Photoluminescence Intensity Fluctuations Research Articles

Temperature-Induced Luminescence Intensity Fluctuation of Protein-Protected Copper Nanoclusters: Role of Scaffold Conformation vs Nonradiative Transition.

Protein-scaffolded atomically precise metal nanoclusters (NCs) have emerged as a promising class of biofriendly nanoprobes at the forefront of modern research, particularly in the area of sensing. The photoluminescence (PL) intensity of several nanoclusters showed a systematic temperature-dependent fluctuation, but the mechanism remains ambiguous and is poorly understood. We tried to shed some light on this mechanistic aspect by testing a couple of hypotheses: (i) conformational fluctuation of the protein scaffold-mediated PL intensity fluctuation and (ii) PL intensity fluctuation due to the variation in the radiative and nonradiative transition rates. Herein, the PL intensity of the lysozyme-capped copper nanocluster (Lys-Cu NC) showed excellent temperature dependency; upon increasing the temperature, the PL intensity gradually decreased. However, contrasting effects can be seen when the nanocluster is exposed to a chemical denaturant (guanidine hydrochloride (GdnHCl)); the PL intensity increased with the increase in the GdnHCl concentration due to the change in the ionic strength of the medium. This discrepancy clearly suggests that the thermal PL intensity fluctuation cannot be explained by a change in the scaffold conformation. Furthermore, upon closer investigation, we observed a 2-fold increase in the nonradiative decay rate of the Lys-Cu NC at the elevated temperature, which could reasonably explain the decrease in the PL intensity of the nanocluster at the higher temperature. Additionally, from the result, it was evident that the protein scaffold-metal core interaction played a key role here in stabilizing each other; hence, the scaffold structure remained unaffected even in the presence of chemical denaturants.

N-doped carbon nanospheres as selective fluorescent probes for mercury detection in contaminated aqueous media: chemistry, fluorescence probing, cell line patterning, and liver tissue interaction.

A precise nano-scale biosensor was developed here to detect Hg2+ in aqueous media. Nitrogen-doped carbon nanospheres (NCS) created from the pyrolysis of melamine-formaldehyde resin were characterized by FESEM, XRD, Raman spectra, EDS, PL, UV-vis spectra, and N2 adsorption-desorption, and were used as a highly selective and sensitive probe for detecting Hg2+ in aqueous media. The sensitivity of NCS to Hg2+ was evaluated by photoluminescence intensity fluctuations under fluorescence emission in the vicinity of 390nm with a λexc of 350nm. The fluorescence intensity of the NCS probe weakened in the presence of Hg2+ owing to the effective fluorescence quenching by that, which is not corresponding to the special covalent liking between the ligand and the metal. The effects of the fluorescence nanoprobe concentration, pH, and sensing time were monitored to acquire the best conditions for determining Hg2+. Surprisingly, NCS revealed excellent selectivity and sensitivity towards Hg2+ in the samples containing Co2+, Na+, K+, Fe2+, Mn2+, Al3+, Pb2+, Ni2+, Ca2+, Cu2+, Mg2+, Cd2+, Cr3+, Li+, Cs+, and Ba2+. The fluorescence response was linearly proportional to Hg2+ concentration in 0.013-0.046µM with a limit of detection of 9.58nM. The in vitro and in vivo toxicological analyses confirmed the completely safe and biocompatible features of NCS, which provides promise for use for water, fruit, vegetable, and/or other forms of natural-connected materials exposed to Hg2+, with no significant toxicity noticed toward different cells/organs/tissues.

Synthesis and Localized Photoluminescence Blinking of Lead‐Free 2D Nanostructures of Cs3Bi2I6Cl3 Perovskite

AbstractTwo‐dimensional (2D) lead‐free halide perovskites have generated enormous perception in the field of optoelectronics due to their fascinating optical properties. However, an in‐depth understanding on their shape‐controlled charge‐carrier recombination dynamics is still lacking, which could be resolved by exploring the photoluminescence (PL) blinking behaviour at the single‐particle level. Herein, we demonstrate, for the first time, the synthesis of nanocrystals (NCs) and 2D nanosheets (NSs) of layered mixed halide, Cs3Bi2I6Cl3, by solution‐based method. We applied fluorescence microscopy and super‐resolution optical imaging at single‐particle level to investigate their morphology‐dependent PL properties. Narrow emission line widths and passivation of non‐radiative defects were evidenced for 2D layered nanostructures, whereas the activation of shallow trap states was recognized at 77 K. Interestingly, individual NCs were found to display temporal intermittency (blinking) in PL emission. On the other hand, NS showed temporal PL intensity fluctuations within localized domains of the crystal. In addition, super‐resolution optical image of the NS from localization‐based method showed spatial inhomogeneity of the PL intensity within perovskite crystal.

