Single Exciton Research Articles

Weakly Confined Semiconductor Nanocrystals Excel in Photochemical and Optoelectronic Properties: Evidence from Single-Dot Studies.

Single-molecule spectroscopy offers state-resolved measurements on charge-transfer reactions of single semiconductor nanocrystals, leading to the discovery of up to six single-charge transfer reactions with seven transient states for single CdSe/CdS core/shell nanocrystals with water (or oxygen) as the hole (or electron) acceptors. Kinetic rates of three photoinduced single-hole transfer reactions decrease significantly upon increasing the number of excess electrons in a nanocrystal, mainly due to efficient Auger nonradiative recombination of the charged single excitons. Conversely, the kinetic rates of three single-electron transfer reactions of an unexcited nanocrystal increase proportionally to the number of excess electrons in it. Results here reveal that charge-transfer reactions of nanocrystals, at the center of nearly all their functions, could only be deciphered at a state-resolved level on a single nanocrystal. Size-dependent studies validate the weakly confined semiconductor nanocrystals, instead of strongly confined ones (quantum dots), as optimal candidates for photochemical and optoelectronic applications.

Strain coupling of a single exciton to a nano-optomechanical resonator

Strain coupling of a single exciton to a nano-optomechanical resonator

CsPbBr3 Perovskite Crack Platelet Nanocrystals and Their Biexciton Generation.

Lead halide perovskite nanocrystals have been extensively studied in recent years as efficient optical materials for their bright and color-tunable emissions. However, these are mostly confined to their 3D nanocrystals and limited to the anisotropic nanostructures. By exploring the Cs-sublattice-induced metal(II) ion exchange with Pb(II), crack CsPbBr3 perovskite platelet nanocrystals having polar surfaces in all three directions are reported here, which remained different than reported standard square platelets. The crack platelets are also passivated with halides to enhance their brightness. Further, as these crack and passivated crack platelets have defects and polar surfaces, the exciton and biexciton generation in these platelets is investigated using femtosecond photoluminescence and transient absorption measurement at ambient as well as cryogenic temperatures, correlated with time-resolved single-particle photoluminescence spectroscopy, and compared with standard square platelets having nonpolar facets. These investigations revealed that the crack platelets and passivated crack platelets possess enhanced biexciton emission compared to square platelets due to the presence of polar surfaces in all three directions. These results provide insights into not only the design of the anisotropic nanostructures of ionic nanocrystals but also the possibility of tuning the single exciton to biexciton generation efficiency, which has potential applications in optoelectronic systems.

Spectator Exciton Effects in Nanocrystals III: Unveiling the Stimulated Emission Cross Section in Quantum Confined CsPbBr3 Nanocrystals.

Quantifying stimulated emission in semiconductor nanocrystals (NCs) remains challenging due to masking of its effects on pump-probe spectra by excited state absorption and ground state bleaching signals. The absence of this defining photophysical parameter in turn impedes assignment of band edge electronic structure in many of these important fluorophores. Here we employ a generally applicable 3-pulse ultrafast spectroscopic method coined the "Spectator Exciton" (SX) approach to measure stimulated-emission efficiency in quantum confined inorganic perovskite CsPbBr3 NCs, the band edge electronic structure of which is the subject of lively ongoing debate. Our results show that in 5-6 nm CsPbBr3 NCs, a single exciton bleaches more than half of the intense band edge absorption band, while the cross section for stimulated emission from the same state is nearly 6 times weaker. Discussion of these findings in light of several recent electronic structure models for this material proves them unable to simultaneously explain both measures, proving the importance of this new input to resolving this debate. Along with femtosecond time-resolved photoluminescence measurements on the same sample, SX results also verify that biexciton interaction energy is intensely attractive with a magnitude of ∼80 meV. In light of this observation, our previous suggestion that biexciton interaction is repulsive is reassigned to hot phonon induced slowdown of carrier relaxation leading to direct Auger recombination from an excited state. The mechanism behind the extreme slowing of carrier cooling after several stages of exciton recombination remains to be determined.

