Conversion of Photoluminescence Blinking Types in Single Colloidal Quantum Dots.

Almost all colloidal quantum dots (QDs) exhibit undesired photoluminescence (PL) blinking, which poses a significant obstacle to their use in numerous luminescence applications. An in-depth study of the blinking behavior, along with the associated mechanisms, can provide critical opportunities for fabricating high-quality QDs for diverse applications. Here the blinking of a large series of colloidal QDs is investigated with different surface ligands, particle sizes, shell thicknesses, and compositions. It is found that the blinking behavior of single alloyed CdSe/ZnS QDs with a shell thickness of up to 2 nm undergoes an irreversible conversion from Auger-blinking to band-edge carrier blinking (BC-blinking). Contrastingly, single perovskite QDs with particle sizes smaller than their Bohr diameters exhibit reversible conversion between BC-blinking and more pronounced Auger-blinking. Changes in the effective trapping sites under different excitation conditions are found to be responsible for the blinking type conversions. Additionally, changes in shell thickness and particle size of QDs have a significant effect on the blinking type conversions due to altered wavefunction overlap between excitons and effective trapping sites. This study elucidates the discrepancies in the blinking behavior of various QD samples observed in previous reports and provides deeper understanding of the mechanisms underlying diverse types of blinking.

Three-dimensional quantum imaging of dynamic targets using quantum compressed sensing.

Quantum imaging based on entangled light sources exhibits enhanced background resistance compared to conventional imaging techniques in low-light conditions. However, direct imaging of dynamic targets remains challenging due to the limited count rate of entangled photons. In this paper, we propose a quantum imaging method based on quantum compressed sensing that leverages the strong correlation characteristics of entangled photons and the randomness inherent in photon pair generation and detection. This approach enables the construction of a compressed sensing system capable of directly imaging high-speed dynamic targets. The results demonstrate that our system successfully achieves imaging of a target rotating at a frequency of 10 kHz, while maintaining an impressive data compression rate of 10-6. This proposed method introduces a pioneering approach for the practical implementation of quantum imaging in real-world scenarios.

Anomalous layer-dependent photoluminescence spectra of supertwisted spiral WS2.

Twisted stacking of two-dimensional materials with broken inversion symmetry, such as spiral MoTe2 nanopyramids and supertwisted spiral WS2, emerge extremely strong second- and third-harmonic generation. Unlike well-studied nonlinear optical effects in these newly synthesized layered materials, photoluminescence (PL) spectra and exciton information involving their optoelectronic applications remain unknown. Here, we report layer- and power-dependent PL spectra of the supertwisted spiral WS2. The anomalous layer-dependent PL evolutions that PL intensity almost linearly increases with the rise of layer thickness have been determined. Furthermore, from the power-dependent spectra, we find the power exponents of the supertwisted spiral WS2 are smaller than 1, while those of the conventional multilayer WS2 are bigger than 1. These two abnormal phenomena indicate the enlarged interlayer spacing and the decoupling interlayer interaction in the supertwisted spiral WS2. These observations provide insight into PL features in the supertwisted spiral materials and may pave the way for further optoelectronic devices based on the twisted stacking materials.

Size-dependent photoluminescence blinking mechanisms and volume scaling of biexciton Auger recombination in single CsPbI3 perovskite quantum dots.

Determining the correlation between the size of a single quantum dot (QD) and its photoluminescence (PL) properties is a challenging task. In the study, we determine the size of each QD by measuring its absorption cross section, which allows for accurate investigation of size-dependent PL blinking mechanisms and volume scaling of the biexciton Auger recombination at the single-particle level. A significant correlation between the blinking mechanism and QD size is observed under low excitation conditions. When the QD size is smaller than their Bohr diameter, single CsPbI3 perovskite QDs tend to exhibit BC-blinking, whereas they tend to exhibit Auger-blinking when the QD size exceeds their Bohr diameter. In addition, by extracting bright-state photons from the PL intensity trajectories, the effects of QD charging and surface defects on the biexcitons are effectively reduced. This allows for a more accurate measurement of the volume scaling of biexciton Auger recombination in weakly confined CsPbI3 perovskite QDs at the single-dot level, revealing a superlinear volume scaling (τXX,Auger ∝ σ1.96).

High-efficiency single-photon compressed sensing imaging based on the best choice scheme.

