Broken Symmetry Optical Transitions in (6,5) Single-Walled Carbon Nanotubes Containing sp3 Defects Revealed by First-Principles Theory.

We present a first-principles many-body perturbation theory study of nitrophenyl-doped (6,5) single-walled nanotubes (SWCNTs) to understand how sp3 doping impacts the excitonic properties. sp3-doped SWCNTs are promising as a class of optoelectronic materials with bright tunable photoluminescence, long spin coherence, and single-photon emission (SPE), motivating the study of spin excitations. We predict that the dopant results in a single unpaired spin localized around the defect site, which induces multiple low-energy excitonic peaks. By comparing optical absorption and photoluminescence from experiment and theory, we identify the transitions responsible for the red-shifted, defect-induced E11* peak, which has demonstrated SPE for some dopants; the presence of this state is due to both the symmetry-breaking associated with the defect and the presence of the defect-induced in-gap state. Furthermore, we find an asymmetry between the contribution of the two spin channels, suggesting that this system has potential for spin-selective optical transitions.

Raman Shifts in Two-Dimensional van der Waals Magnets Reveal Magnetic Texture Evolution.

Two-dimensional (2D) van der Waals magnets comprise rich physics that can be exploited for spintronic applications. We investigate the interplay between spin-phonon coupling and spin textures in a 2D van der Waals magnet by combining magneto-Raman spectroscopy with cryogenic Lorentz transmission electron microscopy. We find that when stable skyrmion bubbles are formed in the 2D magnet, a field-dependent Raman shift can be observed, and this shift is absent for the 2D magnet prepared in its ferromagnetic state. Correlating these observations with numerical simulations that take into account field-dependent magnetic textures and spin--phonon coupling in the 2D magnet, we associate the Raman shift to field-induced modulations of the skyrmion bubbles and derive the existence of inhomogeneity in the skyrmion textures over the film thickness.

Nanosecond Structural Dynamics during Electrical Melting of Charge Density Waves in 1T-TaS_{2}.

Electrical control of charge density waves has been of immense interest, as the strong underlying electron-lattice interactions potentially open new, efficient pathways for manipulating their ordering and, consequently, their electronic properties. However, the transition mechanisms are often unclear as electric field, current, carrier injection, heat, and strain can all contribute and play varying roles across length scales and timescales. Here, we provide insight on how electrical stimulation melts the room temperature charge density wave order in 1T-TaS_{2} by visualizing the atomic and mesoscopic structural dynamics from quasi-static to nanosecond pulsed melting. Using a newly developed ultrafast electron microscope setup with electrical stimulation, we reveal the order and strain dynamics during voltage pulses as short as 20 ns. The order parameter dynamics across a range of pulse amplitudes and durations support a thermally driven mechanism even for fields as high as 19 kV cm^{-1}. In addition, time-resolved imaging reveals a heterogeneous, mesoscopic strain response across the flake, including MHz-scale acoustic resonances that emerge during sufficiently short pulsed excitation which may modulate the order. These results suggest that metallic charge density wave phases like studied here may be more robust to electronic switching pathways than insulating ones, motivating further investigations at higher fields and currents in this and other related systems.

Encapsulating Semiconductor Quantum Dots in Supramolecular Cages Enables Ultrafast Guest-Host Electron and Vibrational Energy Transfer.

In the field of supramolecular chemistry, host-guest systems have been extensively explored to encapsulate a wide range of substrates, owing to emerging functionalities in nanoconfined space that cannot be achieved in dilute solutions. However, host-guest chemistry is still limited to encapsulation of small guests. Herein, we construct a water-soluble metallo-supramolecular hexagonal prism with a large hydrophobic cavity by anchoring multiple polyethylene glycol chains onto the building blocks. Then, assembled prisms are able to encapsulate quantum dots (QDs) with diameters of less than 5.0 nm. Furthermore, we find that the supramolecular cage around each QD strongly modifies the photophysics of the QD by universally increasing the rates of QD relaxation processes via ultrafast electron and vibrational energy transfer. Taken together, these efforts expand the scope of substrates in host-guest systems and provide a new approach to tune the optical properties of QDs.

Thermal Hysteresis and Ordering Behavior of Magnetic Skyrmion Lattices.

The physics of phase transitions in two-dimensional (2D) systems underpins research in diverse fields including statistical mechanics, nanomagnetism, and soft condensed matter. However, many aspects of 2D phase transitions are still not well understood, including the effects of interparticle potential, polydispersity, and particle shape. Magnetic skyrmions are chiral spin-structure quasi-particles that form two-dimensional lattices. Here, we show, by real-space imaging using in situ cryo-Lorentz transmission electron microscopy coupled with machine learning image analysis, the ordering behavior of Néel skyrmion lattices in van der Waals Fe3GeTe2. We demonstrate a distinct change in the skyrmion size distribution during field-cooling, which leads to a loss of lattice order and an evolution of the skyrmion liquid phase. Remarkably, the lattice order is restored during field heating and demonstrates a thermal hysteresis. This behavior is explained by the skyrmion energy landscape and demonstrates the potential to control the lattice order in 2D phase transitions.