Deterministic positioning and alignment of a single-molecule exciton in plasmonic nanodimer for strong coupling.

Experimental realization of strong coupling between a single exciton and plasmons remains challenging as it requires deterministic positioning of the single exciton and alignment of its dipole moment with the plasmonic fields. This study aims to combine the host-guest chemistry approach with the cucurbit[7]uril-mediated active self-assembly to precisely integrate a single methylene blue molecule in an Au nanodimer at the deterministic position (gap center of the nanodimer) with the maximum electric field (EFmax) and perfectly align its transition dipole moment with the EFmax, yielding a large spectral Rabi splitting of 116 meV for a single-molecule exciton-matching the analytical model and numerical simulations. Statistical analysis of vibrational spectroscopy and dark-field scattering spectra confirm the realization of the single exciton strong coupling at room temperature. Our work may suggest an approach for achieving the strong coupling between a deterministic single exciton and plasmons, contributing to the development of room-temperature single-qubit quantum devices.

Fine structure splitting cancellation in highly asymmetric InAs/InP droplet epitaxy quantum dots

We find the fine structure splitting (FSS) of a single exciton, which splits its degenerate ground-state manifold into singlets, nearly vanishes in highly asymmetric quantum dots (QDs) due to the cancellation of splitting effects with markedly different origin. The dots simulated are those that emerge on top of etch pits through the droplet epitaxy growth process; these etch pit dots break square (C4v) spatial symmetry, which has been previously associated with small FSS. Configuration interaction calculations predict a vanishing FSS at a specific finite etch pit displacement from the center of the dot, for a structure far from square symmetry. We thus predict that highly asymmetric QDs may still display negligible FSS, providing avenues for high-fidelity generation of indistinguishable, polarization entangled photon pairs on demand. Published by the American Physical Society 2024

Green Light from Red-Emitting Nanocrystals: Broadband, Low-Threshold Lasing from Colloidal Quantum Shells in Optical Nanocavities.

Spherical semiconductor nanoplatelets, known as quantum shells (QSs), have captured significant interest for their strong suppression of Auger recombination, which leads to long multiexciton lifetimes and wide optical gain bandwidth. Yet, the realization of benefits associated with the multiexciton lasing regime using a suitably designed photonic cavity remains elusive. Here, we demonstrate broadly tunable lasing from close-packed films of CdS/CdSe/CdS QSs deposited over nanopillar arrays on Si substrates. Wide spectral tuning of the stimulated emission in QSs with a fixed bandgap value was achieved by engaging single exciton (λX ∼ 634 nm), biexciton (λBX ∼ 627 nm), and multiple exciton (λMX ∼ 615-565 nm) transitions. The ensemble-averaged gain threshold of <N> ∼ 2.6 electron-hole pairs per QS particle and the low photonic cavity fluence threshold of ∼4 μJ/cm2 were attributed to Auger suppression. The tuning of the lasing emission closely aligns with our model predictions achieved by varying the array period while preserving mode confinement and quality (Q) factors. These results mark a notable step toward the development of colloidal nanocrystal lasers.

Investigation of Exciton Dynamics to Confirm Coupling Effects Using a Comparison between Ensemble and Single Laterally‐Coupled GaAs Quantum Dot Molecules

Herein, time‐integrated and time‐resolved photoluminescence (PL) measurement experiments are performed on coupled GaAs quantum dot (QD) molecules with larger laser spot size and a single‐coupled QD molecule to investigate the dynamics of exciton states. A linearly polarized laser along the coupled direction of a laterally‐coupled GaAs QD molecule [10] is used to determine the coupling effects of the different exciton states. For the ensemble of coupled QD molecules, the exciton PL peak shifts to lower energy (≈70 meV) and shows a linear increase in the PL intensity, demonstrating the properties of exciton states as a function of the laser excitation power. In addition, a power‐dependent redshift is observed in the single‐coupled GaAs QD molecule as a function of the excitation power; however, the two distinguished exciton states become resolved and show different power factors when the laser excitation power is linearly increased. This result clearly indicates the presence of energy transfer between the two different exciton states, X1 and X2. Furthermore, when the polarized laser excitation power is increased, a coupled biexciton consisting of two different localized exciton states (X1 and X2) is clearly observed, and a power‐dependent spectral redshift is detected in the exciton and biexciton states. At a high excitation power (15 I0), the decay times of the two different localized exciton states clearly show different lifetimes; and the decay time difference due to the size difference can be ignored at a low excitation power. Theoretically, the decay times of the two different exciton states, wherein the size deviation can be ignored, should be the same. Based on the results of the time‐integrated and time‐resolved PL measurements and the comparison between the ensemble and single exciton PL peaks, it is concluded that the coupling process in laterally‐coupled GaAs QD molecules is strongly supported against long‐range separation.

