High Q-Factor Single-Mode Lasing in Inorganic Perovskite Microcavities with Microfocusing Field Confinement.

The realization of high-Q single-mode lasing on the microscale is significant for the advancement of on-chip integrated light sources. It remains a challenging trade-off between Q-factor enhancement and light-field localization to raise the lasing emission rate. Here, we fabricated a zero-dimensional perovskite microcavity integrated with a nondamage pressed microlens to three-dimensionally tailor the intracavity light field and demonstrated linearly and nonlinearly (two-photon) pumped lasing by this microfocusing configuration. Notably, the microlensing microcavity experimentally achieves a high Q-factor (16700), high polarization (99.6%), and high Purcell factor (11.40) single-mode lasing under high-repetition pulse pumping. Three-dimensional light-field confinement formed by the microlens and plate microcavity simultaneously reduces the mode volume (∼3.66 µm3) and suppresses diffraction and transverse walk-off loss, which induces discretization on energy-momentum dispersions and spatial electromagnetic-field distributions. The Q factor and Purcell factor of our lasing come out on top among most of the reported perovskite microcavities, paving a promising avenue toward further studying electrically driven on-chip microlasers.

Regulating Phase Distribution of Dion-Jacobson Perovskite Colloidal Multiple Quantum Wells Toward Highly Stable Deep-Blue Emission.

Metal halide perovskite colloidal quantum wells (CQWs) hold great promise for modern photonics and optoelectronics. However, current studies focus on Ruddlesden-Popper (R-P) phase perovskite CQWs that contain bilayers of monovalent long-chain alkylamomoniums between the separated perovskite octahedra layers. The bilayers are packed back-to-back via weak van der Waals interaction, resulting in inferior charge carrier transport and easier decomposition of perovskite. This report first creates a new type of perovskite colloidal multiple QWs (CMQWs) in the form of Dion-Jacobson (D-J) structure by introducing an asymmetric diammonium cation. Furthermore, the phase distribution is optimized by the synergistic effect of valeric acid and zwitterionic lecithin, finally achieving pure deep-blue emission at 435 nm with narrow full width at half maximum. The diammonium layer in D-J perovskite CMQWs features extremely short width of only ≈0.6 nm, thereby contributing to more effective charge carrier transport and higher stability. Through the continuous photoluminescence (PL) measurement and corresponding theoretical calculation, the higher stability of D-J perovskite CMQWs than that of R-P structural CMQWs is confirmed. This work reveals the inherent superior stability of D-J structural CMQWs, which opens a new direction for fabricating stable perovskite optoelectronics.

Persistent Charging of CsPbBr3 Perovskite Nanocrystals Confined in Glass Matrix.

Manipulation of persistent charges in semiconductor nanostructure is the key point to obtain quantum bits towards the application of quantum memory and information devices. However, realizing persistent charge storage in semiconductor nano-systems is still very challenge due to the disturbance from crystal defects and environment conditions. Herein, the two-photon persistent charging induced long-lasting afterglow and charged exciton formation are observed in CsPbBr3 perovskite nanocrystals (NCs) confined in glass host with effective lifetime surpassing one second, where the glass inclosure provides effective protection. A method combining the femtosecond and second time-resolved transient absorption spectroscopy is explored to determine the persistent charging possibility of perovskite NCs unambiguously. Meanwhile, with temperature-dependent spectroscopy, the underlying mechanism of this persistent charging is elucidated. A two-channel carrier transfer model is proposed involving athermal quantum tunneling and slower thermal-assisted channel. On this basis, two different information storage devices are demonstrated with the memory time exceeding two hours under low-temperature condition. These results provide a new strategy to realize persistent charging in perovskite NCs and deepen the understanding of the underlying carrier kinetics, which may pave an alternative way towards novel information memory and optical data storage applications.

Mapping the Identity of Transition Metal Doping and Surface Passivation in Indium Phosphide with Theoretical Calculation.

