Spectral Jumps Research Articles

Sub-millielectronvolt Line Widths in Polarized Low-Temperature Photoluminescence of 2D PbS Nanoplatelets.

Colloidal semiconductor nanocrystals are promising materials for classical and quantum light sources due to their efficient photoluminescence (PL) and versatile chemistry. While visible emitters are well-established, excellent (near-infrared) sources are still being pursued. We present the first comprehensive analysis of low-temperature PL from two-dimensional (2D) PbS nanoplatelets (NPLs). Ultrathin 2D PbS NPLs exhibit high crystallinity confirmed by scanning transmission electron microscopy, revealing Moiré patterns in overlapping NPLs. At 4 K, unique PL features are observed in single PbS NPLs, including narrow zero-phonon lines with line widths down to 0.6 meV and a linear degree of polarization up to 90%. Time-resolved measurements identify trions as the dominant emission source with a 2.3 ns decay time. Sub-meV spectral diffusion and no inherent blinking over minutes are observed, as well as discrete spectral jumps without memory effects. These findings advance the understanding and underscore the potential of colloidal PbS NPLs for optical and quantum technologies.

Single-Molecule Spectral Fluctuation Originates from the Variation in Dipole Orientation Connected to Accessible Vibrational Modes.

Fluctuation in fluorescence emission of an immobilized single molecule is typically ascribed to the chromophore's intrinsic structural conformations and the influence of local environmental factors. Despite extensive research since its initial observation, a direct connection between these spectral fluctuations and the rearrangement of emission dipole orientations has remained elusive. Here, we elucidate this fundamental molecular behavior and its underlying mechanisms by employing unique single-molecule multidimensional tracking to simultaneously monitor both the emission spectrum and the three-dimensional dipole orientation of individual fluorophores. We present compelling evidence demonstrating a correlation between spectral fluctuations and dipolar rearrangements at room temperature. Our observations reveal that variations in the radiative relaxation probabilities among different vibronic emission bands, coupled with the interaction of associated vibrational modes, drive these spectral fluctuations. We identify significant out-of-plane dipole reorientations during pronounced spectral fluctuations, commonly known as spectral jumps, which primarily arise from transitions between dominant vibrational modes. Furthermore, we emphasize the potential for constructing vibrational spectra and optical nanoscopy with vibrational specificity, leveraging the vibronic emissions from single emitters.

Investigating the fast spectral diffusion of a quantum emitter in hBN using resonant excitation and photon correlations

The ability to identify and characterize homogeneous and inhomogeneous dephasing processes is crucial in solid-state quantum optics. In particular, spectral diffusion leading to line broadening is difficult to evidence when the associated timescale is shorter than the inverse of the photon detection rate. Here, we show that a combination of resonant laser excitation and second-order photon correlations allows to access such fast dynamics. The resonant laser drive converts spectral diffusion into intensity fluctuations, leaving a signature in the second-order coherence function $g^{(2)}(\tau)$ of the scattered light that can be characterized using two-photon coincidences -- which simultaneously provides the homogeneous dephasing time. We experimentally implement this method to investigate the fast spectral diffusion of a color center generated by an electron beam in the two-dimensional material hexagonal boron nitride. The $g^{(2)}(\tau)$ function of the quantum emitter measured over more than ten orders of magnitude of delay times, at various laser powers, establishes that the color center experiences spectral diffusion at a characteristic timescale of a few tens of microseconds, while emitting Fourier-limited single photons ($T_2/2T_1 \sim 1$) between spectral jumps.

Dynamic Polymer Free Volume Monitored by Single-Molecule Spectroscopy of a Dual Fluorescent Flapping Dopant.

Single-molecule spectroscopy (SMS) of a dual fluorescent flapping molecular probe (N-FLAP) enabled real-time nanoscale monitoring of local free volume dynamics in polystyrenes. The SMS study was realized by structural improvement of a previously reported flapping molecule by nitrogen substitution, leading to increased brightness (22 times) of the probe. In a polystyrene thin film at the temperature of 5 K above the glass transition, the spectra of a single N-FLAP molecule undergo frequent jumps between short- and long-wavelength forms, the latter one indicating planarization of the molecule in the excited state. The observed spectral jumps were statistically analyzed to reveal the dynamics of the molecular environment. The analysis together with MD and QM/MM calculations show that the excited-state planarization of the flapping probe occurs only when sufficiently large polymer free volume of more than, at least, 280 Å3 is available close to the molecule, and that such free volume lasts for an average of 1.2 s.