Methylation of Si(111) Modulates Molecular Orientation in Perylenediimide Thin Films.

Singlet fission produces a pair of low-energy spin-triplet excitons from a single high-energy spin-singlet exciton. While this process offers the potential to enhance the efficiency of silicon solar cells by ∼30%, meeting this goal requires overlayer materials that can efficiently transport triplet excitons to an underlying silicon substrate. Herein, we demonstrate that the chemical functionalization of silicon surfaces controls the structure of vapor-deposited thin films of perylenediimide (PDI) dyes, which are prototypical singlet fission materials. Using a combination of atomic force microscopy (AFM) and grazing-incidence wide-angle X-ray scattering (GIWAXS), we find terminating Si(111) with either a thin, polar oxide layer (SiOx) or with hydrophobic methyl groups (Si-CH3) alters the structures of the resulting PDI films. While PDI films grown on SiOx are comprised of small crystalline grains that largely adopt an "edge-on" orientation with respect to the silicon surface, films grown on Si-CH3 contain large grains that prefer to align in a "face-on" manner with respect to the substrate. This "face-on" orientation is expected to enhance exciton transport to silicon. Interestingly, we find that the preferred mode of growth for different PDIs correlates with the space group associated with bulk crystals of these compounds. While PDIs that inhabit a monoclinic (P21/c) space group nucleate films by forming tall and sparse crystalline columns, PDIs that inhabit triclinic (P1̅) space groups afford films comprised of uniform, lamellar PDI domains. The results highlight that silicon surface functionalization profoundly impacts PDI thin film growth, and rational selection of a hydrophobic surface that promotes "face-on" adsorption may improve energy transfer to silicon.

Exciton and biexciton transient absorption spectra of CdSe quantum dots with varying diameters.

Transient absorption (TA) spectroscopy of semiconductor nanocrystals (NCs) is often used for excited state population analysis, but recent results suggest that TA bleach signals associated with multiexcitons in NCs do not scale linearly with exciton multiplicity. In this manuscript, we probe the factors that determine the intensities and spectral positions of exciton and biexciton components in the TA spectra of CdSe quantum dots (QDs) of five diameters. We find that, in all cases, the peak intensity of the biexciton TA spectrum is less than 1.5 times that of the single exciton TA spectrum, in stark contrast to a commonly made assumption that this ratio is 2. The relative intensities of the biexciton and exciton TA signals at each wavelength are determined by at least two factors: the TA spectral intensity and the spectral offset between the two signals. We do not observe correlations between either of these factors and the particle diameter, but we find that both are strongly impacted by replacing the native organic surface-capping ligands with a hole-trapping ligand. These results suggest that surface trapping plays an important role in determining the absolute intensities of TA features for CdSe QDs and not just their decay kinetics. Our work highlights the role of spectral offsets and the importance of surface trapping in governing absolute TA intensities. It also conclusively demonstrates that the biexciton TA spectra of CdSe QDs at the band gap energy are less than twice as intense as those of the exciton.

How to recognize clustering of luminescent defects in single-wall carbon nanotubes.