Understanding the electronic structure of doped InP quantum dots (QDs) is essential to optimize the material for specific optoelectronic applications. However, current synthesis approaches are often tedious and unfavorable for rational tunning. Herein, a combination of experimental and computational studies was conducted to address the doping mechanism and surface passivation of InP QDs. The successful dopant introduction requires low Cu doping concentration and heavy Mn doping, while the Ag doping amount is relatively moderate. This may correspond to the theoretical doping formation energy presented as Cu (-2.52 eV) < Ag (-1.76 eV) < Mn (-0.38 eV). As for surface passivation, inorganic ions and shell-like ZnS are unraveled through simulational investigation. Chloride ion promotes oriented growth toward tetrahedron morphology while nitrate-passivated InP QDs exhibit blurry transmission electron microscope (TEM) morphology. Correspondingly, the binding energy of chloride ion with (111) facet is -2.13 eV significantly lower than those of (110) and (100) facets. Further, the additional Zn 3d bands are more involved in the formation of conduction band, which optimized the Mn-doped InP with a 0.32 eV bandgap. These experimental and model results provide more microscopic details of doped InP, which can motivate theoretically exact control of guest ion stoichiometry with optimized characteristics for electrical devices.

Recent Advances in Blue Perovskite Quantum Dots for Light-Emitting Diodes.

Metal halide perovskite nanostructures have sparked intense research interest due to their excellent optical properties. In recent years, although the green and red perovskite light-emitting diodes (PeLEDs) have achieved a significant breakthrough with the external quantum efficiency exceeding 20%, the blue PeLEDs still suffer from inferior performance. Previous reviews about blue PeLEDs focus more on 2D/quasi-2D or 3D perovskite materials. To develop more stable and efficient blue PeLEDs, a systematic review of blue perovskite quantum dots (PQDs) is urgently demanded to clarify how PQDs evolve. In this review, the recent advances in blue PQDs involving mixed-halide, quantum-confined all-bromide, metal-doped and lead-free PQDs as well as their applications in PeLEDs are highlighted. Although several excellent PeLEDs based on these PQDs have been demonstrated, there are still many problems to be solved. A deep insight into the advantages and disadvantages of these four types of blue-emitting PQDs is provided. Then, their respective potential and issues for blue PeLEDs have been discussed. Finally, the challenges and outlook for efficient and stable blue PeLEDs based on PQDs are addressed.

Synergistic Effect of Halogen Ions and Shelling Temperature on Anion Exchange Induced Interfacial Restructuring for Highly Efficient Blue Emissive InP/ZnS Quantum Dots.

InP quantum dots (QDs) have attracted much attention owing to their nontoxic properties and shown great potential in optoelectronic applications. Due to the surface defects and lattice mismatch, the interfacial structure of InP/ZnS QDs plays a significant role in their performance. Herein, the formation of In-S and Sx -In-P1-x interlayers through anion exchange at the shell-growth stage is revealed. More importantly, it is proposed that the composition of interface is dependent on the synergistic effect of halogen ions and shelling temperature. High shelling temperature contributes to the optical performance improvement resulting from the formation of interlayers, besides the thicker ZnS shell. Moreover, the effect relates to the halogen ions where I- presents more obvious enhancement than Br- and Cl- , owing to their different ability to coordinate with In dangling bonds, which are inclined to form In-S and Sx -In-P1-x bonds. Further, the anion exchange under I- -rich environment causes a blue-shift of emission wavelength with shelling temperature increasing, unobserved in a Cl- - or Br- -rich environment. It contributes to the preparation of highly efficient blue emissive InP/ZnS QDs with emission wavelength of 473 nm, photoluminescence quantum yield of ≈50% and full width at half maximum of 47 nm.

A novel material Cs2RbxAg1-xIn0.875Bi0.125Cl6 with a special blue shift and application for white light LED devices.

