Unraveling sources of emission heterogeneity in Silicon Vacancy color centers with cryo-cathodoluminescence microscopy.

Diamond color centers have proven to be versatile quantum emitters and exquisite sensors of stress, temperature, electric and magnetic fields, and biochemical processes. Among color centers, the silicon-vacancy (SiV[Formula: see text]) defect exhibits high brightness, minimal phonon coupling, narrow optical linewidths, and high degrees of photon indistinguishability. Yet the creation of reliable and scalable SiV[Formula: see text]-based color centers has been hampered by heterogeneous emission, theorized to originate from surface imperfections, crystal lattice strain, defect symmetry, or other lattice impurities. Here, we advance high-resolution cryo-electron microscopy combined with cathodoluminescence spectroscopy and 4D scanning transmission electron microscopy (STEM) to elucidate the structural sources of heterogeneity in SiV[Formula: see text] emission from nanodiamond with sub-nanometer-scale resolution. Our diamond nanoparticles are grown directly on TEM membranes from molecular-level seedings, representing the natural formation conditions of color centers in diamond. We show that individual subcrystallites within a single nanodiamond exhibit distinct zero-phonon line (ZPL) energies and differences in brightness that can vary by 0.1 meV in energy and over 70% in brightness. These changes are correlated with the atomic-scale lattice structure. We find that ZPL blue-shifts result from tensile strain, while ZPL red shifts are due to compressive strain. We also find that distinct crystallites host distinct densities of SiV[Formula: see text] emitters and that grain boundaries impact SiV[Formula: see text] emission significantly. Finally, we interrogate nanodiamonds as small as 40 nm in diameter and show that these diamonds exhibit no spatial change to their ZPL energy. Our work provides a foundation for atomic-scale structure-emission correlation, e.g., of single atomic defects in a range of quantum and two-dimensional materials.

Accelerating Quantum Materials Development with Advances in Transmission Electron Microscopy.

Quantum materials are driving a technology revolution in sensing, communication, and computing, while simultaneously testing many core theories of the past century. Materials such as topological insulators, complex oxides, superconductors, quantum dots, color center-hosting semiconductors, and other types of strongly correlated materials can exhibit exotic properties such as edge conductivity, multiferroicity, magnetoresistance, superconductivity, single photon emission, and optical-spin locking. These emergent properties arise and depend strongly on the material's detailed atomic-scale structure, including atomic defects, dopants, and lattice stacking. In this review, we describe how progress in the field of electron microscopy (EM), including in situ and in operando EM, can accelerate advances in quantum materials and quantum excitations. We begin by describing fundamental EM principles and operation modes. We then discuss various EM methods such as (i) EM spectroscopies, including electron energy loss spectroscopy (EELS), cathodoluminescence (CL), and electron energy gain spectroscopy (EEGS); (ii) four-dimensional scanning transmission electron microscopy (4D-STEM); (iii) dynamic and ultrafast EM (UEM); (iv) complementary ultrafast spectroscopies (UED, XFEL); and (v) atomic electron tomography (AET). We describe how these methods could inform structure-function relations in quantum materials down to the picometer scale and femtosecond time resolution, and how they enable precision positioning of atomic defects and high-resolution manipulation of quantum materials. For each method, we also describe existing limitations to solve open quantum mechanical questions, and how they might be addressed to accelerate progress. Among numerous notable results, our review highlights how EM is enabling identification of the 3D structure of quantum defects; measuring reversible and metastable dynamics of quantum excitations; mapping exciton states and single photon emission; measuring nanoscale thermal transport and coupled excitation dynamics; and measuring the internal electric field and charge density distribution of quantum heterointerfaces- all at the quantum materials' intrinsic atomic and near atomic-length scale. We conclude by describing open challenges for the future, including achieving stable sample holders for ultralow temperature (below 10K) atomic-scale spatial resolution, stable spectrometers that enable meV energy resolution, and high-resolution, dynamic mapping of magnetic and spin fields. With atomic manipulation and ultrafast characterization enabled by EM, quantum materials will be poised to integrate into many of the sustainable and energy-efficient technologies needed for the 21st century.

Theory of Photoluminescence Spectral Line Shapes of Semiconductor Nanocrystals.