Semiconducting single-wall carbon nanotubes (SWCNTs) are a promising material platform for near-infrared in vivo imaging, optical sensing, and single-photon emission at telecommunication wavelengths. The functionalization of SWCNTs with luminescent defects can lead to significantly enhanced photoluminescence (PL) properties due to efficient trapping of highly mobile excitons and red-shifted emission from these trap states. Among the most studied luminescent defect types are oxygen and aryl defects that have largely similar optical properties. So far, no direct comparison between SWCNTs functionalized with oxygen and aryl defects under identical conditions has been performed. Here, we employ a combination of spectroscopic techniques to quantify the number of defects, their distribution along the nanotubes and thus their exciton trapping efficiencies. The different slopes of Raman D/G+ ratios versus calculated defect densities from PL quantum yield measurements indicate substantial dissimilarities between oxygen and aryl defects. Supported by statistical analysis of single-nanotube PL spectra at cryogenic temperatures they reveal clustering of oxygen defects. The clustering of 2-3 oxygen defects, which act as a single exciton trap, occurs irrespective of the functionalization method and thus enables the use of simple equations to determine the density of oxygen defects and defect clusters in SWCNTs based on standard Raman spectroscopy. The presented analytical approach is a versatile and sensitive tool to study defect distribution and clustering in SWCNTs and can be applied to any new functionalization method.

Elucidating the photophysics behind the stimulated emission processes in CsPbBr3 nanocrystals films

Thanks to their excellent photoluminescence quantum yields, their facile and low-cost production, and their processing versatility, CsPbBr3 perovskite nanocrystals (NCs) stand out as excellent candidates to implement light-emitting devices. Elucidating their stimulated emission mechanisms is fundamental to achieve much more efficient and versatile perovskite lasers. In particular, two questions remain open: why the Amplified Spontaneous Emission (ASE) band is significantly shifted from the fluorescence one, and why the former seems to suddenly emerge from, and coexist with, the latter. These characteristic features have led to a debate, which is not settled yet, on which is the mechanism behind the ASE band shift. In this communication, we try to settle this debate and address these questions through experimental ASE measurements combined with numerical simulations. We show that the ASE behaviour in CsPbBr3 NCs thin films stems from a combination of reabsorption, excited state absorption, excitation of differently polarized waveguide modes, and the coexistence of short- and long-lived localized single excitons. The results in this work help understanding the stimulated emission mechanisms in perovskites and provide insightful information on research avenues to increase the efficiency of the light-emitting devices based on these materials.

Excitonic Quantum Coherence in Light Emission from CsPbBr3 Metal-Halide Perovskite Nanocrystals.

The decay of excited states via radiative and nonradiative paths is well understood in molecules and bulk semiconductors but less so in nanocrystals. Here, we perform time-resolved photoluminescence (t-PL) experiments on CsPbBr3 metal-halide perovskite nanocrystals, with a time resolution of 3 ps, sufficient to observe the decay of both excitons and biexcitons as a function of temperature. The striking result is that the radiative rate constant of the single exciton increases at low temperatures with an exponential functional form, suggesting quantum coherent effects with dephasing at high temperatures. The opposing directions of the radiative and nonradiative decay rate constants enable enhanced brightening of PL from excitons to biexcitons due to quantum effects, promoting a faster approach to the quantum theoretical limits of light emission. Ab initio quantum dynamics simulations reproduce the experimental observations of radiation controlled by quantum spatial coherence enhanced at low temperatures.

Optical gain and lasing from bulk cadmium sulfide nanocrystals through bandgap renormalization.

Strongly confined colloidal quantum dots have been investigated for low-cost light emission and lasing for nearly two decades. However, known materials struggle to combine technologically relevant metrics of low-threshold and long inverted-state lifetime with a material gain coefficient fit to match cavity losses, particularly under electrical excitation. Here we show that bulk nanocrystals of CdS combine an exceptionally large material gain of 50,000 cm-1 with best-in-class gain thresholds below a single exciton per nanocrystal and 3 ns gain lifetimes not limited by non-radiative Auger processes. We quantitatively account for these findings by invoking a strong bandgap renormalization effect, unobserved in nanocrystals to date, to the best of our knowledge. Next, we demonstrate broadband amplified spontaneous emission and lasing under quasi-continuous-wave conditions. Our results highlight the prospects of bulk nanocrystals for lasing from solution-processable materials.