Perovskite microcrystals have attracted wide attention and have been applied in extensive optical applications. The CsPbX3 perovskite poses a great threat to the environment due to the presence of lead (Pb), and there is an urgent need to improve the photoluminescence quantum yield. Therefore, a lead-free perovskite microcrystal material Cs2RbxAg1-xIn0.875Bi0.125Cl6 with a high photoluminescence quantum yield (PLQY) was synthesized by a convenient hydrothermal method, with comprehensive characterization of both the structure and optical performance at varying Rb ratios. Optimal properties were observed at x = 0.15 with bright white emission and a PLQY of 32.15%. Superior stability of the novel material in ethanol was observed under the radiation of an excitation light of 365 nm. Interestingly, a blue shift of the emission peak occurred after exposure to humid air, possibly due to the reconstruction of the crystal structure. Moreover, a LED device packaged with this novel material was developed with a desirable color temperature of 3190 K, promising for further lighting applications.

Advances of Nonlinear Photonics in Low-Dimensional Halide Perovskites.

Hybrid halide perovskites emerging as a highly promising class of functional materials for semiconductor optoelectronic applications have drawn great attention from worldwide researchers. In the past few years, prominent nonlinear optical properties have been demonstrated in perovskite bulk structures indicating their bright prospect in the field of nonlinear optics (NLO). Following the surge of 3D perovskites, more recently, the low-dimensional perovskites (LDPs) materials ranging from two-, one-, to zero-dimension such as quantum-wells or colloidal nanostructures have displayed unexpectedly attractive NLO response due to the strong quantum confinement, remarkable exciton effect, and structural diversity. In this perspective, the current state of the art is reviewed in the field of NLO for LDP materials. The relationship between confinement effect and NLO is analyzed systematically to give a comprehensive understanding of the function of dimension reduction. Furthermore, future directions and challenges toward the improvement of the NLO in LDP materials are discussed to provide an outlook in this rapidly developing field.

Phase Tailoring of Ruddlesden-Popper Perovskite at Fixed Large Spacer Cation Ratio.

Ruddlesden-Popper (RP) metal halide perovskites are considered as promising optoelectronic materials due to their good environmental stability and desirable optoelectronic properties. However, the phase composition and ordering in the deposited film, with a fixed ratio of large organic spacer cation in the precursor solution, are hard to be further tailored for specific optoelectronic applications. Herein, it is shown that even with a fixed spacer cation ratio, the phase composition and ordering can still be largely regulated by utilizing different crystallization kinetics of various cations with the inorganic octahedral lead halide. By using two different short cations to compete with the large spacer cation, the phase composition can be continuously tailored from thin multiple quantum wells (MQWs) dominated to 3D perovskite dominated. The phase ordering can be reversed from small n phases' prior to large n phases' prior near the substrate. Finally, with the same amount of large spacer cation protection, the perovskite can be tailored for both high-performance electroluminescence and photovoltaics with favorable energetic landscape for the corresponding desired first-order excitonic recombination and second-order free electron-hole recombination, respectively. This exploration substantially contributes to the understanding of precise phase engineering in RP perovskite and may provide a new insight into the design of multiple functional devices.

Optical and Morphological Properties of Single-Phased and Dual-Emissive InP/ZnS Quantum Dots via Transition Metallic and Inorganic Ions.

Single-phased and dual-emissive nanocrystals with broad emission are attractive fluorescent materials for optoelectronic devices due to their unique properties. Until now, the effect of different metallic cations and inorganic anions on III-V group quantum dots (QDs) concerning luminescence features and crystalline growth has been less explored. In this work, dual-emissive InP/ZnS QDs single-doped with transition-metal compounds (Cu2+, Ag+, or Mn2+) are synthesized to compare their optical and morphological properties. The corresponding doping concentrations to realize dual emission with comparative intensity for Cu, Ag, and Mn are 0.8, 6, and 80%, which vary greatly and might be attributed to different precursor reactivities. As for the morphological and internal structures, transmission electron microscopy (TEM) images indicate that transition-metal ions have no obvious effect on the morphological properties and a higher concentration of chloride anions binding with an In-rich interface could conduce to a homogeneous distribution and triangular growth through the comparison of different metal chlorides as precursors. X-ray photoelectron spectroscopy (XPS) results further demonstrate that the high-resolution In 3d spectrum of Mn-doped InP/ZnS QDs with MnCl2 is mainly dominated by In-P bonds, indicating fewer intermediate chemical states. These results concerning well-defined InP/ZnS QDs could promote more diverse insight into surface chemistry and help to better understand the growth mechanism, thus making it possible to regulate InP/ZnS QDs into desired formats for different practical applications like white light-emitting diodes (LEDs).