Single-molecule photoluminescence (PL) spectroscopy of semiconductor nanocrystals (NCs) reveals the nature of exciton-phonon interactions in NCs. Understanding the homogeneous spectral line shapes and their temperature dependence remains an open problem. Here, we develop an atomistic model to describe the PL spectrum of NCs, accounting for excitonic effects, phonon dispersion relations, and exciton-phonon couplings. We validate our model using single-NC measurements on CdSe/CdS NCs from T = 4 to 290 K, and we find that the slightly asymmetric main peak at low temperatures is comprised of a narrow zero-phonon line (ZPL) and acoustic phonon sidebands. Furthermore, we identify the specific phonon modes that give rise to the optical phonon sidebands. At temperatures above 200 K, the spectral line width shows a stronger dependence upon the temperature, which we demonstrate to be correlated with higher order exciton-phonon couplings. We also identify the line width dependence upon reorganization energy, NC core sizes, and shell thicknesses.

Elastic Phonon Scattering Dominates Dephasing in Weakly Confined Cesium Lead Bromide Nanocrystals at Cryogenic Temperatures.

Cesium lead halide perovskite nanocrystals (PNCs) have emerged as a potential next-generation single quantum emitter (QE) material for quantum optics and quantum information science. Optical dephasing processes at cryogenic temperatures are critical to the quality of a QE, making a mechanistic understanding of coherence losses of fundamental interest. We use photon-correlation Fourier spectroscopy (PCFS) to obtain a lower bound to the optical coherence times of single PNCs as a function of temperature. We find that 20 nm CsPbBr3 PNCs emit nearly exclusively into a narrow zero-phonon line from 4 to 13 K. Remarkably, no spectral diffusion is observed at time scales of 10 µs to 5 ms. Our results suggest that exciton dephasing in this temperature range is dominated by elastic scattering from phonon modes with characteristic frequencies of 1-3 meV, while inelastic scattering is minimal due to weak exciton-phonon coupling.

Lead Halide Perovskite Nanocrystals with Low Inhomogeneous Broadening and High Coherent Fraction through Dicationic Ligand Engineering.

Lead halide perovskite nanocrystals (LHP NCs) are an emerging materials system with broad potential applications, including as emitters of quantum light. We apply design principles aimed at the structural optimization of surface ligand species for CsPbBr3 NCs, leading us to the study of LHP NCs with dicationic quaternary ammonium bromide ligands. Through the selection of linking groups and aliphatic backbones guided by experiments and computational support, we demonstrate consistently narrow photoluminescence line shapes with a full-width-at-half-maximum below 70 meV. We observe bulk-like Stokes shifts throughout our range of particle sizes, from 7 to 16 nm. At cryogenic temperatures, we find sub-200 ps lifetimes, significant photon coherence, and the fraction of photons emitted into the coherent channel increasing markedly to 86%. A 4-fold reduction in inhomogeneous broadening from previous work paves the way for the integration of LHP NC emitters into nanophotonic architectures to enable advanced quantum optical investigation.

Narrow Intrinsic Line Widths and Electron-Phonon Coupling of InP Colloidal Quantum Dots.

InP quantum dots (QDs) are the material of choice for QD display applications and have been used as active layers in QD light-emitting diodes (QDLEDs) with high efficiency and color purity. Optimizing the color purity of QDs requires understanding mechanisms of spectral broadening. While ensemble-level broadening can be minimized by synthetic tuning to yield monodisperse QD sizes, single QD line widths are broadened by exciton-phonon scattering and fine-structure splitting. Here, using photon-correlation Fourier spectroscopy, we extract average single QD line widths of 50 meV at 293 K for red-emitting InP/ZnSe/ZnS QDs, among the narrowest for colloidal QDs. We measure InP/ZnSe/ZnS single QD emission line shapes at temperatures between 4 and 293 K and model the spectra using a modified independent boson model. We find that inelastic acoustic phonon scattering and fine-structure splitting are the most prominent broadening mechanisms at low temperatures, whereas pure dephasing from elastic acoustic phonon scattering is the primary broadening mechanism at elevated temperatures, and optical phonon scattering contributes minimally across all temperatures. Conversely for CdSe/CdS/ZnS QDs, we find that optical phonon scattering is a larger contributor to the line shape at elevated temperatures, leading to intrinsically broader single-dot line widths than for InP/ZnSe/ZnS. We are able to reconcile narrow low-temperature line widths and broad room-temperature line widths within a self-consistent model that enables parametrization of line width broadening, for different material classes. This can be used for the rational design of more spectrally narrow materials. Our findings reveal that red-emitting InP/ZnSe/ZnS QDs have intrinsically narrower line widths than typically synthesized CdSe QDs, suggesting that these materials could be used to realize QDLEDs with high color purity.

A room-temperature polarization-sensitive CMOS terahertz camera based on quantum-dot-enhanced terahertz-to-visible photon upconversion.