PH-controlled construction of 2D and 3D micro-nano hybrid carbon architectures with fluorescence/phosphorescence dual-mode emission for white-emitting diodes

Developing nanocarbon-based white-emitting diodes (WLEDs) with high energy conversion efficiency is still extremely challenging due to the issue of Kasha's rule and serious self-aggregation caused luminescent quenching of nanocarbon in a solid-state. Herein, the synergistic strategy of framework and intercalator between nanosheets and carbon dots (CDs) was adopted. Three novel 2D nanosheets, 3D nanoflowers and 3D parasa consocia-like micro-nano carbon architectures decorated with dispersive CDs were successfully fabricated through one-step hydrothermal reaction at different pH medium. The pH-regulated mechanisms of morphology and structure, via degree modulation of condensation and carbonization, were further proposed. All samples exhibited bright white emission, derived from fluorescence/phosphorescence dual-mode emission. The hybrid emission made sufficient utilization of single and triplet excitons with the quantum yield of 16%–30%. The superior white light with CIE coordinates of (0.331,0.334) was recorded for neutral sample (p-CNDs-N), ascribed to the multiple energy level transitions from polydisperse luminescence centers. The luminous efficiency was remarkably improved in HCl (p-CNDs-H) and NaOH treated samples (p-CNDs-OH), resulting from inner carbonization, external cross-linked network and the passivation of surface defect sites. This is the first example for pH-controlled fabrication of multi-dimension hybrid nanocarbon structures and pH-controlled fluorescence/phosphorescence dual-mode emission for highly efficient carbon-based WLEDs.

Bosonic Delocalization of Dipolar Moiré Excitons.

In superlattices of twisted semiconductor monolayers, tunable moiré potentials emerge, trapping excitons into periodic arrays. In particular, spatially separated interlayer excitons are subject to a deep potential landscape and they exhibit a permanent dipole providing a unique opportunity to study interacting bosonic lattices. Recent experiments have demonstrated density-dependent transport properties of moiré excitons, which could play a key role for technological applications. However, the intriguing interplay between exciton-exciton interactions and moiré trapping has not been well understood yet. In this work, we develop a microscopic theory of interacting excitons in external potentials allowing us to tackle this highly challenging problem. We find that interactions between moiré excitons lead to a delocalization at intermediate densities, and we show how this transition can be tuned via twist angle and temperature. The delocalization is accompanied by a modification of optical moiré resonances, which gradually merge into a single free exciton peak.

Slipping-Free Halide Perovskite Supercrystals from Supramolecularly-Assembled Nanocrystals.

Supramolecularly assembled high-order supercrystals (SCs) help control the dielectric, electronic, and excitonic properties of semiconductor nanocrystals (NCs) and quantum dots (QDs). Ligand-engineered perovskite NCs (PNCs) assemble into SCs showing shorter excitonic lifetimes than strongly dielectric PNC films showing long photoluminescence (PL) lifetimes and long-range carrier diffusion. Monodentate to bidentate ligand exchange on ≈ 8nm halide perovskite (APbX3 ; A:Cs/MA, X:Br/I) PNCs generates mechanically stable SCs with close-packed lattices, overlapping electronic wave functions, and higher dielectric constant, providing distinct excitonic properties from single PNCs or PNC films. From Fast Fourier Transform (FFT) images, time-resolved PL, and small-angle X-ray scattering, structurally and excitonically ordered large SCs are identified. An Sc shows a smaller spectral shift (<35 meV) than a PNC film (>100 meV), a microcrystal (>100 meV), or a bulk crystal (>100 meV). Also, the exciton lifetime (<10ns) of an SC is excitation power-independent in the single exciton regime 〈N〉<1, comparable to an isolated PNC. Therefore, bidentate-ligand-assisted SCs help overcome delayed exciton or carrier recombination in halide perovskite nanocrystal assemblies or films.