Dual-emission of silicon nanoparticles encapsulated lanthanide-based metal-organic frameworks for ratiometric fluorescence detection of bacterial spores.

Dipicolinic acid (DPA) is employed as a significant biomarker to detect Bacillus anthracis, which can do serious damages to the health of human beings. Hence, it is crucial to develop a fast and highly efficient strategy for DPA monitoring. In this work, based on silicon nanoparticles (Si NPs) and terbium metal-organic frameworks (Tb-MOFs), a hybrid structure (Si NPs/Tb-MOFs) as a novel dual-emitting fluorescence probe was fabricated for ratiometric detection of DPA, where blue light-emitting Si NPs (Ex: 280 nm; Em: 422 nm) are encapsulated into green light-emitting Tb-MOFs (Ex: 280 nm; Em: 547 nm). The optical properties and chemical composition of the as-obtained Si NPs/Tb-MOFs were characterized in detail. The Si NPs/Tb-MOFs probe not merely possesses the merits of a facile synthesis method but also is an excellent fluorescence probe. The response time towards DPA is less than 30 s, revealing that the process of detecting DPA can be completed in such a short time. The limit of detection for DPA is 5.3 nM, which is four orders of magnitude lower than an infectious dosage of anthrax spores for human beings (60 µM). This dual-emitting Si NPs/Tb-MOFs probe with interference-free and self-calibrating properties may be a potential candidate for further development in medical diagnosis. Graphical abstract.

Carbon Quantum Dots for Long-Term Protection against UV Degradation and Acidification in Paper-Based Relics.

Paper-based cultural relics constitute a significant and invaluable part of human civilization and cultural heritage. However, they are highly vulnerable to environmental factors such as ultraviolet (UV) photodegradation and acidification degradation, posing substantial threats to their long-term preservation. Carbon quantum dots (CQDs), known for their outstanding optical properties, high water solubility, and good safety, offer a promising solution for slowing down UV damage and acidification of paper-based relics during storage and transportation. Herein, we propose a feasible strategy for the simple preparation of CQDs with high dispersion stability, excellent UV absorption, room-temperature phosphorescence, and photostability for the safety protection of paper. Accelerated aging experiments were conducted using UV and dry-heat aging methods on both CQD-protected paper and unprotected paper, respectively, to evaluate the effectiveness of CQD protection. The results demonstrate a slowdown in both the oxidation and acid degradation processes of the protected paper under both UV-aging and dry-heat aging conditions. Notably, CQDs with complex luminescence patterns of both fluorescence and room-temperature phosphorescence also endue them as enhanced optical anticounterfeiting materials for multifunctional paper protection. This research provides a new direction for the protection of paper-based relics with emerging carbon nanomaterials.

White-Light GaN-µLEDs Employing Green/Red Perovskite Quantum Dots as Color Converters for Visible Light Communication.

