Air-Stable Ultrabright Inverted Organic Light-Emitting Devices with Metal Ion-Chelated Polymer Injection Layer

Here,this work presents an air-stable ultrabright inverted organic lightemitting device(OLED)by using zinc ionchelated polyethylenimine(PEI)as electron injection layer.The zinc chelation is demonstrated to increase the conductivity of the PEI by three orders of magnitude and passivate the polar amine groups.With these physicochemical properties,the inverted OLED shows a record-high external quantum efficiency of 10.0% at a high brightness of 45,610 cd m^(-2) and can deliver a maximum brightness of 121,865 cd m^(-2).Besides,the inverted OLED is also demonstrated to possess an excellent air stability(humidity,35%)with a half-brightness operating time of 541 h@1000 cd m^(-2) without any protection nor encapsulation.

Fabricating Na/In/C Composite Anode with Natrophilic Na-In Alloy Enables Superior Na Ion Deposition in the EC/PC Electrolyte

In conventional ethylene carbonate(EC)/propylene carbonate(PC)electrolyte,sodium metal reacts spontaneously and deleteriously with solvent molecules.This significantly limits the practical feasibility of high-voltage sodium metal batteries based on Na metal chemistry.Herein,we present a sodium metal alloy strategy via introducing NaIn and Na_(2)In phases in a Na/In/C composite,aiming at boosting Na ion deposition stability in the common EC/PC electrolyte.Symmetric cells with Na/In/C electrodes achieve an impressive long-term cycling capability at 1 mA cm^(-2)(>870 h)and 5 mA cm^(-2)(>560 h),respectively,with a capacity of 1 mAh cm^(-2).In situ optical microscopy clearly unravels a stable Na ion dynamic deposition process on the Na/In/C composite electrode surface,attributing to a dendrite-free and smooth morphology.Furthermore,theoretical simulations reveal intrinsic mechanism for the reversible Na ion deposition behavior with the composite Na/In/C electrode.Upon pairing with a highvoltage NaVPOF cathode,Na/In/C anode illustrates a better suitability in SMB s.This work promises an alternative alloying strategy for enhancing Na metal interfacial stability in the common EC/PC electrolyte for their future applications.

Ionic covalent organic frameworks with tailored anionic redox chemistry and selective ion transport for high-performance Na-ion cathodes

Employing cathode materials with multiple redox couples and electrolytes with efficient cation transport kinetics are two effective approaches to improving the electrochemical performance of batteries.In this work,for the first time,we present a design strategy of simultaneously realizing reversible cationic and anionic redox chemistries as well as selective anion/cation transport in the viologen-based COFs(BAVCOF:X,coordinated anions of X=Cl^(-),Br^(-),I^(-),and ClO_(4)^(-))for high-performance Na-ion cathodes.Besides the cationic redox of viologen segments,the different redox activities of anions effectively tune the total capacities of the COFs.Meanwhile,electrochemical analysis and ab-initial molecular dynamics(AIMD)calculation illustrate that the anion/cation transport kinetics of electrolytes caged in the COFs'channels can be selectively tuned by the coordinated anions.As a result,combining high-potential Br-/Br_(2)redox couple,cationic redox of viologen segments,and enhanced Na+transport kinetics,the BAV-COF:Brdemonstrates stable performance with energy densities of 358.7 and 145.2 Wh kg^(-1)at power densities of 116.5 and 2124.1 W kg^(-1),respectively.This study offers new insight into the fabrication of organic cathodes with anionic redox and the advantages of COFs electrode materials in anion/cation transport selectivity for energy storage applications.

Anion-hosting cathodes for current and late-stage dual-ion batteries

Anion-hosting cathodes capable of reversibly storing large-size anions play a leading role in dual-ion batteries(DIBs). The purpose of the present review is to summarize the most promising anion-hosting cathodes for current and late-stage DIBs. This review first summarizes the developments in conventional graphite cathodes, especially the latest advances in the graphiterelated research. Next, organic cathodes for the anion storage are discussed, including aromatic amine polymers, heterocyclic polymers, bipolar compounds, and all-carbon-unsaturated compounds. Then, the review focuses on the conversion-type cathodes with high theoretical specific capacities. Finally, the future research directions of the cathodes of DIBs are proposed.

