Multifunctional interfacial molecular bridge enabled by an aggregation-induced emission strategy for enhancing efficiency and UV stability of perovskite solar cells

The interface defects between the electron transport layer(ETL)and the perovskite layer,as well as the low ultraviolet(UV)light utilization rate of the perovskite absorption layer,pose significant challenges for the commercialization of perovskite solar cells(PSCs).To address this issue,this paper proposes an innovative multifunctional interface modulation strategy by introducing aggregation-induced emission(AIE)molecule 5-[4-[1,2,2-tri[4-(3,5-dicarboxyphenyl)phenyl]ethylene]phenyl]benzene-1,3-dicarboxylic acid(H_(8)ETTB)at the SnO_(2)ETL/perovskite interface.Firstly,the interaction of H_(8)ETTB with the SnO_(2)surface,facilitated by its carboxyl groups,is effective in passivating surface defects caused by noncoord inated Sn and O vacancies.This interaction enhances the conductivity of the SnO_(2)film and adjusts energy levels,leading to enhanced charge carrier transport.Simultaneously,H_(8)ETTB can passivate noncoord inated Pb^(2+)ions at the perovskite interface,promoting perovskite crystallization and reducing the interface energy barrier,resulting in a perovskite film with low defects and high crystalline quality.More importantly,the H_(8)ETTB molecule,can convert UV light into light absorbable by the perovskite,thereby reducing damage caused by UV light and improving the device's utilization of UV.Consequently,the champion PSC based on SnO_(2)-H_(8)ETTB achieves an impressing efficiency of 23.32%and significantly improved photostability compared with the control device after continuous exposure to intense UV radiation.In addition,the Cs_(0.05)(FA_(0.95)MA_(0.05))_(0.95)Pb(I_(0.95)Br_(0.05))_(3)based device can achieve maximum efficiency of 24.01%,demonstrating the effectiveness and universality of this strategy.Overall,this innovative interface bridging strategy effectively tackles interface defects and low UV light utilization in PSCs,presenting a promising approach for achieving highly efficient and stable PSCs.

Utilization of aggregation-induced emission materials in urinary system diseases

With the development of aggregation-induced emission(AIE)materials,the draw-backs of conventionalfluorescence materials subjected to aggregation-caused quenching(ACQ)have been resolved.This has allowed for the improvement of novel AIEfluorescent materials that exhibit enhanced photostability,a higher signal-to-noise ratio,and better imaging quality.Meanwhile,the enhanced phototherapeutic effect of AIE materials has garnered widespread attention in the realm of tumor treatment.The distinct physiological and anatomical characteristics of the urinary system make it suitable for the use of AIE materials.Additionally,AIE-based pho-totherapy provides a superior solution to deal with the weaknesses of conventional treatments for urologic neoplasms.In this review,the scientific advancement on the use of AIE materials in urinary system diseases since the emergence of the AIE con-cept is reviewed in detail.The review highlights the promise of AIE materials for biomarkers detection,fluorescence imaging(FLI)in vivo and in vitro,AIE-based phototherapy,and synergistic therapy from both diagnostic and therapeutic view-points.It isfirmly believed that AIE materials hold immense untapped potential for the diagnosis and treatment of urologic disease,as well as all diseases of the human body.

1,1’-Binaphthol annulated perylene diimides: Aggregation-induced emission enhancement and chirality inversion

Aggregation-induced emission enhancement and aggregation-induced chirality inversion are two individ-ual phenomena for the enantiomerically pure organic dyes in the aggregates.Herein we reported for the first time that these two interesting phenomena could be observed simultaneously in the aggregated states of enantiomerically pure S/R-1,1?-binaphthol annulated perylene diimides,in which two perylene diimides moieties were bridged by S/R-1,1?-binaphthol(BINOL)at the bay positions.Owing to the rotat-able C2 axes between two naphthol annulated perylene diimides moieties,both of them display intrinsic behaviors of aggregation-induced emission enhancements.At the same time,due to the steric hindrances in the imide and methoxy positions,the neighboring twoπ-systems of these two unique polycyclic aro-matic imides in poor solvents are preferable to adopt a cross-stacking mode and thus form helical X-aggregates of opposite chirality(M/P)with chirality inversion characteristics in their circular dichroism and circularly polarized luminescence spectroscopic studies.