Observation of Binary Spectral Jumps in Color Centers in Diamond

AbstractOptical “blinking” normally refers to a switching behavior of fluorescence for quantum emissions between “ON” and “OFF” state. For quantum dots, single molecules, and nitrogen‐vacancy centers in diamond, it usually stems from conversions between two different charge states, with one emitting strong and bright fluorescence while the other scattering weak or no fluorescence. Here, a different type of blinking from single emitters in ion implanted diamond is reported, with both blinking states exhibiting detectable photoluminescence under nonresonant excitation. Thanks to the low jumping rates, the dynamics of the emission can be directly monitored. The quadratic power dependence of the conversion rates suggests the possibility of two‐photon ionization process in quantum jumps. This work provides extra insights into the photodynamics of the spectral jumps on defect‐based single‐photon emitters hosted in wide‐bandgap semiconductors.

Observation of Electron Shakeup in CdSe/CdS Core/Shell Nanoplatelets.

While ensembles of CdSe nanoplatelets (NPLs) show remarkably narrow photoluminescence line widths at room temperature, adding a CdS shell to increase their fluorescence efficiency and photostability causes line width broadening. Moreover, ensemble emission spectra of CdSe/CdS core/shell NPLs become strongly asymmetric at cryogenic temperatures. If the origin of these effects were understood, this could potentially lead to stable core/shell NPLs with narrower emission, which would be advantageous for applications. To move in this direction, we report time-resolved emission spectra of individual CdSe/CdS core/shell NPLs at 4 K. We observe surprisingly complex emission spectra that contain multiple spectrally narrow emission features that change during the experiment. With machine-learning algorithms, we can extract characteristic peak energy differences in these spectra. We show that they are consistent with electron "shakeup lines" from negatively charged trions. In this process, an electron-hole pair recombines radiatively but gives part of its energy to the remaining electron by exciting it into a higher single-electron level. This "shakeup" mechanism is enabled in our NPLs due to strong exciton binding and weak lateral confinement of the charge carriers. Time-resolved single-photon-counting measurements and numerical calculations suggest that spectral jumps in the emission features originate from fluctuations in the confinement potential caused by microscopic structural changes on the NPL surface (e.g., due to mobile surface charges). Our results provide valuable insights into line width broadening mechanisms in colloidal NPLs.

Suppression of spectral diffusion by anti-Stokes excitation of quantum emitters in hexagonal boron nitride

Solid-state quantum emitters are garnering a lot of attention due to their role in scalable quantum photonics. A notable majority of these emitters, however, exhibit spectral diffusion due to local, fluctuating electromagnetic fields. In this work, we demonstrate efficient anti-Stokes (AS) excitation of quantum emitters in hexagonal boron nitride (hBN) and show that the process results in the suppression of a specific mechanism responsible for spectral diffusion of the emitters. We also demonstrate an all-optical gating scheme that exploits Stokes and anti-Stokes excitation to manipulate spectral diffusion so as to switch and lock the emission energy of the photon source. In this scheme, reversible spectral jumps are deliberately enabled by pumping the emitter with high energy (Stokes) excitation; AS excitation is then used to lock the system into a fixed state characterized by a fixed emission energy. Our results provide important insights into the photophysical properties of quantum emitters in hBN and introduce a strategy for controlling the emission wavelength of quantum emitters.

3D Localized Trions in Monolayer WSe2 in a Charge Tunable van der Waals Heterostructure.

Monolayer transition metal dichalcogenides (TMDCs) have recently emerged as a host material for localized optically active quantum emitters that generate single photons. (1-5) Here, we investigate fully localized excitons and trions from such TMDC quantum emitters embedded in a van der Waals heterostructure. We use direct electrostatic doping through the vertical heterostructure device assembly to generate quantum confined trions. Distinct spectral jumps as a function of applied voltage bias, and excitation power-dependent charging, demonstrate the observation of the two different excitonic complexes. We also observe a reduction of the intervalley electron-hole exchange interaction in the confined trion due to the addition of an extra electron, which is manifested by a decrease in its fine structure splitting. We further confirm this decrease of exchange interaction for the case of the charged states by a comparative study of the circular polarization resolved photoluminescence from individual excitonic states. The valley polarization selection rules inherited by the localized trions will provide a pathway toward realizing a localized spin-valley-photon interface.