Acceptor-planarized typeⅠphotosensitizer for lipid droplet-targeted two-photon photodynamic therapy by ferroptosis

Two-photon photodynamic therapy(TP-PDT)has garnered significant attention because of its excellent depth of tissue penetration and high spatiotemporal selectivity.However,the limited targeting ability and oxygen dependency of photosensitizers(PSs)significantly hinder the effectiveness of photodynamic therapy in hypoxic tumor treatment.Herein,we designed and synthesized two lipid droplet(LD)-targeted two-photon PSs(TBPCP and TBCP)by reducing benzene rings to achieve“acceptor planarization”.Notably,acceptor planarization not only enhanced the intramolecular charge transfer but also transferred the photochemical reaction from typeⅡ(TBPCP)to typeⅠ(TBCP).Under the irradiation of 940 nm femtosecond pulsed laser,TBPCP and TBCP showed bright two-photon-excited fluorescence and excellent LD targeting in living cells.Comparing TBPCP(typeⅡPS),the outstanding TP-PDT efficacy of TBCP(typeⅠPS)under hypoxic conditions could be obtained in both cellular experiments and multicellular tumor spheroids(MCTS)model.Additionally,both TBPCP and TBCP could induce the lipid peroxidation in the typeⅠor typeⅡPDT due to the location of LD,depleting GSH and inactivating GPX4 to induce nonprogrammed ferroptosis in cells.

Molecular Conformational Isomerization:An Efficient Way to Design Novel Emitters with Dual-Thermally Activated Delayed Fluorescence Characteristics and Their Optoelectronic and Bioimaging Applications

Single-molecule luminophores with dual-thermally activated delayed fluorescence(TADF)properties are receiving increasing attention.However,how to achieve these goals requires more in-depth studies.Herein,we demonstrate a novel example emitter,10-(5-(2-(pyridin-3-yl)-[4,5′-bipyrimidin]-6-yl)pyridin-2-yl)-10Hphenoxazine(PmPy-PXZ),enabling dual-TADF properties due to its key feature of conformational isomerization.Introducing a pyridine bridge can greatly reduce the steric hindrance and facilitate dual-stable conformations in the ground state,where the quasi-axial(QA)forms predominate.Moreover,unlike previously reported TADF molecules with dual confirmations,both theoretical and experimental measurements show that not only the quasi-equatorial(QE)forms but also the QA forms exhibit distinct TADF characteristics,which can be attributed to an additional higher reverse intersystem crossing pathway.This is the first time that dual-TADF properties of single molecules have been achieved based on conformational isomerism.Its applications in“self-doping”organic light-emitting diode and biomedical imaging have further been investigated.All these results show the good potential of such dual-band TADF emitters based on molecular conformational isomerization.

Thermally activated delayed fluorescence materials for nondoped organic light-emitting diodes with nearly 100%exciton harvest

High-performance nondoped organic light-emitting diodes(OLEDs)are promising technologies for future commercial applications.Herein,we synthesized two new thermally activated delayed fluorescence(TADF)emitters that enable us,for the first time,to combine three effective approaches for enhancing the efficiency of nondoped OLEDs.First,the two emitters are designed to have high steric hindrances such that their emitting cores will be suitably isolated from those of their neighbors to minimize concentration quenching.On the other hand,each of the two emitters has two stable conformations in solid films.In their neat films,molecules with the minority conformation behave effectively as dopants in the matrix composing of the majority conformation.One hundred percent exciton harvesting is thus theoretically feasible in this unique architecture of“self-doped”neat films.Furthermore,both emitters have relatively high aspect ratios in terms of their molecular shapes.This leads to films with preferred molecular orientations enabling high populations of horizontal dipoles beneficial for optical outcoupling.With these three factors,OLEDs with nondoped emitting layers of the respective emitters both achieve nearly 100%exciton utilization and deliver over 30%external quantum efficiencies and ultralow efficiency roll-off at high brightness,which have not been observed in reported nondoped OLEDs.