Aggregation-induced emission enhancement of yellow photoluminescent carbon dots for highly selective detection of environmental and intracellular copper(Ⅱ) ions

Carbon dots (CDs) are prepared through a simple one-step hydrothermal treatment of o-phenylendiamine (OPD) and show yellow photoluminescent (PL) emission under the ultraviolet excitation, which can be further enhanced by Cu2+ ions owing to Cu2+ ions induced aggregation of OPD-CDs through the coordination of Cu2+ with amino groups on the surface of OPD-CDs. The aggregation induced emission enhancement (AIEE) property enables it feasible to develop a simple, sensitive and selective method to detect environmental and intracellular copper (Ⅱ) ions. The limit of detection as lowas 0.28 μmol/L (3σ/k) and a dynamic range from 0.5 μmol/L to 40 μmol/L make it veryeasy to detect the copper content inwater samples, such as river closure reservoir. Furthermore, fluorescence imaging of intracellular Cu2+ suggests that the AIEE features of OPD-CDs specific to Cu2+ ions can be also applied in biological systems.

AGGREGATION-INDUCED EMISSION ENHANCEMENT IN POLY(PHENYLENE ETHYNYLENE)S BEARING ANILINE GROUPS

Poly（phenylene ethynylene）s （P1） with 4-vinylaniline pendant groups were successfully prepared by the Sonogashira coupling polymerization bevween 1,4-diethynyl-2,5-bis（pentyloxy）benzene and 4-[2-（2,5-dibromophenyl）vinyl]- aniline. In comparison with its analogue P2 without amino group, the emission of F＇I is only enihanced by aggregation when adding n-hexane into its THF solution, exhibiting an aggregation-induced emission enhancement （AIEE） effect. When methanol or water instead of hexane was added into THF solution, P1, however, didn＇t show AII：~E. The results indicated that amino groups strengthen the inter-chain and intra-chain interactions in P1 and restrict the no^-radiative energy transition. This strategy can provide a platform for developing highly sensitive and efficient bio- and chemosensors.

Highly specific characterization and discrimination of monosodium urate crystals in gouty arthritis based on aggregation-induced emission luminogens

Existing technologies used to detect monosodium urate(MSU)crystals for gout diagnosis are not ideal due to their low sensitivity and complexity of operation.The purpose of this study was to explore whether aggregation-induced emission luminogens(AIEgens)can be used for highly specific imaging of MSU crystals to assist in the diagnosis of gout.First,we developed a series of luminogens(i.e.,tetraphenyl ethylene(TPE)-NH_(2),TPE-2NH_(2),TPE-4NH_(2),TPE-COOH,TPE-2COOH,TPE-4COOH,and TPE-Ketoalkyne),each of which was then evenly mixed with MSU crystals.Next,optimal fluorescence imaging of each of the luminogens was characterized by a confocal laser scanning microscope(CLSM).This approach was used for imaging standard samples of MSU,hydroxyapatite(HAP)crystals,and mixed samples with 1:1 mass ratio of MSU/HAP.We also imaged samples from mouse models of acute gouty arthritis,HAP deposition disease,and comorbidities of interest.Subsequently,CLSM imaging results were compared with those of compensated polarized light microscopy,and we assessed the biosafety of TPE-Ketoalkyne in the RAW264.7 cell line.Finally,CLSM time series and three-dimensional imaging were performed on MSU crystal samples from human gouty synovial fluid and tophi.As a promising candidate for MSU crystal labeling,TPE-Ketoalkyne was found to detect MSU crystals accurately and rapidly in standard samples,animal samples,and human samples,and could precisely distinguish gout from HAP deposition disease.This work demonstrates that TPE-Ketoalkyne is suitable for highly specific and timely imaging of MSU crystals in gouty arthritis and may facilitate future research on MSU crystal-related diseases.