With single-photon sensitivity and picosecond resolution, single-photon imaging technology is an ideal solution for extreme conditions and ultra-long distance imaging. However, the current single-photon imaging technology has the problem of slow imaging speed and poor quality caused by the quantum shot noise and the fluctuation of background noise. In this work, an efficient single-photon compressed sensing imaging scheme is proposed, in which a new mask is designed by the Principal Component Analysis algorithm and the Bit-plane Decomposition algorithm. By considering the effects of quantum shot noise, dark count on imaging, the number of masks is optimized to ensure high-quality single-photon compressed sensing imaging with different average photon counts. The imaging speed and quality are greatly improved compared with the commonly used Hadamard scheme. In the experiment, a 64 × 64 pixels' image is obtained with only 50 masks, the sampling compression rate reaches 1.22%, and the sampling speed increases by 81 times. The simulation and experimental results demonstrated that the proposed scheme will effectively promote the application of single-photon imaging in practical scenarios.

High frequency near-infrared up-conversion single-photon imaging based on the quantum compressed sensing.

Infrared up-conversion single-photon imaging has potential applications in remote sensing, biological imaging, and night vision imaging. However, the used photon counting technology has the problem of long integration time and sensitivity to background photons, which limit its application in real-world scenarios. In this paper, a novel passive up-conversion single-photon imaging method is proposed, in which the high frequency scintillation information of a near infrared target is captured by using the quantum compressed sensing. Through the frequency domain characteristic imaging of the infrared target, the imaging signal-to-noise ratio is significantly improved with strong background noise. In the experiment, the target with flicker frequency on the order of GHz is measured, and the signal-to-background ratio of the imaging reaches up to 1:100. Our proposal greatly improved the robustness of near-infrared up-conversion single-photon imaging and will promote its practical application.

Optical interference effect in the hybrid quantum dots/two-dimensional materials: photoluminescence enhancement and modulation.

The optical interference effect originating from the multiple reflections between the two-dimensional (2D) materials and the substrates has been used to dramatically enhance their Raman signal. However, this effect in the hybrid structures of colloidal quantum dots (QD) coupled to 2D materials is always overlooked. Here we theoretically prove that the photoluminescence (PL) intensities of the QD films in the QD-2D hybrid structures can be strongly enhanced and modulated by the optical interference effect between QD and 2D interfaces, breaking the inherent standpoint that PL intensities of the QD films are always prominently quenched in these hybrid structures. The theoretical predictions have been well confirmed by experimental measurements of PL properties of CdSe/ZnS and CdSeTe/ZnS QD on different 2D materials (such as WSe2, MoS2, and h-BN). PL intensities of these QD films have been periodically modulated from almost disappearing to strong enhancement (with the enhancement of about 6 times). The optical interference effect uncovered in this work enables a powerful method to manipulate the PL property of the QD films in the different QD-2D hybrid structures. These results can boost the optical performance of the QD-based electronic and optoelectronic devices in the hybrid QD-2D structures.

Underestimated effect of the polymer encapsulation process on the photoluminescence of perovskite revealed by in situ single-particle detection.

Photostability has always been an important issue that limits the performance of organo-metal halide perovskites in optoelectronic devices. Although the photostability can be partially improved by polymer coating/encapsulation, one rising question that needs to be considered is whether the improvement of photostability is accessed at the expense of intangible loss in photoluminescence (PL) properties. By in situ analyzing the evolution of PL properties of individual perovskite crystals during the polymer encapsulation procedure, we demonstrate here that poly(methyl methacrylate), a common polymeric encapsulant, would passivate the surface defects of perovskite crystals, leading to the suppress of PL blinking. However, somewhat counterintuitive, the toluene solvent will induce the PL decline of individual perovskite crystals via accumulation of the number of quenchers that, most probably, are related to the ion migration in perovskite. The findings at the single-particle level emphasize the often-neglected role of the polymer matrix and the solvent in the optical properties of perovskite material during the polymer encapsulation process, and will guide the further design of more stable and high-performance devices based on perovskite.

Exploration of exciton dynamics in GaTe nanoflakes via temperature- and power-dependent time-resolved photoluminescence spectra.

GaTe nanoflakes have been receiving much research attention recently due to their applications in optoelectronic devices, such as anisotropic non-volatile memory, solar cells, and high-sensitivity photodetectors from the ultraviolet to the visible region. Further applications, however, have been impeded due to the limited understanding of their exciton dynamics. In this work we perform temperature- and power-dependent time-resolved photoluminescence (PL) spectra to comprehensively investigate the exciton dynamics of GaTe nanoflakes. Temperature-dependent PL measurements manifest that spectral profiles of GaTe nanoflakes change dramatically from cryogenic to room temperature, where the bound exciton and donor-to-acceptor pair transition normally disappear above 100 K, while the charged exciton survives to room temperature. The lifetimes of these excitons and their evolution vs temperature have been uncovered by time-resolved PL spectra. Further measurements reveal the entirely different power-dependent exciton behaviors of GaTe nanoflakes between room and cryogenic temperatures. The underlying mechanisms have been proposed to explore the sophisticated exciton dynamics within GaTe nanoflakes. Our results offer a more thorough understanding of the exciton dynamics of GaTe nanoflakes, enabling further progress in engineering GaTe-based applications, such as photodetectors, light-emitting diodes, and nanoelectronics.