Revealing the crystallization process and realizing uniform 1.8 eV MA-based wide-bandgap mixed-halide perovskites via solution engineering

Wide-bandgap perovskites are recently drawing tremendous attention in the community for high-efficiency all-perovskite tandem solar cells.However,the formamidinium (FA^+) and methylammonium (MA^+) based wide-bandgap mixed halide perovskites suffered from high density of traps and pin-holes,respectively.Fundamental understanding on the crystallization and film formation processes are keys to overcome those challenges but not yet clearly understood.In this study,an in-situ photoluminescence technique was used to investigate the perovskite crystallization during the thermal annealing process.It is found that the crystallization of a mixed halide perovskite with bromide (Br^-) and iodine (I^-) ions following the Ostward ripening crystal growth.Interestingly,it is found that the initial nucleation reaction is quickly completed in the first few seconds,however,leaving the small crystals with inhomogeneous composition.The different aggregation affinities of such inhomogeneous small crystals provoke the formation of pin-holes during the thermal annealing process.By engineering the precursor solution to control the nucleation rate,the chemical composition of the small crystals has become homogenous.Uniform pin-hole free high Br-composited wide-bandgap MA0.9Cs0.1Pb(I0.6Br0.4)3 perovskite films with bandgap energy of 1.8 eV have been realized.The corresponding photovoltaic devices have achieved an encouraging device efficiency of 15.1% with superb photostability.

Top-emitting thermally activated delayed fluorescence organic light-emitting devices with weak light-matter coupling

Resonance interaction between a molecular transition and a confined electromagnetic field can lead to weak or strong light-matter coupling.Considering the substantial exciton–phonon coupling in thermally activated delayed fluorescence(TADF)materials,it is thus interesting to explore whether weak light-matter coupling can be used to redistribute optical density of states and to change the rate of radiative decay.Here,we demonstrate that the emission distribution of TADF emitters can be reshaped and narrowed in a top-emitting organic light-emitting device(OLED)with a weakly coupled microcavity.The Purcell effect of weak microcavity is found to be different for TADF emitters with different molecular orientations.We demonstrate that radiative rates of the TADF emitters with vertical orientation can be substantial increased in weakly coupled organic microcavity.These observations can enhance external quantum efficiencies,reduce efficiency roll-off,and improve color-purities of TADF OLEDs,especially for emitters without highly horizontal orientation.

2D materials for conducting holes from grain boundaries in perovskite solar cells

Grain boundaries in organic-inorganic halide perovskite solar cells(PSCs)have been found to be detrimental to the photovoltaic performance of devices.Here,we develop a unique approach to overcome this problem by modifying the edges of perovskite grain boundaries with flakes of high-mobility two-dimensional(2D)materials via a convenient solution process.A synergistic effect between the 2D flakes and perovskite grain boundaries is observed for the first time,which can significantly enhance the performance of PSCs.We find that the 2D flakes can conduct holes from the grain boundaries to the hole transport layers in PSCs,thereby making hole channels in the grain boundaries of the devices.Hence,2D flakes with high carrier mobilities and short distances to grain boundaries can induce a more pronounced performance enhancement of the devices.This work presents a cost-effective strategy for improving the performance of PSCs by using high-mobility 2D materials.

Novel metastable Bi:Co and Bi:Fe alloys nanodots@carbon as anodes for high rate K-ion batteries

Bi is a promising anode material for potassium-ion batteries(PIBs)due to its high theoretical capacity.However,severe pulverization upon cycling limits its practical applications.In this work,we propose a new approach of using metastable alloys with Bi elements.Metastable Bi:Co and Bi:Fe alloys nanodots@carbon anode materials(Bi:Co and Bi:Fe@C)are synthesized for the first time via simple annealing of their metal-organic frameworks(MOF)precursors.These prepared materials are demonstrated as ideal hosts for high-rate K-ion storage.Bi_(0.85)Co_(0.15)@C and Bi_(0.83)Fe_(0.17)@C electrodes respectively deliver superior 178 and 253 mAh·g^(−1)at 20 A·g^(−1),as well as stable cycling performance at 2 A·g^(−1).Ex situ scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),and transmission electron microscopy(TEM)studies on Bi:Co@C indicate that the elemental Co separates out during the initial potassiation and stands during the following discharge/charge cycles.In situ formed Co precipitates can act as(1)“conductive binders”as well as(2)“separators”to prevent the severe aggregation of adjacent active elemental Bi nanoparticles and(3)accelerate the potassiation/de-potassiation kinetics in elemental Bi precipitates after initial discharge/charge cycles.This work could inspire the development of metal-type anodes.