Experimental investigation for temperature and emissivity by flame emission spectrum in a cavity of rocket based combined cycle combustor chamber

Flame temperature and spectral emissivity were the important parameters characterizing the sufficient degree of fuel combustion and the particle radiative characteristics in the Rocket Based Combined Cycle(RBCC)combustor.To investigate the combustion characteristics of the complex supersonic flame in the RBCC combustor,a new radiation thermometry combined with Levenberg-Marquardt(LM)algorithm and the least squares method was proposed to measure the temperature,emissivity and spectral radiative properties based on the flame emission spectrum.In-situ measurements of the flame temperature,emissivity and spectral radiative properties were carried out in the RBCC direct-connected test bench with laser-induced plasma combustion enhancement(LIPCE)and without LIPCE.The flame average temperatures at fuel global equivalence ratio(a)of 1.0b and 0.6 with LIPCE were 4.51%and 2.08%higher than those without LIPCE.The flame combustion oscillation of kerosene tended to be stable in the recirculation zone of cavity with the thermal and chemical effects of laser induced plasma.The differences of flame temperature at a=1.0b and 0.6 were 503 K and 523 K with LIPCE,which were 20.07%and42.64%lower than those without LIPCE.The flame emissivity with methane assisted ignition was 80.46%lower than that without methane assisted ignition,due to the carbon-hydrogen ratio of kerosene was higher than that of methane.The spectral emissivities at 600 nm with LIPCE were 1.25%,22.2%,and 4.22%lower than those without LIPCE at a=1.0a(with methane assisted ignition),1.0b(without methane assisted ignition)and 0.6.The effect of concentration in the emissivity was removed by normalization to analyze the flame radiative properties in the RBCC combustor chamber.The maximum differences of flame normalized emissivity were 50.91%without LIPCE and 27.53%with LIPCE.The flame radiative properties were stabilized under the thermal and chemical effects of laser induced plasma at a=0.6.

Visualizing Photodynamic Therapy in Transgenic Zebrafish Using Organic Nanoparticles with Aggregation-Induced Emission

Photodynamic therapy(PDT) employs accumulation of photosensitizers(PSs) in malignant tumor tissue followed by the light-induced generation of cytotoxic reactive oxygen species to kill the tumor cells. The success of PDT depends on optimal PS dosage that is matched with the ideal power of light. This in turn depends on PS accumulation in target tissue and light administration time and period.As theranostic nanomedicine is driven by multifunctional therapeutics that aim to achieve targeted tissue delivery and image-guided therapy, fluorescent PS nanoparticle(NP)accumulation in target tissues can be ascertained through fluorescence imaging to optimize the light dose and administration parameters. In this regard, zebrafish larvae provide a unique transparent in vivo platform to monitor fluorescent PS bio-distribution and their therapeutic efficiency. Using fluorescent PS NPs with unique aggregation-induced emission characteristics, we demonstrate for the first time the real-time visualization of polymeric NP accumulation in tumor tissue and, more importantly, the best time to conduct PDT using transgenic zebrafish larvae with inducible liver hyperplasia as an example.

Aggregation-induced emission luminogen for in vivo three-photon fuorescence lifetime microscopic imaging

Compared with visible light,near infrared(NIR)light has deeper penetration in biological tisues.Three-photon fuorescence microscopy(3PFM)can effectively utilize the NIR excitation to obtain high-contrast images in the deep tisue.However,the weak three photon fluorescence signals may be not well presented in the traditional fuorescence intensity imaging mode.Fluorescence lifetime of certain probes is insensitive to the intensity of the excitation laser.Moreover,fluorescence lifetimne imaging microscopy(FLIM)can detect weak signals by utilizing time correlated single photon counting(TCSPC)technique.Thus,it would be an improved strategy to combine the 3PFM imaging with the FLIM together.Herein,DCDPP-2TPA,a novel agegation-induced emission luminogen(AIEgen),was adopted as the fluorescent probes.The three-photon absorption cros-section of the AlEgen,which has a deep-red fluorescence emission,was proved to be large.DCDPP-2TPA nanoparticles were synthesized,and the three photon fluorescence lifetime of which was measured in water.Moreover,in vrivo thre-photon fuorescence lifetime microscopic imaging of a craniotomy mouse was conducted via a home made optical system.High contrast cerebrovascular images of different vertical depths were obtained and the maximun depth was about 600 pumn.Even reaching the depth of 600 pum,tiny capillary vessels as small as 1.9 pum could still be distinguished.The three photon fuorescence lifetimes of the capillaries in some representative images were in accord with that of DCDPP-2TPA nanoparticles in water.A vivid 3D reconstruction was further organized to present a wealth of lifetime information.In the future,the combination strategy of 3PFM and FLIM could be further applied in the brain functional imaging.