Detection of terahertz (THz) radiation has many potential applications, but presently available detectors are limited in many aspects of their performance, including sensitivity, speed, bandwidth and operating temperature. Most do not allow the characterization of THz polarization states. Recent observation of THz-driven luminescence in quantum dots offers a possible detection mechanism via field-driven interdot charge transfer. We demonstrate a room-temperature complementary metal-oxide-semiconductor THz camera and polarimeter based on quantum-dot-enhanced THz-to-visible upconversion mechanism with optimized luminophore geometries and fabrication designs. Besides broadband and fast responses, the nanoslit-based sensor can detect THz pulses with peak fields as low as 10 kV cm-1. A related coaxial nanoaperture-type device shows a to-date-unexplored capability to simultaneously record the THz polarization state and field strength with similar sensitivity.

Terahertz Field-Induced Reemergence of Quenched Photoluminescence in Quantum Dots.

The continuous and concerted development of colloidal quantum dot light-emitting diodes over the past two decades has established them as a bedrock technology for the next generation of displays. However, a fundamental issue that limits the performance of these devices is the quenching of photoluminescence due to excess charges from conductive charge transport layers. Although device designs have leveraged various workarounds, doing so often comes at the cost of limiting efficient charge injection. Here we demonstrate that high-field terahertz (THz) pulses can dramatically brighten quenched QDs on metallic surfaces, an effect that persists for minutes after THz irradiation. This phenomenon is attributed to the ability of the THz field to remove excess charges, thereby reducing trion and nonradiative Auger recombination. Our findings show that THz technologies can be used to suppress and control such undesired nonradiative decay, potentially in a variety of luminescent materials for future device applications.

All-optical fluorescence blinking control in quantum dots with ultrafast mid-infrared pulses.

Photoluminescence intermittency is a ubiquitous phenomenon, reducing the temporal emission intensity stability of single colloidal quantum dots (QDs) and the emission quantum yield of their ensembles. Despite efforts to achieve blinking reduction by chemical engineering of the QD architecture and its environment, blinking still poses barriers to the application of QDs, particularly in single-particle tracking in biology or in single-photon sources. Here, we demonstrate a deterministic all-optical suppression of QD blinking using a compound technique of visible and mid-infrared excitation. We show that moderate-field ultrafast mid-infrared pulses (5.5 µm, 150 fs) can switch the emission from a charged, low quantum yield grey trion state to the bright exciton state in CdSe/CdS core-shell QDs, resulting in a significant reduction of the QD intensity flicker. Quantum-tunnelling simulations suggest that the mid-infrared fields remove the excess charge from trions with reduced emission quantum yield to restore higher brightness exciton emission. Our approach can be integrated with existing single-particle tracking or super-resolution microscopy techniques without any modification to the sample and translates to other emitters presenting charging-induced photoluminescence intermittencies, such as single-photon emissive defects in diamond and two-dimensional materials.

Resolving the Triexciton Recombination Pathway in CdSe/CdS Nanocrystals through State-Specific Correlation Measurements.

As luminescence applications of colloidal semiconductor nanocrystals push toward higher excitation flux conditions, there is an increased need to both understand and potentially control emission from multiexciton states. We develop a spectrally resolved correlation method to study the triply excited state that enables direct measurements of the recombination pathway for the triexciton, rather than relying on indirect extraction of rates. We demonstrate that, for core-shell CdSe-CdS nanocrystals, triexciton emission arises exclusively from the band-edge S-like state. Time-dependent density functional theory and extended particle-in-a-sphere calculations demonstrate that reduced carrier overlap induced by the core-shell heterostructure can account for the lack of emission observed from the P-like state. These results provide a potential avenue for the control of nanocrystal luminescence, where core-shell heterostructures can be leveraged to control carrier separation and therefore maintain emission color purity over a broader range of excitation fluxes.

Lifetime-resolved photon-correlation Fourier spectroscopy.

The excited state population of single solid-state emitters is subjected to energy fluctuations around the equilibrium driven by the bath and relaxation through the emission of phonons or photons. Simultaneous measurement of the associated spectral dynamics requires a technique with a high spectral and temporal resolution with an additionally high temporal dynamic range. We propose a pulsed excitation-laser analog of photon-correlation Fourier spectroscopy (PCFS), which extracts the linewidth and spectral diffusion dynamics along the emission lifetime trajectory of the emitter, effectively discriminating spectral dynamics from relaxation and bath fluctuations. This lifetime-resolved PCFS correlates photon-pairs at the output arm of a Michelson interferometer in both their time-delay between laser-excitation and photon-detection T and the time-delay between two photons τ. We propose the utility of the technique for systems with changing relative contributions to the emission from multiple states, for example, quantum emitters exhibiting phonon-mediated exchange between different fine-structure states.