Highly stable organic fluorescent nanorods for living- cell imaging

Metal-free, organic-dye-based fluorescent nanorods were fabricated through a simple solvent-exchange procedure. The as-prepared nanorods exhibit low toxicity to living cells and excellent photostability. Furthermore, they are stable in solutions of various pHs and high ionic strength and in solutions with interfering metal ions. Compared with the free DPP-Br molecules in THF, these nanorods exhibit larger Stokes shift, broader absorption spectra, and greatly improved photostability. We successfully demonstrated the application of the nanorods, including their aforementioned beneficial characteristics, as a good fluorescence probe for bio-imaging.

Confocal visible/NIR photoacoustic microscopy of tumors with structural, functional, and nanoprobe contrasts

Distinguishing early-stage tumors from normal tissues is of great importance in cancer diagnosis.We report fiberbased confocal visible/near-infrared(NIR)optical-resolution photoacoustic microscopy that can image tumor microvasculature,oxygen saturation,and nanoprobes in a single scanning.We develop a cost-efficient single laser source that provides 532,558,and 1064 nm pulsed light with sub-microseconds wavelength switching time.Via dual-fiber illumination,we can focus the three beams to the same point.The optical and acoustic foci are confocally aligned to optimize the sensitivity.The visible and NIR wavelengths enable simultaneous tumor imaging with three different contrast modes.Results show obvious angiogenesis,significantly elevated oxygen saturation,and accumulated nanoparticles in the tumor regions,which offer comprehensive information to detect the tumor.This approach also allows us to identify feeding and draining vessels of the tumor and thus to determine local oxygen extraction fraction.In the tumor region,the oxygen extraction fraction significantly decreases along with tumor growth,which can also assist in tumor detection and staging.Fiber-based confocal visible/NIR photoacoustic microscopy offers a new tool for early detection of cancer.

Vapor phase epitaxy of PbS single-crystal films on water-soluble substrates and application to photodetectors

Lead sulfide(PbS),a typical functional semiconductor material,has attracted serious attention due to its great potential in optoelectronics applications.However,controllable growth of PbS single-crystal film still remains a great challenge.Here,we report heteroepitaxial growth of large-scale highly crystalline PbS films on alkali salt(NaCl and KCl)substrates via chemical vapor deposition(CVD).Structural characterizations demonstrate that the as-grown PbS films exhibit an atomically sharp interface with the underlying substrates.The epitaxial relationships between the epilayers and substrates were determined to be PbS(100)//NaCl(100)or KCl(100),PbS[010]//NaCl[010]or KCl[010].Owing to the high solubility of alkali salt,the epitaxial PbS films can be rapidly released from the underlying substrates and transferred to other substrates of interest while maintaining good integrity and crystallinity,the process of which is particularly attractive in the fields of electronics and optoelectronics.Furthermore,photodetectors based on the transferred PbS films were fabricated,exhibiting a high photoresponsivity of 7.5 A/W,a detectivity of 1.44×10^(12)Jones,and a rapid response time of approximately 0.25 s.This work sheds light on the batch production,green transfer,and optoelectronic application of PbS films.

Novel bipolar host for highly efficient green,yellow,orange,red and deep-red phosphorescent organic light-emitting devices

A novel bipolar host tris(4-(pyrimidin-5-yl)phenyl)amine(TPMTPA) constructed by incorporating triphenylamine as the electron-donating core and pyrimidine as the electron-accepting peripheries was designed and synthesized.TPMTPA achieves excellent bipolar charge transport properties and has high enough triplet energy level to sensitize green,yellow,orange,red and deep-red phosphors.By using TPMTPA as a host,high performance green,yellow,orange,red and deep-red phosphorescent organic light-emitting devices(PhOLEDs) were demonstrated with maximum external quantum efficiencies of 20.4%,17.6%,15.1%,15.3%and 15.7%respectively.These results suggested that TPMTPA is a versatile high performance host for PhOLEDs of different emission colors.