Great enhancement on two-photon photoluminescence imaging contrast of Au nanoparticles via double-pulse femtosecond laser excitation with controlled phase differences.

Au nanoparticles are attractive contrast agents for noninvasive living tissue imaging with deep penetration because of their strong two-photon photoluminescence (TPPL) intensity and excellent biocompatibility. However, the inevitable phototoxicity and huge auto-fluorescence are consistently associated with laser excitation. Therefore, enhancement of TPPL intensity and suppression of backgrounds are always highly desired under the demand of reducing excitation powers. In this work, we develop a double-pulse TPPL (DP-TPPL) scheme with controlled phase differences (Δφ) between the double pulses to significantly improve the signal-to-noise ratio (SNR) of TPPL imaging. Under the modulated phase (Δφ periodically varying between 0-2π), our results show that SNR can be improved from 4.3 to 1715, with an enhancement of up to 400 folds at the integration of 50 ms. More importantly, this enhancement can be unlimitedly lifted by increasing the number of photons or integration times in principle. Further boosting has been achieved by reducing the magnitude of background noises; subsequently, SNR is improved by more than 104 times. Our schemes offer great potential for reducing phototoxicity and extracting extremely weak signals from huge backgrounds and open up a new possibility for a rapid, flexible, and reliable medical diagnosis by TPPL imaging with diminished laser powers.

Coherent Interference Fringes of Two-Photon Photoluminescence in Individual Au Nanoparticles: The Critical Role of the Intermediate State.

The interaction between light and metal nanoparticles enables investigations of microscopic phenomena on nanometer length and ultrashort timescales, benefiting from strong confinement and enhancement of the optical field. However, the ultrafast dynamics of these nanoparticles are primarily investigated by multiphoton photoluminescence on picoseconds or photoemission on femtoseconds independently. Here, we presented two-photon photoluminescence (TPPL) measurements on individual Au nanobipyramids (AuNP) to reveal their ultrafast dynamics by double-pulse excitation on a global timescale ranging from subfemtosecond to tens of picoseconds. Two orders of magnitude photoluminescence enhancement, namely, coherent interference fringes, has been demonstrated. Power-dependent measurements uncovered the transform of the nonlinearity from 1 to 2 when the interpulse delay varied from tens of femtoseconds to tens of picoseconds. We proved that the real intermediate state plays a critical role in the observed phenomena, supported by numerical simulations with a three-state model. Our results provide insight into the role of intermediate states in the ultrafast dynamics of noble metal nanoparticles. The presence of the intermediate states in AuNP and the coherent control of state populations offer interesting perspectives for imaging, sensing, nanophotonics, and in particular, for preparing macroscopic superposition states at room temperature and low-power superresolution stimulated emission depletion microscopy.

Dithienocoronene diimide (DTCDI)-derived triads for high-performance air-stable, solution-processed balanced ambipolar organic field-effect transistors.

Developing ambipolar organic semiconducting materials is essential for use in complementary-like inverters and light-emitting transistors. In this study, three new dithienocoronenediimide (DTCDI)-derived triads, DTCDI-BT, DTCDI-BBT and DTCDI-BNT, were designed and synthesized, in which various sizes of terminal groups, i.e., thiophene (T), benzo[b]thiophene (BT) and naphtha[2,3-b]thiophene (NT) were substituted at the α-positions of the two thiophene rings of DTCDI, respectively. The DFT calculations reveal that the HOMO energy levels of the three triads when compared to that of the parent DTCDI-core (-5.99 eV) are significantly increased to -5.59, -5.59 and -5.45 eV for DTCDI-BT, DTCDI-BBT and DTCDI-BNT, respectively, whereas the LUMO energy levels (-3.07 eV ∼ -3.14 eV) are almost identical with that of the DTCDI-core (-3.10 eV). The results predict that the triads could possess ambipolar transport properties in organic field-effect transistor (OFET) applications. In fact, under an ambient atmosphere, solution-processed bottom-gate top-contact (BGTC) transistors exhibit ambipolar charge transport properties by tuning the HOMOs of the DTCDI-based triads so that they were suitable for hole injection, resulting in balanced maximum electron and hole mobilities of 1.66 × 10-3 and 1.02 × 10-3 cm2 V-1 s-1 for DTCDI-BT, 2.60 × 10-2 and 3.60 × 10-2 cm2 V-1 s-1 for DTCDI-BBT, and 2.43 × 10-3 and 4.15 × 10-3 cm2 V-1 s-1 for DTCDI-BNT, respectively. This is the first time that the DTCDI building block has been used to develop ambipolar small molecular semiconductors, and achieved a device performance comparable to that of the DTCDI-based polymeric semiconductors. In addition, DTCDI-BBT-based complementary-like inverters were made, and the inverter devices operated well in both p-mode and n-mode under ambient conditions. The results show that the DTCDI is a promising π-electron-deficient building block which could be further used to develop ambipolar semiconducting materials for OFET devices.