Nanocrystal synthesis, µfluidic sample dilution and direct extraction of single emission linewidths in continuous flow.

The rational design of semiconductor nanocrystal populations requires control of their emission linewidths, which are dictated by interparticle inhomogeneities and single-nanocrystal spectral linewidths. To date, research efforts have concentrated on minimizing the ensemble emission linewidths, however there is little knowledge about the synthetic parameters dictating single-nanocrystal linewidths. In this direction, we present a flow-based system coupled with an optical interferometry setup for the extraction of single nanocrystal properties. The platform has the ability to synthesize nanocrystals at high temperature <300 °C, adjust the particle concentration after synthesis and extract ensemble-averaged single nanocrystal emission linewidths using flow photon-correlation Fourier spectroscopy.

Effect of Spectral Diffusion on the Coherence Properties of a Single Quantum Emitter in Hexagonal Boron Nitride.

Quantum emitters capable of producing single photons on-demand with high color purity are the building blocks of emerging schemes in secure quantum communications, quantum computing, and quantum metrology. Such solid-state systems, however, are usually prone to effects of spectral diffusion (SD), i.e., fast modulation of the emission wavelength due to the presence of localized, fluctuating electric fields. Two-dimensional materials are especially vulnerable to SD by virtue of the proximity of the emitters to the outside environment. In this study we report measurements of SD in a single hexagonal boron nitride (hBN) quantum emitter on the nanosecond to second time scales using photon correlation Fourier spectroscopy. We demonstrate that the spectral diffusion dynamics can be modeled by a two-component Gaussian random jump model, suggesting multiple sources of local fluctuations. We provide a lower limit of ∼0.13 for the ratio of the emitter's coherence time (T2) to twice its radiative lifetime (2T1) when it is measured on submicrosecond time scales. These results suggest that attaining transform-limited line widths could be achieved with moderate enhancement of the radiative rate. Moreover, the complex SD dynamics identified in our work inspires further exploration of the dephasing mechanisms in hBN as a viable quantum emitter platform.

Blue Light Emitting Defective Nanocrystals Composed of Earth-Abundant Elements.

Copper-based ternary (I-III-VI) chalcogenide nanocrystals (NCs) are compositionally-flexible semiconductors that do not contain lead (Pb) or cadmium (Cd). Cu-In-S NCs are the dominantly studied member of this important materials class and have been reported to contain optically-active defect states. However, there are minimal reports of In-free compositions that exhibit efficient photoluminescence (PL). Here, we report a novel solution-phase synthesis of ≈4 nm defective nanocrystals (DNCs) composed of copper, aluminum, zinc, and sulfur with ≈20 % quantum yield and an attractive PL maximum of 450 nm. Extensive spectroscopic characterization suggests the presence of highly localized electronic states resulting in reasonably fast PL decays (≈1 ns), large vibrational energy spacing, small Stokes shift, and temperature-independent PL linewidth and PL lifetime (between room temperature and ≈5 K). Furthermore, density functional theory (DFT) calculations suggest PL transitions arise from defects within a CuAl5 S8 crystal lattice, which supports the experimental observation of highly-localized states. The results reported here provide a new material with unique optoelectronic characteristics that is an important analog to well-explored Cu-In-S NCs.

Discovery of blue singlet exciton fission molecules via a high-throughput virtual screening and experimental approach.

Singlet exciton fission is a mechanism that could potentially enable solar cells to surpass the Shockley-Queisser efficiency limit by converting single high-energy photons into two lower-energy triplet excitons with minimal thermalization loss. The ability to make use of singlet exciton fission to enhance solar cell efficiencies has been limited, however, by the sparsity of singlet fission materials with triplet energies above the bandgaps of common semiconductors such as Si and GaAs. Here, we employ a high-throughput virtual screening procedure to discover new organic singlet exciton fission candidate materials with high-energy (>1.4 eV) triplet excitons. After exploring a search space of 4482 molecules and screening them using time-dependent density functional theory, we identify 88 novel singlet exciton fission candidate materials based on anthracene derivatives. Subsequent purification and characterization of several of these candidates yield two new singlet exciton fission materials: 9,10-dicyanoanthracene (DCA) and 9,10-dichlorooctafluoroanthracene (DCOFA), with triplet energies of 1.54 eV and 1.51 eV, respectively. These materials are readily available and low-cost, making them interesting candidates for exothermic singlet exciton fission sensitization of solar cells. However, formation of triplet excitons in DCA and DCOFA is found to occur via hot singlet exciton fission with excitation energies above ∼3.64 eV, and prominent excimer formation in the solid state will need to be overcome in order to make DCA and DCOFA viable candidates for use in a practical device.