Amplified spontaneous emission from CdSe/CdS/CdZnS quantum dot films

The dynamic and spectral characteristics of close-packed quantum dots excited by a ∼30 ps long laser pulse in a film prepared by a drop casting method from toluene solution were investigated. The photoluminescence wavelength of single excitons and the wavelength of amplified spontaneous radiation associated with a stimulated decay of biexcitons were obtained. From the spectrogram of the time-resolved photoluminescence the information was obtained about the dynamics of these two types of radiation. It was shown that the radiation peak maximum of single excitons appears by 60 ps later than the maximum of amplified spontaneous radiation, then it slowly becomes narrower and diminishes. The amplified spontaneous radiation lasts for 200 ps.

Surface Passivation for Promotes Bi-Excitonic Amplified Spontaneous Emission in CsPb(Br/Cl)3 Perovskite at Room Temperature.

Perovskite-type lead halides exhibit promising performances in optoelectronic applications, for which lasers are one of the most promising applications. Although the bulk structure has some advantages, perovskite has additional advantages at the nanoscale owing to its high crystallinity given by a lower trap density. Although the nanoscale can produce efficient light emission, its comparatively poor chemical and colloidal stability limits further development of devices based on this material. Nevertheless, bulk perovskites are promising as optical amplifiers. There has been some developmental progress in the study of optical response and amplified spontaneous emission (ASE) as a benchmark for perovskite bulk phase laser applications. Therefore, to achieve high photoluminescence quantum yields (PLQYs) and large optical gains, material development is essential. One of the aspects in which these goals can be achieved is the incorporation of a bulk structure of high-quality crystallization films based on inorganic perovskite, such as cesium lead halide (CsPb(Br/Cl)3), in polymethyl methacrylate (PMMA) polymer and encapsulation with the optimal thickness of the polymer to achieve complete surface coverage, prevent degradation, surface states, and surface defects, and suppress emission at depth. Sequential evaporation of the perovskite precursors using a single-source thermal evaporation technique (TET) effectively deposited two layers. The PL and ASEs of the bare and modified films with a thickness of 400 nm PMMA were demonstrated. The encapsulation layer maintained the quantum yield of the perovskite layer in the air for more than two years while providing added optical gain compared to the bare film. Under a picosecond pulse laser, the PL wavelength of single excitons and ASE wavelength associated with the stimulated decay of bi-excitons were achieved. The two ASE bands were highly correlated and competed with each other; they were classified as exciton and bi-exciton recombination, respectively. According to the ASE results, bi-exciton emission could be observed in an ultrastable CsPb(Br/Cl)3 film modified by PMMA with a very low excitation energy density of 110 µJ/cm2. Compared with the bare film, the ASE threshold was lowered by approximately 5%. A bi-exciton has a binding energy (26.78 meV) smaller than the binding energy of the exciton (70.20 meV).

Pressure-induced core defects and photoluminescent quenching in carbon quantum dots

Carbon quantum dots (CDs) with favorable luminescent features for biphotonic applications have attracted much interest in modulating their photoluminescence (PL) efficiency. A surface state with various defects is believed to play a key role in the emissive intensity. Here, pressure-induced quenching of PL is observed in red emissive CDs (R-CDs) and is ascribed to defects in carbon cores upon compression. In the power-law fitting to the excitation power-dependent PL of R-CDs at high pressure, the coefficient k parameter related to the emissive mechanism decreases from 1 under ambient pressure to much less than 1 under the application of pressure, suggesting a transition from single exciton recombination to defect-related emission. With the k parameter decreasing to 0.69 at 1.6 GPa, the pressure-induced defects reduce the PL intensity by approximately one order of magnitude. Furthermore, the attenuation and broadening of the G band characterizing the sp2 hybrid structure of carbon cores in the Raman spectra for R-CDs at high pressure support that the pressure-induced lattice relaxation impairs the crystalline symmetry of the carbon core and results in the dramatic quenching of PL. Our results highlight the importance of the well-crystallized carbon core in designing CDs with high quantum yields.