Click-Formed Polymer Gels with Aggregation-Induced Emission and Dual Stimuli-Responsive Behaviors

Stimuli-responsive polymer gels have recently attracted great attention due to their heat/solvent resistance,dimensional stability,and unique sensitivity to external stimuli.In this work,we synthesized thiol-functionalized tetraphenylethylene(TPE)and constructed polymer gels through thiol-ene click reaction.The synthetic process of the polymer gels could be monitored by fluorescence emission of TPE moieties based on aggregation-induced emission mechanism.In addition,due to the dual redox-and acid responsiveness of the polymer gels,in the presence of dithiothreitol and trifluoroacetic acid,fluorescence quenching of the polymer gels can be observed.This stimuli-responsive characteristics endows the polymer gels with potential applications in fluorescent sensing and imaging,cancer diagnosis and selfhealing materials.

Time-resolved measurement of atomic emission enhancement by fs-ns dual-pulsed laser-induced breakdown spectroscopy

Time-resolved measurement of atomic emission enhancement is performed by using a 500-fs KrF laser pulse incident upon a high density supersonic O2 gas jet, synchronized with an orthogonal ns frequency-doubled Nd：YAG laser pulse. The ultra-short pulse serves as an igniter of the gas jet, and the subsequent ns-laser pulse significantly enhances the atomic emission. Analysis shows that the contributions to the enhancement effect are made mainly by the bremsstrahlung radiation and cascade ionization.

Aggregation-Induced Emission with Large Redshift in 2,7-Diphenylfluorenone:Reality or Artifact?

The luminescence property of 2,7-diphenyl-fluorenone(DPFO)was previously reported to be very unusual with a large aggregationinduced effect associated with a fluorescence redshift of 150 nm.The phenomenon is reexamined in this work.It is found that the abnormal observations are caused by the presence of a trace amount of impurity 2,7-diphenyl-fluorene(DPF)in the as-synthesized DPFO.The pure DPFO molecule does have an intense fluorescence(FL)in solid(528 nm),about 4−5 times larger than in its dilute dichloromethane solutions(542 nm),but with a blueshifted rather than redshifted FL wavelength in solid.The enormous FL enhancement and redshifted FL wavelength of the as-synthesized DPFO solid are due to the presence of impurity DPF.The FL of DPF is much stronger than that of DPFO in dilute solutions and it also has shorter FL wavelengths.In a dilute solution of DPFO with a trace amount of DPF(∼1%),the dominant FL peaks are from DPF.Because the electronic absorption peaks of DPF overlaps with DPFO,the electronic energy of DPF can transfer to DPFO.The energy transfer is faster with the increase of concentration because DPF and surrounding DPFO molecules become closer,which quenches the FL of DPF(356 and 372 nm)and enhances the FL of DPFO(542 nm in solution and 528 nm in solid).Therefore,at high concentrations or in solids,only peak at about 542 or 528 nm shows up,and peaks at 356 and 372 nm disappear.