Synthesis and Localized Photoluminescence Blinking of Lead-Free 2D Nanostructures of Cs3 Bi2 I6 Cl3 Perovskite.

Two-dimensional (2D) lead-free halide perovskites have generated enormous perception in the field of optoelectronics due to their fascinating optical properties. However, an in-depth understanding on their shape-controlled charge-carrier recombination dynamics is still lacking, which could be resolved by exploring the photoluminescence (PL) blinking behaviour at the single-particle level. Herein, we demonstrate, for the first time, the synthesis of nanocrystals (NCs) and 2D nanosheets (NSs) of layered mixed halide, Cs3 Bi2 I6 Cl3 , by solution-based method. We applied fluorescence microscopy and super-resolution optical imaging at single-particle level to investigate their morphology-dependent PL properties. Narrow emission line widths and passivation of non-radiative defects were evidenced for 2D layered nanostructures, whereas the activation of shallow trap states was recognized at 77 K. Interestingly, individual NCs were found to display temporal intermittency (blinking) in PL emission. On the other hand, NS showed temporal PL intensity fluctuations within localized domains of the crystal. In addition, super-resolution optical image of the NS from localization-based method showed spatial inhomogeneity of the PL intensity within perovskite crystal.

Fluorescence Polarization Switching from a Single Silicon Vacancy Colour Centre in Diamond.

Single-photon emitters with stable and uniform photoluminescence properties are important for quantum technology. However, in many cases, colour centres in diamond exhibit spectral diffusion and photoluminescence intensity fluctuation. It is therefore essential to investigate the dynamics of colour centres at the single defect level in order to enable the on-demand manipulation and improved applications in quantum technology. Here we report the polarization switching, intensity jumps and spectral shifting observed on a negatively charged single silicon-vacancy colour centre in diamond. The observed phenomena elucidate the single emitter dynamics induced by photoionization of nearby electron donors in the diamond.

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.

Photoluminescence Stability of Colloidal CdTe Quantum Dots in Various Buffer Solutions

Mercaptoacetic acid-capped CdTe quantum dots (QDs) are potential luminescent markers for biological analysis. The photoluminescence (PL) stability of the QDs in buffer solutions determines their practicability as markers in electrophoresis. The stability of the QDs was thus investigated in electrophoresis buffers including tris–borate–ethylenediaminetetraacetic acid (TBE) and tris–acetate–ethylenediaminetetraacetic acid (TAE). The QDs were completely unstable in high-concentrated buffers (≥0.1×). In the case of low concentrations (≤0.07× for TAE, ≤0.035× for TBE), the PL intensity of the QDs in two kinds of buffers decreased with increasing buffer concentrations. A red-shifted PL peak wavelength and PL intensity fluctuation were observed after dispersing the QDs in diluted TAE buffer solutions with concentrations of ≤0.07× for long time. According to the Stern–Volmer plots of PL degradation, the factors leading to the degradation were complicated, which was attributed to the actions of the components including tris, borate or acetic acid, and ethylenediaminetetraacetic acid as well as their mutual effects.

PL Spatial Variation in InGaN/GaN MQWs Studied by Confocal Microscopy and TRPL Spectroscopy

Confocal laser scanning microscopy and time-resolved photoluminescence (TRPL) spectroscopy were used to study blue-emitting InGaN/GaN multiple quantum wells. Spatial and spectral variations of photoluminescence (PL) were observed over submicron-scale regions. Spectral measurements showed that the bright regions have a higher PL intensity as well as smaller peak energy than the dark regions. Correlations among the bright region-dark region PL peak energy difference, the average PL intensity, the PL FWHM, the bright region PL intensity, and the extent of PL intensity fluctuation were observed. As the energy difference increased, the average PL intensity, the PL FWHM, and the bright region PL intensity increased, with a higher degree of areal PL intensity fluctuations. TRPL measurements and calculations showed that the effective PL lifetime at bright regions was longer than that at dark regions, and bright region lifetime increases as energy difference increases, possibly as a result of stronger confinement.

