattice with space group R3m and a trigonal cell angle of 106.2°. Individual NCs orient themselves in a manner of atomic Pt[111] parallel to superlattice Rh[111]. We analyzed the superlattice structure in context of three spatial relationships of proximate NCs including face-to-face, edge-to-edge, and corner-to-corner configurations. Detailed analysis of supercrystal structure reveals nearly direct corner-to-corner contacts and a tight interlocking NC structure. We employed the correlations between strain and lattice distortion and established the first structural correlating mechanism between five superlattice polymorphs to elucidate the superlattice transformations and associated developing pathways. Together, the experimental and modeling results provide comprehensive structural information toward controlling design and efficient materials-processing for large fabrication of nanobased functional materials with tailored structures and desired properties.

Elucidation of two giants: challenges to thick-shell synthesis in CdSe/ZnSe and ZnSe/CdS core/shell quantum dots.

Core/thick-shell giant quantum dots (gQDs) possessing type II electronic structures exhibit suppressed blinking and diminished nonradiative Auger recombination. We investigate CdSe/ZnSe and ZnSe/CdS as potential new gQDs. We show theoretically and experimentally that both can exhibit partial or complete spatial separation of an excited-state electron-hole pair (i.e., type II behavior). However, we reveal that thick-shell growth is challenged by competing processes: alloying and cation exchange. We demonstrate that these can be largely avoided by choice of shelling conditions (e.g., time, temperature, and QD core identity). The resulting CdSe/ZnSe gQDs exhibit unusual single-QD properties, principally emitting from dim gray states but having high two-exciton (biexciton) emission efficiencies, whereas ZnSe/CdS gQDs show characteristic gQD blinking suppression, though only if shelling is accompanied by partial cation exchange.

Quantum Optical Signature of Plasmonically Coupled Nanocrystal Quantum Dots.

Small clusters of two to three silica-coated nanocrystals coupled to plasmonic gap-bar antennas can exhibit photon antibunching, a characteristic of single quantum emitters. Through a detailed analysis of their photoluminescence emissions characteristics, it is shown that the observed photon antibunching is the evidence of coupled quantum dot formation resulting from the plasmonic enhancement of dipole-dipole interaction.

3-Dimensional Tracking of Non-blinking 'Giant' Quantum Dots in Live Cells.

While semiconductor quantum dots (QDs) have been used successfully in numerous single particle tracking (SPT) studies due to their high photoluminescence efficiency, photostability, and broad palette of emission colors, conventional QDs exhibit fluorescence intermittency or 'blinking,' which causes ambiguity in particle trajectory analysis and limits tracking duration. Here, non-blinking 'giant' quantum dots (gQDs) are exploited to study IgE-FcεRI receptor dynamics in live cells using a confocal-based 3D SPT microscope. There is a 7-fold increase in the probability of observing IgE-FcεRI for longer than 1 min using the gQDs compared to commercially available QDs. A time-gated photon-pair correlation analysis is implemented to verify that selected SPT trajectories are definitively from individual gQDs and not aggregates. The increase in tracking duration for the gQDs allows the observation of multiple changes in diffusion rates of individual IgE-FcεRI receptors occurring on long (>1 min) time scales, which are quantified using a time-dependent diffusion coefficient and hidden Markov modeling. Non-blinking gQDs should become an important tool in future live cell 2D and 3D SPT studies, especially in cases where changes in cellular dynamics are occurring on the time scale of several minutes.

Competition between auger recombination and hot-carrier trapping in PL intensity fluctuations of type II nanocrystals.

Performing time-tagged, time-correlated, single-photon-counting studies on individual colloidal nanocrystal quantum dots (NQDs), the evolution of photoluminescence (PL) intensity-fluctuation behaviors in near-infrared (NIR) emitting type II, InP/CdS core-shell NQDs is investigated as a function of shell thickness. It is observed that Auger recombination and hot-carrier trapping compete in defining the PL intensity-fluctuation behavior for NQDs with thin shells, whereas the role of hot-carrier trapping dominates for NQDs with thick shells. These studies further reveal the distinct ramifications of altering either the excitation fluence or repetition rate. Specifically, an increase in laser pump fluence results in the creation of additional hot-carrier traps. Alternately, higher repetition rates cause a saturation in hot-carrier traps, thus activating Auger-related PL fluctuations. Furthermore, it is shown that Auger recombination of negatively charged excitons is suppressed more strongly than that of positively charged excitons because of the asymmetry in the electron-hole confinement in type II NQDs. Thus, this study provides new understanding of how both NQD structure (shell thickness and carrier-separation characteristics) and excitation conditions can be used to tune the PL stability, with important implications for room-temperature single-photon generation. Specifically, the first non-blinking NQD capable of single-photon emission in the near-infrared spectral regime is described.

Inducing Circularly Polarized Single-Photon Emission via Chiral-Induced Spin Selectivity.

One of the central aims of the field of spintronics is the control of individual electron spins to effectively manage the transmission of quantized data. One well-known mechanism for controlling electronic spin transport is the chiral-induced spin-selectivity (CISS) effect in which a helical nanostructure imparts a preferential spin orientation on the electronic transport. One potential application of the CISS effect is as a transduction pathway between electronic spin and circularly polarized light within nonreciprocal photonic devices. In this work, we identify and quantify the degree of chiral-induced spin-selective electronic transport in helical polyaniline films using magnetoconductive atomic force microscopy (mcAFM). We then induce circularly polarized quantum light emission from CdSe/CdS core/shell quantum dots placed on these films, demonstrating a degree of circular polarization of up to ∼21%. Utilizing time-resolved photoluminescence microscopy, we measure the radiative lifetime difference associated with left- and right-handed circular polarizations of single emitters. These lifetime differences, in combination with Kelvin probe mapping of the variation of surface potential with magnetization of the substrate, help establish an energy level diagram describing the spin-dependent transport pathways that enable the circularly polarized photoluminescence.

Disentangling the effects of clustering and multi-exciton emission in second-order photon correlation experiments.

In single particle spectroscopy, the degree of observed fluorescence anti-bunching in a second-order cross correlation experiment is indicative of its bi-exciton quantum yield and whether or not a particle is well isolated. Advances in quantum dot synthesis have produced single particles with bi-exciton quantum yields approaching unity. Consequently, this creates uncertainty as to whether a particle has a high bi-exciton quantum yield or if it exists as a cluster. We report on a time-gated anti-bunching technique capable of determining the relative contributions of both multi-exciton emission and clustering effects. In this way, we can now unambiguously determine if a particle is single. Additionally, this time-gated anti-bunching approach provides an accurate way for the determination of bi-exciton lifetime with minimal contribution from higher order multi-exciton states.