Brightening of Dark States in CsPbBr3 Quantum Dots Caused by Light-Induced Magnetism.

Lead halide perovskite quantum dots (QDs) have shown great potential for optoelectronic and quantum photonic applications. Although controversy remains about the electronic fine structures of bulk perovskites due to the strong spin-orbit coupling affecting the conduction bands, compelling evidence indicates that the ground states of perovskite QDs remain dark, limiting their applications in optoelectronic devices. Here, it is demonstrated that photoexcitation can induce large intrinsic magnetic fields in Mn-doped CsPbBr3 perovskite QDs. Equivalent to applying an external magnetic field, the light-induced field causes giant Zeeman splitting to the bright triplet states and brightens the dark singlet ground state, thus effectively rendering a partially bright ground state in the doped QDs. These findings here may contribute to the understanding of the electronic fine structures in perovskite QDs and demonstrate a potential approach for creating semiconductor nanostructures that can serve as bright light sources.

Achieving extreme light confinement in low-index dielectric resonators through quasi-bound states in the continuum.

Obtaining large field enhancement in low-refractive-index dielectric materials is highly relevant to many photonic and quantum optics applications. However, confining light in these materials is challenging, owing to light leakage through coupling to continuum modes in the surrounding environment. We investigate the possibility of achieving high quality factors in low-index dielectric resonators through the bound states in the continuum (BIC). Our simulations demonstrate that destructive interference between leaky modes can be achieved by tuning the geometrical parameters of the resonator arrays, leading to the emergence of quasi-BIC in resonators that have a small index contrast to the underlying substrates. The resultant large field enhancement gives rise to giant quality factors and Purcell effects. By introducing vertical mirror symmetry, the quasi-BIC can be tuned into an ideal BIC. In addition, the quasi-BIC can modify the emission patterns of the coupled emitters, rendering highly directional and focused far-field emission. These findings may provide a path for the practical implementation of photonic and quantum devices based on low-index dielectric materials.

Spontaneous formation of anisotropic microrods from paraffin wax in an aqueous environment.

The construction of functional nano-/micro-architectures through self-assembly and self-organization of organic molecules and polymeric materials plays an important role in the development of many technologies. In this study, we report the spontaneous formation of uniform polymer microrods with lengths of up to a few tens of micrometers from paraffin wax. Through a solvent attrition approach, colloidal structures of paraffin wax are introduced into water. After the initial growth stage, the microrods undergo morphological transformation and end-to-end aggregation, processes likely driven by thermodynamics to create equilibrium structures with minimal interfacial energies. The polymer microrods can effectively absorb hydrophobic nanoparticles, indicating their potential to serve as host materials for functional components. The formation of polymer microrods from paraffin wax and their spontaneous growth mechanism discovered in this study may provide new insights to the self-assembly of microstructures.

Creation of Single-Photon Emitters in WSe2 Monolayers Using Nanometer-Sized Gold Tips.

Due to their tunable bandgaps and strong spin-valley locking, transition metal dichalcogenides constitute a unique platform for hosting single-photon emitters. Here, we present a versatile approach for creating bright single-photon emitters in WSe2 monolayers by the deposition of gold nanostars. Our molecular dynamics simulations reveal that the formation of the quantum emitters is likely caused by the highly localized strain fields created by the sharp tips of the gold nanostars. The surface plasmon modes supported by the gold nanostars can change the local electromagnetic fields in the vicinity of the quantum emitters, leading to their enhanced emission intensities. Moreover, by correlating the emission energies and intensities of the quantum emitters, we are able to associate them with two types of strain fields and derive the existence of a low-lying dark state in their electronic structures. Our findings are highly relevant for the development and understanding of single-photon emitters in transition metal dichalcogenide materials.

Reaching 90% Photoluminescence Quantum Yield in One-Dimensional Metal Halide C4N2H14PbBr4 by Pressure-Suppressed Nonradiative Loss.