Multimodal optical studies of single and clustered colloidal quantum dots for the long-term optical property evaluation of quantum dot-based molecular imaging phantoms

Understanding the optical properties of clustered quantum dots (QDs) is essential to the design of QD-based optical phantoms for molecular imaging. Single and clustered core/shell colloidal QDs of dimers, trimers, and tetramers are self-assembled, separated, and preferentially collected using electrospray differential mobility analysis (ES-DMA) with electrostatic deposition. Multimodal optical characterization and analysis of their dynamical photoluminescence (PL) properties enables the long-term evaluation of the physicochemical and optical properties of QDs in a single or a clustered state. A multimodal time-correlated spectroscopic confocal microscope capable of simultaneously measuring the time evolution of PL intensity fluctuation, PL lifetime, and emission spectra reveals the long-term dynamic optical properties of interacting QDs in individual dimeric clusters of QDs. This new method will benefit research into the quantitative interpretation of fluorescence intensity and lifetime results in QD-based molecular imaging techniques. The process of photooxidation leads to coupling of the QDs in a dimer, leading to unique optical properties when compared to an isolated QD. These results guide the design and evaluation of QD-based phantom materials for the validation of the PL measurements for quantitative molecular imaging of biological samples labeled with QD probes.

Near-Unity Quantum Yields of Biexciton Emission fromCdSe/CdSNanocrystals Measured Using Single-Particle Spectroscopy

Biexciton photoluminescence (PL) quantum yields (Q(2X)) of individual CdSe/CdS core-shell nanocrystal quantum dots with various shell thicknesses are derived from independent PL saturation and two-photon correlation measurements. We observe a near-unity Q(2X) for some nanocrystals with an ultrathick 19-monolayer shell. High Q(2X)'s are, however, not universal and vary widely among nominally identical nanocrystals indicating a significant dependence of Q(2X) upon subtle structural differences. Interestingly, our measurements indicate that high Q(2X)'s are not required to achieve complete suppression of PL intensity fluctuations in individual nanocrystals.

Subsecond Luminescence Intensity Fluctuations of Single CdSe Quantum Dots

Photoluminescence (PL) intermittency characteristics are examined for single quantum dots (QDs) in a CdSe QD sample synthesized at a slow rate at 75 degrees C. Although the PL quantum efficiency was relatively low ( approximately 0.25), we noticed that the PL intensity of single CdSe QDs fluctuated on a subsecond time scale with short-lived "on" and "off" states. The subsecond PL intensity fluctuations of CdSe QDs are different from "on" and "off" PL blinking generally observed for QDs fluctuating on a millisecond to minute time scale. We characterized single QDs by identifying polarized excitations, topographic imaging using atomic force microscopy (AFM), and transmission electron microscopy (TEM). From analysis of the PL intensity trajectories from >100 single CdSe QDs, the average intermittency time was 213 ms. From the PL quantum efficiency, slow growth of QDs, intensity trajectory analyses, and previous reports relating surface trap states and PL properties of QDs, we attribute the subsecond PL intensity fluctuations of single CdSe QDs and short-lived "on" and "off" states to a high-density distribution of homogeneous surface trap states.

Photoluminescence intermittency in an individual single-walled carbon nanotube at room temperature

We described the photoluminescence (PL) properties of individual micelle-encapsulated single-walled carbon nanotubes (SWNTs) at room temperature. Single PL peak from isolated individual SWNT with a chiral index of (6, 5) showed a linear increase and saturation behavior of the PL intensity. Unusual PL intensity fluctuation in the temporal evolutions of the PL intensity, referred to as PL intermittency, was seen with some SWNTs, while the PL intensity with most SWNTs remained at a constant amplitude. The mechanism of the PL intermittency was discussed.

Photoluminescence intensity fluctuations and electric-field-induced photoluminescence quenching in individual nanoclusters of poly(phenylenevinylene).

Substantial fluctuations of the fluorescence intensity have been detected for single clusters of poly(phenylenevinylene) containing more than 75 polymer chains or 30,000 monomer units. To the best of our knowledge, this is the first time such fluctuations (which resemble the "blinking" effect in single-molecule fluorescence) have been reported for such a large molecular ensemble containing several macromolecules. Together with the distinct jumps, smooth fluctuations of the fluorescence intensity, with characteristic times from milliseconds to seconds, were observed. This fact distinguishes the fluorescence behaviour of the polymer clusters from that of other multichromophoric systems such as the single chains of conjugated polymers reported in the literature. The consecutive or simultaneous switching of one or several emitting sites from the "on" to "off" state does not explain the character of the fluctuations observed. We suggest that the quenching of the light-emitting exciton by a long-lived species, such as, for example, polarons, plays an important role in these unusual fluctuations. Electric field induced fluorescence quenching differs significantly for different clusters. It is proposed that this fluorescence was mainly quenched by polarons injected from the electrodes in the presence of an electric field. The specific behaviour of each cluster is explained by suggesting a different position of the clusters with respect to the electrodes.