Amplitude concentration in a phase-modulated spectrum due to femtosecond filamentation

We present a method by which the spectral intensity of an ultrafast laser pulse can be accumulated at selected frequencies by a controllable amount. Using a 4-f pulse shaper we modulate the phase of the frequency components of a femtosecond laser. By inducing femtosecond filamentation with the modulated pulse, we can concentrate the spectral amplitude of the pulse at various frequencies. The phase mask applied by the pulse shaper determines the frequencies for which accumulation occurs, as well as the intensity of the spectral concentration. This technique provides a way to obtain pulses with adjustable amplitude using only phase modulation and the nonlinear response of a medium. This provides a means whereby information which is encoded into spectral phase jumps may be decoded into measurable spectral intensity spikes.

Investigation of Line Width Narrowing and Spectral Jumps of Single Stable Defect Centers in ZnO at Cryogenic Temperature.

Finding new solid state defect centers in novel host materials is crucial for realizing integrated hybrid quantum photonic devices. We present a preparation method for defect centers with photostable bright single photon emission in zinc oxide, a material with promising properties in terms of processability, availability, and applications. A detailed optical study reveals a complex dynamic of intensity fluctuations at room temperature. Measurements at cryogenic temperatures show very sharp (<60 GHz) zero phonon lines (ZPLs) at 580 nm to 620 nm (≈ 2.0 eV) with frozen out fast fluctuations. Remaining discrete jumps of the ZPL, which depend on the excitation power, are observed. The low temperature results will narrow down speculations on the origin of visible-near-infrared (NIR) wavelength defect emission in zinc oxide and provide a basis for improved theoretical models.

Stable single-molecule lines of terrylene in polycrystalline para-dichlorobenzene at 1.5 K.

The spectroscopic properties of single terrylene (Tr) molecules are studied in a polycrystalline matrix of para-dichlorobenzene (p-DCB) at 1.5 K. Samples grown in a glass capillary show a very strong site at 597 nm, which is redshifted by more than 700 cm(-1) from the observed transition energy for Tr in p-DCB prepared as a film on a coverslip (572 nm). Each of these two sites is characterized by measuring their single-molecule spectroscopic parameters at 1.5 K. Lifetime-limited linewidths of 45±5 MHz are found for both sites. Fluorescence detection rates reach 8×10(4) count s(-1) at saturation. The spectral trails of the majority of single molecules show no spectral jumps, indicating an absence of interacting two-level systems; however, the small distribution of linewidths may indicate weak interactions with low-frequency modes. Frequency jumps are observed for 10 % of the molecules. The complete emission spectra from two different single molecules at the center of each of the two sites is presented. Debye-Waller factors of αDW=0.33±0.05 for the normal site (572 nm) and αDW=0.30±0.05 for the red site (597 nm) are reported. This new host-guest system provides a quick and easy way to obtain lifetime-limited single-molecule lines.

Phase measurement in long chirped pulses with spectral phase jumps

Characterization of the chirp in stretched laser pulses is performed with a novel, simple method, based on the use of a plasma mirror switch coupled with a spectrometer. For a 36nm full width half maximum bandwidth and 360ps chirped laser pulse, the spectral phase of the pulse was measured in few hundred of points. Besides the chirp measurement, the approach allows the detection of jumps in the optical path, hence spectral phase jumps corresponding to less than 3ps.

Low temperature spectral dynamics of single molecules in ultrathin polymer films.

We studied the spectral dynamics of single fluorescent dye molecules embedded in ultrathin films (5 - 100 nm) of the amorphous polymer polyisobutylene at cryogenic temperatures and its variation with film thickness. Noticeable portion of molecules in the ensemble shows a behavior which is inconsistent with the standard tunneling model: Their spectral lines are subject to irreversible spectral jumps, continuous shifting, and abrupt chaotic changes of the linewidth or jumping rate. In films thinner than 100 nm, the occurrence of "non-standard" spectral behavior increases with decreasing sample thickness at fixed excitation intensity. In addition, it also increases with laser intensity.