GaN-based µLEDs with superior properties have enabled outstanding achievements in emerging micro-display, high-quality illumination, and communication applications, especially white-light visible light communication (WL-VLC). WL-VLC systems can simultaneously provide white-light solid-state lighting (SSL) while realizing high-speed wireless optical communication. However, the bandwidth of conventional white-light LEDs is limited by the long-lifetime yellow yttrium aluminum garnet (YAG) phosphor, which restricts the available communication performance. In this paper, white-light GaN-µLEDs combining blue InGaN-µLEDs with green/red perovskite quantum dots (PQDs) are proposed and experimentally demonstrated. Green PQDs (G-PQDs) and red PQDs (R-PQDs) with narrow emission spectrum and short fluorescence lifetime as color converters instead of the conventional slow-response YAG phosphor are mixed with high-bandwidth blue InGaN-µLEDs to generate white light. The communication and illumination performances of the WL-VLC system based on the white-light GaN-based µLEDs are systematically investigated. The VLC properties of monochromatic light (green/red) from G-PQDs or R-PQDs are studied in order to optimize the performance of the white light. The modulation bandwidths of blue InGaN-µLEDs, G-PQDs, and R-PQDs are up to 162 MHz, 64 MHz, and 90 MHz respectively. Furthermore, the white-light bandwidth of 57.5 MHz and the Commission Internationale de L'Eclairage (CIE) of (0.3327, 0.3114) for the WL-VLC system are achieved successfully. These results demonstrate the great potential and the direction of the white-light GaN-µLEDs with PQDs as color converters to be applied for VLC and SSL simultaneously. Meanwhile, these results contribute to the implementation of full-color micro-displays based on µLEDs with high-quality PQDs as color-conversion materials.

Facile synthesis of red-emissive carbon dots with theoretical understanding for cellular imaging.

Recently, red emissive carbon dots (R-CDs) have drawn widespread attention on account of their desirable fluorescence properties and good biocompatibility. Despite great efforts, facile synthesis of R-CDs for cellular imaging remains challenging and the fluorescence mechanism of R-CDs is still elusive. Herein, p-phenylenediamine-derived R-CDs with excitation-independency were successfully obtained through a facile solvothermal approach together with proportional precipitation. The fluorescent solvatochromism of R-CDs is realized, while high polarity leads to higher degree of dipole interaction between R-CDs and different solvents, favoring for emissive red-shift. Furthermore, density functional theory is adopted to explore the optical and electronic characteristics of some polycyclic aromatic molecules. Among different configurations, pyridine nitrogen and carbonyl bonds could relatively increase the charge density and significantly narrow the band gap, which can provide a crucial theoretical basis for the precise preparation of R-CDs. Moreover, R-CDs possess favorable cellular imaging ability, which indicates their potential for a promising candidate as fluorescence probes in bioimaging.

Gadolinium-doped carbon dots with high-performance in dual-modal molecular imaging.

Carbon dots (CDs), possessing unexpected advantages of photostability, biocompatibility and low toxicity, are regarded as novel nanomaterials in fluorescence (FL) imaging. Doping Gd element in CDs makes them have the ability to be used for magnetic resonance (MR) and FL imaging simultaneously. However, CDs reported before exhibit obvious defects like low photoluminescence (PL) quantum yield (QY) or biotoxicity. In this work, we use gadolinium meglumine, a material with relatively low biotoxicity, along with citric acid and diethylenetriamine to synthesize Gd-doped CDs (Gd-CDs) by a one-step hydrothermal method. The prepared Gd-CDs exhibit excitation-independent emission with a PL QY of 78.05% and a longitudinal relaxivity of 7.37 mM-1 S-1, which endows the composite with high-performance in MR/FL imaging. Meanwhile, the FL intensity of Gd-CDs remains stable in the presence of multiple amino acids, which indicates that the FL imaging effect should not be impacted significantly in microenvironments in vivo. In addition to the inconspicuous cytotoxicity, Gd-CDs could be used efficiently for dual-modal molecular imaging to detect diseases such as tumors in the early stages.

Correction: Gadolinium-doped carbon dots with high-performance in dual-modal molecular imaging.

Correction for 'Gadolinium-doped carbon dots with high-performance in dual-modal molecular imaging' by Le Wang et al., Anal. Methods, 2021, 13, 2442-2449, DOI: 10.1039/d1ay00270h.