Low-dimensional perovskite-related metal halides have emerged as a new class of light-emitting materials with tunable broadband emission from self-trapped excitons (STEs). Although various types of low-dimensional structures have been developed, fundamental understating of the structure-property relationships for this class of materials is still very limited, and further improvement of their optical properties remains greatly important. Here, we report a significant pressure-induced photoluminescence (PL) enhancement in a one-dimensional hybrid metal halide C4N2H14PbBr4, and the underlying mechanisms are investigated using in situ experimental characterization and first-principles calculations. Under a gigapascal pressure scale, the PL quantum yields (PLQYs) were quantitatively determined to show a dramatic increase from the initial value of 20% at ambient conditions to over 90% at 2.8 GPa. With in situ characterization of photophysical properties and theoretical analysis, we found that the PLQY enhancement was mainly attributed to the greatly suppressed nonradiative decay. Pressure can effectively tune the energy level of self-trapped states and increase the exciton binding energy, which leads to a larger Stokes shift. The resulting highly localized excitons with stronger binding reduce the probability for carrier scattering, to result in the significantly suppressed nonradiative decay. Our findings clearly show that the characteristics of STEs in low-dimensional metal halides can be well-tuned by external pressure, and enhanced optical properties can be achieved.

Large-Scale Plasmonic Hybrid Framework with Built-In Nanohole Array as Multifunctional Optical Sensing Platforms.

Light coupling with patterned subwavelength hole arrays induces enhanced transmission supported by the strong surface plasmon mode. In this work, a nanostructured plasmonic framework with vertically built-in nanohole arrays at deep-subwavelength scale (6 nm) is demonstrated using a two-step fabrication method. The nanohole arrays are formed first by the growth of a high-quality two-phase (i.e., Au-TiN) vertically aligned nanocomposite template, followed by selective wet-etching of the metal (Au). Such a plasmonic nanohole film owns high epitaxial quality with large surface coverage and the structure can be tailored as either fully etched or half-way etched nanoholes via careful control of the etching process. The chemically inert and plasmonic TiN plays a role in maintaining sharp hole boundary and preventing lattice distortion. Optical properties such as enhanced transmittance and anisotropic dielectric function in the visible regime are demonstrated. Numerical simulation suggests an extended surface plasmon mode and strong field enhancement at the hole edges. Two demonstrations, including the enhanced and modulated photoluminescence by surface coupling with 2D perovskite nanoplates and the refractive index sensing by infiltrating immersion liquids, suggest the great potential of such plasmonic nanohole array for reusable surface plasmon-enhanced sensing applications.

Anisotropic Photoluminescence from Isotropic Optical Transition Dipoles in Semiconductor Nanoplatelets.

Many important light-matter coupling and energy-transfer processes depend critically on the dimensionality and orientation of optical transition dipoles in emitters. We investigate individual quasi-two-dimensional nanoplatelets (NPLs) using higher-order laser scanning microscopy and find that absorption dipoles in NPLs are isotropic in three dimensions at the excitation wavelength. Correlated polarization studies of the NPLs reveal that their emission polarization is strongly dependent on the aspect ratio of the lateral dimensions. Our simulations reveal that this emission anisotropy can be readily explained by the electric field renormalization effect caused by the dielectric contrast between the NPLs and the surrounding medium, and we conclude that emission dipoles in NPLs are isotropic in the plane of the NPLs. Our study presents an approach for disentangling the effects of dipole degeneracy and electric field renormalization on emission anisotropy and can be adapted for studying the intrinsic optical transition dipoles of various nanostructures.

Silicon-Phosphorene Nanocavity-Enhanced Optical Emission at Telecommunications Wavelengths.

Generating and amplifying light in silicon (Si) continues to attract significant attention due to the possibility of integrating optical and electronic components in a single material platform. Unfortunately, silicon is an indirect band gap material and therefore an inefficient emitter of light. With the rise of integrated photonics, the search for silicon-based light sources has evolved from a scientific quest to a major technological bottleneck for scalable, CMOS-compatible, light sources. Recently, emerging two-dimensional materials have opened the prospect of tailoring material properties based on atomic layers. Few-layer phosphorene, which is isolated through exfoliation from black phosphorus (BP), is a great candidate to partner with silicon due to its layer-tunable direct band gap in the near-infrared where silicon is transparent. Here we demonstrate a hybrid silicon optical emitter composed of few-layer phosphorene nanomaterial flakes coupled to silicon photonic crystal resonators. We show single-mode emission in the telecommunications band of 1.55 µm ( Eg = 0.8 eV) under continuous wave optical excitation at room temperature. The solution-processed few-layer BP flakes enable tunable emission across a broad range of wavelengths and the simultaneous creation of multiple devices. Our work highlights the versatility of the Si-BP material platform for creating optically active devices in integrated silicon chips.

Light-Gated Synthetic Protocells for Plasmon-Enhanced Chemiosmotic Gradient Generation and ATP Synthesis.