Photostable fluorescent molecules on layered hexagonal boron nitride: Ideal single-photon sources at room temperature.

Photoblinking and photobleaching are commonly encountered problems for single-photon sources. Numerous methods have been devised to suppress these two impediments; however, either the preparation procedures or the operating conditions are relatively harsh, making them difficult to apply to practical applications. Here, we reported giant suppression of both photoblinking and photobleaching of a single fluorescent molecule, terrylene, via the utilization of hexagonal boron nitride (h-BN) flakes as substrates. Experimentally, a much-prolonged survival time of terrylene has been determined, which can have a photostable emission over 2 h at room temperature under ambient atmospheres. Compared with single molecules on a SiO2/Si substrate or glass coverslip, a more than 100-fold increase in the total number of photons collected from each terrylene on h-BN flakes has been demonstrated. We also proved that the photostability of terrylene molecules can be well maintained for more than 6 months even under ambient conditions without any further protection. Our results demonstrate that the utilization of h-BN flakes to suppress photoblinking and photobleaching of fluorescent molecules has promising applications in the production of high-quality single-photon sources at room temperature.

Blinking Mechanisms and Intrinsic Quantum-Confined Stark Effect in Single Methylammonium Lead Bromide Perovskite Quantum Dots.

Lead halide perovskite quantum dots (QDs) are promising materials for next-generation photoelectric devices because of their low preparation costs and excellent optoelectronic properties. In this study, the blinking mechanisms and the intrinsic quantum-confined Stark effect (IQCSE) in single organic-inorganic hybrid CH3 NH3 PbBr3 perovskite QDs using single-dot photoluminescence (PL) spectroscopy is investigated. The PL quantum yield-recombination rates distribution map allows the identification of different PL blinking mechanisms and their respective contributions to the PL emission behavior. A strong correlation between the excitation power and the blinking mechanisms is reported. Most single QDs exhibit band-edge carrier blinking under a low excitation photon fluence. While under a high excitation photon fluence, different proportions of Auger-blinking emerge in their PL intensity trajectories. In particular, significant IQCSEs in the QDs that exhibit more pronounced Auger-blinking are observed. Based on these findings, an Auger-induced IQCSE model to explain the observed IQCSE phenomena is observed.

Proof-of-Principle Experimental Demonstration of Twin-Field Type Quantum Key Distribution.

The twin-field (TF) quantum key distribution (QKD) protocol and its variants are highly attractive because they can beat the well-known fundamental limit of the secret key rate for point-to-point QKD without quantum repeaters (repeaterless bound). In this Letter, we perform a proof-of-principle experimental demonstration of TFQKD based on the protocol proposed by Curty, Azuma, and Lo, which removes the need for postselection on the matching of a global phase from the original TFQKD scheme and can deliver a high secret key rate. Furthermore, we employ a Sagnac loop structure to help overcome the major difficulty in the practical implementation of TFQKD, namely, the need to stabilize the phase of the quantum state over kilometers of fiber. As a proof-of-principle demonstration, the estimated secure key rate from our experimental TFQKD data at the high loss region surpasses the repeaterless bound of QKD with current technology.

Performance of single-photons communication using the multi-channel frequency coding scheme.

In this paper, optical communication at the single-photon level is experimentally demonstrated by using a multi-channel frequency coding scheme in which the information is decoded by using the single-photons modulation spectrum. By using the modulation spectrum, the coding scheme could work normally in a channel with high loss and noise. Besides, multiple modulation frequency components could be used in a wide bandwidth regardless of frequency aliasing; therefore, the multi-channel frequency coding scheme makes it possible for high-capacity single-photons communication.

Design and Synthesis of a Novel n-Type Polymer Based on Asymmetric Rylene Diimide for the Application in All-Polymer Solar Cells.