Cation Crosslinking-Induced Stable Copper Nanoclusters Powder as Latent Fingerprints Marker.

Luminescent copper nanoclusters (Cu NCs) have shown great potential in light-emitting devices (LEDs), chemical sensing, catalysis and biological fields. However, their practical use has been restricted by poor stability, and study on the stability of Cu NCs solid powder along with the mechanism is absent. In this study, stablized Cu NCs powder was first obtained by cation crosslinking method. Compared with the powder synthesized by solvent precipitation method, the stability of Cu NCs powder crosslinked by ionic inducer Ce3+ was enhanced around 100-fold. The storage time when the fluorescence intensity decreased to 85% (T85) was improved from 2 h to 216 h, which is the longest so far. The results of characterizations indicated that the aggregation structure was formed by the binding of Ce3+ with the capping ligands of Cu NCs, which helped in obtaining Ce-Cu NCs powder from aggregate precipitation in solution. Furthermore, this compact structure could avoid the destruction of ambient moisture resulting in long-lasting fluorescence and almost unchanged physical form. This demonstrated that phosphor, with excellent characteristics of unsophisticated synthesis, easy preservation and stable fluorescence, showed great potential in light sources, display technology and especially in latent fingerprints visualization on different substrates for forensic science.

Surface States Induced Photoluminescence Enhancement of Nitrogen-Doped Carbon Dots Via Post-Treatments.

The tunable photoluminescence (PL) of nitrogen-doped carbon dots (NCDs) has attracted much attention in recent years while the specific mechanism is still in dispute. Herein, NCDs with yellow emission were successfully synthesized via a facile hydrothermal approach. Three kinds of post-treatment routes were investigated to verify the influence of surface states on the PL emission of NCDs including solvent-dependent, reduced-reaction and metal-enhanced effect. The interaction mechanism was studied by absorption spectrum, structural characterizations, steady-state and time-resolved spectroscopy. When dispersed in different solvents, the as-prepared NCDs show tunable emission and PL enhancement attributed to hydrogen bonding between solvents and NCDs. Besides, the addition of NaBH4 can induce the reduction of the C=O bonds existing in original NCDs to C-O bonds and thus result in the enhancement of the intrinsic (n-π*) emission. Moreover, metal-enhanced fluorescence of NCDs can also be observed when adding Ag+ into initial NCD solution, which might be ascribed to aggregation-induced emission enhancement. These results for post-treated NCDs demonstrate that surface functional groups are responsible for PL emission and provide new possibilities like multi-image sensing and lighting application.

Facile Synthesis and Optical Properties of CsPbX3/ZIF-8 Composites for Wide-Color-Gamut Display.

All-inorganic CsPbX3 (X = Cl, Br, and I) perovskite quantum dots (QDs), an emerging type of luminescent materials, have drawn extensive attention in recent years. However, the amelioration of their stability is becoming a critical issue. Herein, we present a facile and efficient approach to prepare novel perovskite QDs/metal-organic frameworks (CsPbX3/ZIF-8) composites under ambient-atmospheric conditions. The obtained composites exhibit better properties including high photoluminescence (PL) quantum yields (QYs) (41.2% for green and 34.8% for red), narrow-band emission (20 nm for green and 31 nm for red), and enhanced stability in comparison to bare QDs. Furthermore, their application in a remote-type white-light-emitting device was explored and a wide color gamut (~137% of the National Television System Committee standard) was achieved, verifying that these novel luminescent composites have great prospect in backlight display application.

Ultraviolet-pumped white light emissive carbon dot based phosphors for light-emitting devices and visible light communication.

Herein, we report UV-pumped white light emissive carbon dot (CD)-based phosphors to prevent blue light hazard in phosphor-converted WLEDs. Then, UV-pumped WLEDs with a color rendering index exceeding 85 and VLC with a modulation bandwidth of 75 MHz and a data transmission rate of 224 Mbps have been realized.