Herein, we present a light-gated protocell model made of plasmonic colloidal capsules (CCs) assembled with bacteriorhodopsin for converting solar energy into electrochemical gradients to drive the synthesis of energy-storage molecules. This synthetic protocell incorporated an important intrinsic property of noble metal colloidal particles, namely, plasmonic resonance. In particular, the near-field coupling between adjacent metal nanoparticles gave rise to strongly localized electric fields and resulted in a broad absorption in the whole visible spectra, which in turn promoted the flux of photons to bacteriorhodopsin and accelerated the proton pumping kinetics. The cell-like potential of this design was further demonstrated by leveraging the outward pumped protons as "chemical signals" for triggering ATP biosynthesis in a coexistent synthetic protocell population. Hereby, we lay the ground work for the engineering of colloidal supraparticle-based synthetic protocells with higher-order functionalities.

Hyperbolic Dispersion Arising from Anisotropic Excitons in Two-Dimensional Perovskites.

Excitations of free electrons and optical phonons are known to permit access to the negative real part of relative permittivities (ϵ^{'}<0) that yield strong light-matter interactions. However, negative ϵ^{'} arising from excitons has been much less explored. Via development of a dielectric-coating based technique described herein, we report fundamental optical properties of two-dimensional hybrid perovskites (2DHPs), composed of alternating layers of inorganic and organic sublattices. Low members of 2DHPs (N=1 and N=2) exhibit negative ϵ^{'} stemming from the large exciton binding energy and sizable oscillator strength. Furthermore, hyperbolic dispersion (i.e., ϵ^{'} changes sign with directions) occurs in the visible range, which has been previously achieved only with artificial metamaterials. Such naturally occurring, exotic dispersion stems from the extremely anisotropic excitonic behaviors of 2DHPs, and can intrinsically support a large photonic density of states. We suggest that several other van der Waals solids may exhibit similar behaviors arising from excitonic response.

Anisotropic Cracking of Nanocrystal Superlattices.

The synthesis colloidal nanocrystals in nonpolar organic solvents has led to exceptional size- and shape-control, enabling the formation of nanocrystal superlattices isostructural to atomic lattices built with nanocrystals rather than atoms. The long aliphatic ligands (e.g., oleic acid) used to achieve this control separate nanocrystals too far in the solid state for most charge-transporting devices. Solid-state ligand exchange, which brings particles closer together and enhances conductivity, necessitates large changes in the total volume of the solid (compressive stress), which leads to film cracking. In this work, truncate octahedral lead selenide nanocrystals are shown to self-assemble into body-centered cubic superlattices in which the atomic axes of the individual nanocrystals are coaligned with the crystal axes of the superlattice. Due to this coalignment, upon ligand exchange of the superlattices, cracking is preferentially observed on ⟨011⟩ superlattice directions. This observation is related to differences in the ligand binding to exposed {100} and {111} planes of the PbSe nanocrystal surfaces. This result has implications for binary and more complex structures in which differential reactivity of the constituent elements can lead to disruption of the desired structure. In addition, cracks in PbSe superlattices occur in a semiregular spacings inversely related to the superlattice domain size and strongly influenced by the presence of twin boundaries, which serve as both emission centers and propagation barriers for fractures. This work shows that defects, similar to behavior in nanotwinned metals, could be used to engineer enhanced mechanical strength and electrical conductivity in nanocrystal superlattices.

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.

Quasiphase Transition in a Single File of Water Molecules Encapsulated in (6,5) Carbon Nanotubes Observed by Temperature-Dependent Photoluminescence Spectroscopy.

Molecules confined inside single-walled carbon nanotubes (SWCNTs) behave quite differently from their bulk analogues. In this Letter we present temperature-dependent (4.2 K up to room temperature) photoluminescence (PL) spectra of water-filled and empty single-chirality (6,5) SWCNTs. Superimposed on a linear temperature-dependent PL spectral shift of the empty SWCNTs, an additional stepwise PL spectral shift of the water-filled SWCNTs is observed at ∼150 K. With the empty SWCNTs serving as an ideal reference system, we assign this shift to temperature-induced changes occurring in the single-file chain of water molecules encapsulated in the tubes. Our molecular dynamics simulations further support the occurrence of a quasiphase transition of the orientational order of the water dipoles in the single-file chain.

Influences of Exciton Diffusion and Exciton-Exciton Annihilation on Photon Emission Statistics of Carbon Nanotubes.

Pump-dependent photoluminescence imaging and second-order photon correlation studies have been performed on individual single-walled carbon nanotubes (SWCNTs) at room temperature. These studies enable the extraction of both the exciton diffusion constant and the Auger recombination coefficient. A linear correlation between these parameters is attributed to the effect of environmental disorder in setting the exciton mean free path and capture-limited Auger recombination at this length scale. A suppression of photon antibunching is attributed to the creation of multiple spatially nonoverlapping excitons in SWCNTs, whose diffusion length is shorter than the laser spot size. We conclude that complete antibunching at room temperature requires an enhancement of the exciton-exciton annihilation rate that may become realizable in SWCNTs allowing for strong exciton localization.

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.