Fluorescence Emission Mediated by Metal-Dielectric-Metal Fishnet Metasurface: Spatially Selective Excitation and Double Enhancement

Enhancement of uorescent radiation is of great importance for applications including biological imaging,high-sensitivity detectors,and integrated light sources.Strong electromagnetic elds can be created around metallic nanoparticles or in gap of nanostructures,where the local state density of radiating mode is then dramatically enhanced.While enhanced uorescent emission has been demonstrated in many metallic nanoparticles and nanoparticle pairs,simultaneous mediation of absorption and emission processes of uorescent emitters remains challenging in metallic nanostructures.Here,we investigate uorescent emission mediated by metal-dielectric-metal fishnet metasurface,in which localized surface plasmon(LSP)and magnetic plasmon polaritons(MPPs)modes are coupled with absorption and emission processes,respectively.For absorption process,coupling of the LSP mode enables spatially-selective excitation of the uorescent emitters by rotating the polarization of the pump laser beam.In addition,the polarization-dependent MPP mode enables manipulation of both polarization and wavelength of the uorescent emission by introducing a rectangular fishnet structure.All the experimental observations are further corroborated by nite-difference time-domain simulations.The structure reported here has great potential for application to color light-emitting devices and nanoscale integrated light sources.

Enhancement of optical emission generated from femtosecond double-pulse laser-induced glass plasma at different sample temperatures in air

In double-pulse laser-induced breakdown spectroscopy(DP-LIBS), the collinear femtosecond double-pulse laser configuration is experimentally investigated with different initial sample temperatures using a Ti:sapphire laser. The glass sample is ablated to produce the plasma spectroscopy. During the experiment, the detected spectral lines include two Na(I) lines(589.0 nm and 589.6 nm) and one Ca(I) line at the wavelength of 585.7 nm. The emission lines are measured at room temperature(22 ℃) and three higher initial sample temperatures(T_s?=?100 ℃, 200 ℃, and 250 ℃). The inter-pulse delay time ranges from-250 ps to 250 ps.The inter-pulse delay time and the sample temperature strongly influence the spectral intensity,and the spectral intensity can be significantly enhanced by increasing the sample temperature and selecting the optimized inter-pulse time. For the same inter-pulse time of 0 ps(single-pulse LIBS), the enhancement ratio is approximately 2.5 at T_s?=?200 ℃ compared with that obtained at T_s?=?22 ℃. For the same inter-pulse time of 150 ps, the enhancement ratio can be up to 4 at T_s?=?200 ℃ compared with that obtained at T_s?=?22 ℃. The combined enhancement effects of the different initial sample temperatures and the double-pulse configuration in femtosecond LIBS are much stronger than that of the different initial sample temperatures or the double-pulse configuration only.

Intracellular Self-assembly of TPE-biotin Nanoparticles Enables Aggregation-Induced Emission Fluorescence for Cancer-Targeted Imaging

Fluorogens with aggregation-induced emission (AIE) characteristics have recently been widely applied for studying biological events, and fluorogens with “smart” properties are especially desirable. Herein, we rationally designed and synthesized a biotinylated and reduction-activatable probe (Cys(StBu)-Lys(biotin)-Lys(TPE)-CBT (1)) with AIE properties for cancer-targeted imaging. The biotinylated probe 1 can be actively uptaken by the biotin receptor-overexpressing cancer cells, and then “smartly” self-assemble into nanoparticles inside cells and turn the fluorescence “On”. Employing this “smart” strategy, we successfully applied probe 1 for cancer-targeted imaging. We envision that this biotinylated intelligent probe 1 might be further developed for cancer-targeted imaging in routine clinical studies in the near future.

Review:Aggregation-Induced Emission——A New Tool to Study Polymer Thermodynamics and Kinetics

Polymer thermodynamics and kinetics are important components in the basic theory of polymer physics, which provide critical support for polymer processing and molding. As an important thermal analysis technology, differential scanning calorimetry(DSC) is a key way to explore the molecular motion of polymer chains, molecular structure, and condensed structure, greatly promoting the development of polymer materials. However, this technique is limited by its ambiguous results, because of inaccurate heat flow measurement and high parameter dependence. As an alternative strategy, aggregation-induced emission luminogens(AIEgens) have been extensively applied in various targets analysis and process monitoring, owing to their weak intermolecular interactions and highly twisted conformation. The optical properties of AIEgens are highly sensitive to the variations of the polymer microenvironment, including characteristic transition, crosslinking reaction, crystallization behavior, and phase separation. In this review, the progress of AIE technology in visualizing polymer molecular motion and structure evolution is summarized, compensating for the limitation of the traditional DSC method to facilitate further research in polymer science and engineering.