Coherent single-photon emission from colloidal lead halide perovskite quantum dots.

Chemically made colloidal semiconductor quantum dots have long been proposed as scalable and color-tunable single emitters in quantum optics, but they have typically suffered from prohibitively incoherent emission. We now demonstrate that individual colloidal lead halide perovskite quantum dots (PQDs) display highly efficient single-photon emission with optical coherence times as long as 80 picoseconds, an appreciable fraction of their 210-picosecond radiative lifetimes. These measurements suggest that PQDs should be explored as building blocks in sources of indistinguishable single photons and entangled photon pairs. Our results present a starting point for the rational design of lead halide perovskite-based quantum emitters that have fast emission, wide spectral tunability, and scalable production and that benefit from the hybrid integration with nanophotonic components that has been demonstrated for colloidal materials.

Multiexciton Lifetimes Reveal Triexciton Emission Pathway in CdSe Nanocrystals.

Multiexcitons in emerging semiconducting nanomaterials play a critical role in potential optoelectronic and quantum computational devices. We describe photon resolved single molecule methods to directly probe the dynamics of biexcitons and triexcitons in colloidal CdSe quantum dots. We confirm that biexcitons emit from a spin-correlated state, consistent with statistical scaling. Contrary to current understanding, we find that triexciton emission is dominated by band-edge 1Se1S3/2 recombination rather than the higher energy 1Pe1P3/2 recombination.

Probing Linewidths and Biexciton Quantum Yields of Single Cesium Lead Halide Nanocrystals in Solution.

Cesium lead halide (CsPbX3, X = Cl, Br, I) perovskite nanocrystals (PNCs) have recently become a promising material for optoelectronic applications due to their high emission quantum yields and facile band gap tunability via both halide composition and size. The spectroscopy of single PNCs enhances our understanding of the effect of confinement on excitations in PNCs in the absence of obfuscating ensemble averaging and can also inform synthetic efforts. However, single PNC studies have been hampered by poor PNC photostability under confocal excitation, precluding interrogation of all but the most stable PNCs, and leading to a lack of understanding of PNCs in the regime of high confinement. Here, we report the first comprehensive spectroscopic investigation of single PNC properties using solution-phase photon-correlation methods, including both highly confined and blue-emitting PNCs, previously inaccessible to single NC techniques. With minimally perturbative solution-phase photon-correlation Fourier spectroscopy (s-PCFS), we establish that the ensemble emission linewidth of PNCs of all sizes and compositions is predominantly determined by the intrinsic single PNC linewidth (homogeneous broadening). The single PNC linewidth, in turn, dramatically increases with increasing confinement, consistent with what has been found for II-VI semiconductor nanocrystals. With solution-phase photon antibunching measurements, we survey the biexciton-to-exciton quantum yield ratio (BX/X QY) in the absence of user-selection bias or photodegradation. Remarkably, the BX/X QY ratio depends both on the PNC size and halide composition, with values between ∼2% for highly confined bromide PNCs and ∼50% for intermediately confined iodide PNCs. Our results suggest a wide range of underlying Auger rates, likely due to transitory charge carrier separation in PNCs with relaxed confinement.

PbS Nanocrystal Emission Is Governed by Multiple Emissive States.

Lead chalcogenide colloidal nanocrystals (NCs) are promising materials for solution processable optoelectronics. However, there is little agreement on the identity and character of PbS NC emission for different degrees of quantum confinement-a critical parameter for realizing applications for these nanocrystals. In this work, we combine ensemble and single NC spectroscopies to interrogate preparations of lead sulfide NCs. We use solution photon correlation Fourier spectroscopy (S-PCFS) to measure the average single NC linewidth of near-infrared-emitting PbS quantum dots and find it to be dominated by homogeneous broadening. We further characterize PbS NCs using temperature-dependent linear and time-resolved emission spectroscopy which demonstrate that a kinetically accessed defect state dominates room temperature emission of highly confined emitting NCs. These experiments, taken together, demonstrate that the linewidth and Stokes shift of PbS NCs are the result of emission from two states: a thermally accessed defect-with an energetically pinned charge carrier-and an inhomogeneously broadened band-edge state.