Direct Observation of Rapid Discrete Spectral Dynamics in Single Colloidal CdSe-CdS Core-Shell Quantum Dots

We measure the anomalous spectral diffusion of single colloidal quantum dots over eight temporal decades simultaneously by combining single-molecule spectroscopy and photon-correlation Fourier spectroscopy. Our technique distinguishes between discrete and continuous dynamics and directly reveals that the quasicontinuous spectral diffusion observed using conventional spectroscopy is composed of rapid, discrete spectral jumps. Despite their multiple time scales, these dynamics can be captured by a single mechanism whose parameters vary widely between dots and over time in individual dots.

Efficient simultaneous fluorescence orientation, spectrum, and lifetime detection for single molecule dynamics

We report on the simultaneous detection of the fluorescence lifetime, spectrum, and three-dimensional dipole orientation determination of single perylene diimide molecules deposited on a silica surface as a model system for studying fluorophore internal and orientational dynamics. We employ a multi-parameter detection scheme to demonstrate how jumps in the orientation of the molecule can be disentangled from spectral jumps, both leading to changes of the detected total fluorescence intensity. The fluorescence lifetime determined simultaneously from the same photons is also sensitive to the orientation of the dipole with respect to the interface between media with different refractive indices. The correlated changes of the lifetime and orientation we observe are in good agreement with theory.

Spontaneous Spectral Diffusion in CdSe Quantum Dots.

Spectral diffusion of the emission line of single colloidal nanocrystals is generally regarded as a random process. Here, we show that each new spectral position has a finite memory of previous spectral positions, as evidenced by persistent anticorrelations in time series of spectral jumps. The anticorrelation indicates that there is an enhanced probability of the charge distribution around the nanocrystal returning to a previous configuration. We show both statistically and directly that this memory manifests as an observable spontaneous "relaxation" in the absence of a pump laser, so that spectral diffusion progresses in a manner of "two steps forward and one step back".

Spectral diffusion of quasi localized excitons in single silicon nanocrystals

Evolution in time of photoluminescence spectra of SiOx capped single silicon nanocrystals has been investigated by means of confocal optical spectroscopy at room temperature. Large spectral jumps between subsequent spectra of up to 40meV have been detected leading to noticeable line broadening and variation in the electron–phonon coupling. Further, a correlation between emission energy and emission intensity has been found and discussed in terms of an intrinsic Stark effect. Anti-correlated variations of the electron–phonon coupling to Si and SiO2 phonons as a function of photoluminescence energy indicate that the nearly localized excition is to some extent coupled to phonons in the shell covering the silicon nanocrystal. However, coupling is reduced upon increasing Stark effect, while at the same time coupling to phonons of the Si core increases.

Spectral multitude and spectral dynamics reflect changing conjugation length in single molecules of oligophenylenevinylenes

Single-molecule study of phenylenevinylene oligomers revealed distinct spectral forms due to different conjugation lengths which are determined by torsional defects. Large spectral jumps between different spectral forms were ascribed to torsional flips of a single phenylene ring. These spectral changes reflect the dynamic nature of electron delocalization in oligophenylenevinylenes and enable estimation of the phenylene torsional barriers.

High-Speed Boundary-Layer Instability: Old Terminology and a New Framework

The discrete spectrum of disturbances in high-speed boundary layers is discussed with emphasis on singularities caused by synchronization of the normal modes. Numerical examples illustrate different spectral structures and jumps from one structure to another with small variations of basic flow parameters. It is shown that this singular behavior is due to branching of the dispersion curves in the synchronization region. Depending on the locations of the branch points, the spectrum contains an unstable mode or two. In connection with this, the terminology used for instability of high-speed boundary layers is clarified. It is emphasized that the spectrum branching may cause difficulties in stability analyses based on traditional linear stability theory and parabolized stability equations methods. Multiple-mode considerations and direct numerical simulations are needed to clarify this issue.

Control and Coherence of the Optical Transition of Single Nitrogen Vacancy Centers in Diamond

We demonstrate coherent control of the optical transition of single nitrogen-vacancy defect centers in diamond. On applying short resonant laser pulses, we observe optical Rabi oscillations with a half period as short as 1 ns, an order of magnitude shorter than the spontaneous emission time. By studying the decay of Rabi oscillations, we find that the decoherence is dominated by laser-induced spectral jumps. By using a low-power probe pulse as a detuning sensor and applying postselection, we demonstrate that spectral diffusion can be overcome in this system to generate coherent photons.