A novel n-type polymer of PTDI-T based on asymmetric rylene diimide and thiophene is designed and synthesized. The highest power conversion efficiency of 4.70% is achieved for PTB7-Th:PTDI-T-based devices, which is obviously higher than those of the analogue polymers of PPDI-2T and PDTCDI. When using PBDB-T as a donor, an open-circuit voltage (VOC ) as high as 1.03 V is obtained. The results indicate asymmetric rylene diimide is a kind of promising building block to construct n-type photovoltaic polymers.

Effect of breviscapine on CYP3A metabolic activity in healthy volunteers.

OBJECTIVE: The purpose of this study was to investigate the influence of breviscapine on the pharmacokinetics of concomitantly administered midazolam (MID) and its associations with and effects on genetic polymorphism of the gene encoding cytochrome P450 3A5 (CYP3A5) in healthy volunteers. METHODS: The study group comprised 17 healthy volunteers who had been genotyped for CYP3A5*3 prior to start of the study. These volunteers were given daily doses of 120 mg (40 mg, three times a day) of breviscapine or a placebo for 14 days, followed by 7.5 mg midazolam (MID) on day 15. The plasma concentrations of MID and the metabolite 1-hydroxy-midazolam (1-OH-MID) were determined by ultra-performance liquid chromatography-mass spectrometry for up to 12 h after drug administration. RESULTS: The pharmacokinetics of MID and 1-OH-MID were significantly different between the breviscapine and placebo groups, with a point estimate for MID AUC(0-12) of 1.56 (90% confidence interval 1.26, 1.87). The pharmacokinetics of MID and 1-OH-MID were not different among the CYP3A5 genotype groups, regardless of whether MID was coadministered with breviscapine or with placebo. CONCLUSIONS: These findings suggest that breviscapine inhibited the metabolism of CYP3A in the volunteers, with no interaction difference among the different CYP3A5 genotypes.

Hybrid host materials for highly efficient electrophosphorescence and thermally activated delayed fluorescence independent of the linkage mode.

Three non-conjugated hybrid host materials, tBu-OXD-o-L-TPA, tBu-OXD-m-L-TPA, and tBu-OXD-p-L-TPA, have been synthesized and characterized for their thermal, electrochemical, fluorescence, phosphorescence, and electroluminescence properties. Due to the non-conjugated spacer, the three hosts have a similar ET value as high as 2.71 eV, which is sufficiently high for blue phosphorescent and thermally activated delayed fluorescent (TADF) emitters. Different from the hosts with a direct linkage between a donor and an acceptor showing significantly distinct properties depending on linkage modes, the three new hosts demonstrate similar photophysical, electrochemical, and organic light-emitting device performances. Both phosphorescent and TADF devices with high efficiencies have been realized using all the three hosts. These results reveal a new merit of employing a non-conjugated spacer, which enables the synthesized hosts to show properties independent of the linkage mode. This might facilitate choosing materials with an economical synthesis process while not influencing their properties and thus enhance the potential of universal host materials.

Functionalization of Pyrene To Prepare Luminescent Materials-Typical Examples of Synthetic Methodology.

Pyrene-based π-conjugated materials are considered to be an ideal organic electro-luminescence material for application in semiconductor devices, such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaics (OPVs), and so forth. However, the great drawback of employing pyrene as an organic luminescence material is the formation of excimer emission, which quenches the efficiency at high concentration or in the solid-state. Thus, in order to obtain highly efficient optical devices, scientists have devoted much effort to tuning the structure of pyrene derivatives in order to realize exploitable properties by employing two strategies, 1) introducing a variety of moieties at the pyrene core, and 2) exploring effective and convenient synthetic strategies to functionalize the pyrene core. Over the past decades, our group has mainly focused on synthetic methodologies for functionalization of the pyrene core; we have found that formylation/acetylation or bromination of pyrene can selectly lead to functionalization at K-region by Lewis acid catalysis. Herein, this Minireview highlights the direct synthetic approaches (such as formylation, bromination, oxidation, and de-tert-butylation reactions, etc.) to functionalize the pyrene in order to advance research on luminescent materials for organic electronic applications. Further, this article demonstrates that the future direction of pyrene chemistry is asymmetric functionalization of pyrene for organic semiconductor applications and highlights some of the classical asymmetric pyrenes, as well as the latest breakthroughs. In addition, the photophysical properties of pyrene-based molecules are briefly reviewed. To give a current overview of the development of pyrene chemistry, the review selectively covers some of the latest reports and concepts from the period covering late 2011 to the present day.