Two different emission enhancement of trans-stilbene crystal under high pressure: Different evolution of structure

Mechanoresponsive luminescent(MRL)materials have drawn extensive concern due to their potential applications in mechanical sensors,memory chips,and security inks;especially these possessing high emission efficiency.In this work,we found trans-stilbene crystal exhibited two different pressure-induced emission enhancement(PIEE)behaviors at different pressure areas.The structural characterizations combined with density functional theory calculation indicate that the first emission enhancement was due to the decrease of nonradiation transition by the weaken of energy exchange process between atoms and lattice.And the second emission enhancement was attributed to the strengthen of C-H...C interactions from the non-planarization comformation.The results regarding the mechanoresponsive behavior of trans-stilbene offered a deep insight into PIEE from the structural point of view,which will facilitate the design of and search for high-performance MRL materials.

Phase Transformation and Enhancing Electron Field Emission Properties in Microcrystalline Diamond Films Induced by Cu Ion Implantation and Rapid Annealing

Cu ion implantation and subsequent rapid annealing at 500℃ in N2 result in low surface resistivity of 1.611 ohm/sq with high mobility of 290 cm2 V-1S-1 for microcrystalline diamond （MCD） films. Its electrical field emission behavior can be turned on at Eo = 2.6 V/μm, attaining a current density of 19.5μA/cm2 at an applied field of 3.5 V/#m. Field emission scanning electron microscopy combined with Raman and x-ray photoelectron mi- croscopy reveal that the formation of Cu nanoparticles in MCD films can catalytically convert the less conducting disorder/a-C phases into graphitic phases and can provoke the formation of nanographite in the films, forming conduction channels for electron transportation.

Aggregation-induced emission (AIE) luminescent materials boosting optical storage into the new era of petabit-level capacity

The recording of information stands as the most significant milestone in human civilization.Historically,the recording and storage of information have undergone a technological evolution from paintings to carvings,scribing,and digitization.The invention of optical compact discs(CDs)was one of the major landmarks in digital information technology.Over the past half-century,scientists have endeavored to enhance optical storage capacity by improving both optical systems and optical storage materials,as shown in Scheme 1.In terms of commercial products,the storage capacity has increased from 700 MB(CDs)to 27 GB(Blu-ray discs)by optimizing the optical system based on the same optical storage medium(polycarbonate).To surpass the conventional optical diffraction limit,the optical systems have evolved from traditional lasers to nonlinear two-photon absorption(TPA)and stimulated emission depletion(STED),which has minified the laser spot size from microns to approximately tens of nanometers,marking a remarkable achievement.

Novel strategy of multidimensional information encryption via multi-color carbon dots aggregation-induced emission

Carbon dots(CDs)with aggregation-induced emission(AIE)have sparked significant interest in multidimensional anti-counterfeiting due to their exceptional fluorescence properties.However,the preparation of AIE CDs with multicolor solid-state fluorescence remains a formidable challenge due to its complicated construction.In the present work,a novel class of multicolor AIE CDs(M-CDs)were fabricated using selected precursor(salicylic acid,thiosalicylic acid,and 2,2'-dithiodibenzoic acid),with an eco-friendly,low-cost one-pot solvothermal method.In the dilute organic solution,M-CDs manifested blue emission,but upon aggregation in the presence of water,the red,yellow,green,and blue emissions were displayed due to the AIE effect.Structural analysis,coupled with theoretical calculations,revealed that the increase in the size of sp2 domains would lower the Eg and cause a red-shift emission wavelength.Significantly,the continuous emission of M-CDs from blue to red can be utilized as ink for multimode printing,enabling the creation of a variety of school badges and quick response codes.These findings hold promising implications for multi-information encryption applications.