Nearly 100% exciton utilization in highly efficient red OLEDs based on dibenzothioxanthone acceptor

Improving the utilization of excitons has always been an important topic for the development of electroluminescence devices.In this work,we designed and synthesized three red TADF emitters TPA-DBT12,TPA-DBT3 and DTPA-DBT by employing dibenzothioxanthone(DBT)acceptor framework to stabilize the locally excited triplet state to participate in the reverse intersystem crossing(RISC)process.The fast RISC process and singlet radiation decay process gave rise to evidently enhanced exciton utilization.All of the red OLEDs based on these materials showed maximum EQE over 11% and high exciton utilization close to 100%.This work not only extend the acceptor framework for red materials but also provide a new perspective for the design of highly efficient red TADF materials with 100% exciton utilization by managing locally excited triplet state.

Flexible and biocompatible poly(vinyl alcohol)/multi-walled carbon nanotubes hydrogels with epsilon-near-zero properties

Epsilon-near-zero(ENZ)material has been a research hotspot in recent years due to unique physical properties such as inverse Doppler effect and negative refractive index,showing great potentials in the fields of flexible electronics,wearable devices,sensors,etc.The ENZ materials are mostly reported at visible,infrared and terahertz wavelengths,while the report about ENZ materials at radio frequency is rare.In this work,flexible and biocompatible poly(vinyl alcohol)/multi-walled carbon nanotubes(PVA/MWCNTs)hydrogels,which were successfully fabricated by an environmentally friendly method,were used as ENZ materials at radio frequency for the first time.Cytotoxicity experiments proved that the experimental process and products are green,environmentally friendly and biocompatible.The microstructure,crystalline structure,chemical composition and dielectric properties were investigated.Two different water states,which were free water molecules and bound water molecules,coexisted in these PVA/MWCNTs hydrogels and accounted for about 37.5 wt%and 15.9 wt%respectively by analyzing the thermogravimetric analysis curves.When the MWCNTs content reached 12 wt%and 15 wt%,the continuous conductive MWCNTs network was formed in the hydrogel,and ENZ phenomenon was observed at about 760 k Hz and 580 k Hz respectively,which was attributed to the interband transition.Considering the flexibility and non-toxicity of PVA/MWCNTs hydrogels,the ENZ properties of this structure at the radio frequency can be well used in wearable invisibility cloak,flexible electronics,skin sensors and other wearable devices.

Room-temperature multiple ligands-tailored SnO_(2) quantum dots endow in situ dual-interface binding for upscaling efficient perovskite photovoltaics with high V_(OC)

The benchmark tin oxide(SnO_(2))electron transporting layers(ETLs)have enabled remarkable progress in planar perovskite solar cell(PSCs).However,the energy loss is still a challenge due to the lack of“hidden interface”control.We report a novel ligand-tailored ultrafine SnO_(2) quantum dots(QDs)via a facile rapid room temperature synthesis.Importantly,the ligand-tailored SnO_(2) QDs ETL with multi-functional terminal groups in situ refines the buried interfaces with both the perovskite and transparent electrode via enhanced interface binding and perovskite passivation.These novel ETLs induce synergistic effects of physical and chemical interfacial modulation and preferred perovskite crystallization-directing,delivering reduced interface defects,suppressed non-radiative recombination and elongated charge carrier lifetime.Power conversion efficiency(PCE)of 23.02%(0.04 cm^(2))and 21.6%(0.98 cm^(2),V_(OC) loss:0.336 V)have been achieved for the blade-coated PSCs(1.54 eV E_(g))with our new ETLs,representing a record for SnO_(2) based blade-coated PSCs.Moreover,a substantially enhanced PCE(V_(OC))from 20.4%(1.15 V)to 22.8%(1.24 V,90 mV higher V_(OC),0.04 cm^(2) device)in the blade-coated 1.61 eV PSCs system,via replacing the benchmark commercial colloidal SnO_(2) with our new ETLs.