Improved Efficiency and Stability of Organic Solar Cells by Interface Modification Using Atomic Layer Deposition of Ultrathin Aluminum Oxide

The interfacial contacts between the electron transporting layers(ETLs)and the photoactive layers are crucial to device performance and stability for OSCs with inverted architecture.Herein,atomic layer deposition(ALD)fabricated ultrathin Al_(2)O_(3)layers are applied to modify the ETLs/active blends(PM6:BTP-BO-4F)interfaces of OSCs,thus improving device performance.The ALD-Al_(2)O_(3)thin layers on ZnO significantly improved its surface morphology,which led to the decreased work function of ZnO and reduced recombination losses in devices.The simultaneous increase in open-circuit voltage(V_(OC)),short-circuit current density(J_(SC))and fill factor(FF)were achieved for the OSCs incorporated with ALD-Al_(2)O_(3)interlayers of a certain thickness,which produced a maximum PCE of 16.61%.Moreover,the ALD-Al_(2)O_(3)interlayers had significantly enhanced device stability by suppressing degradation of the photoactive layers induced by the photocatalytic activity of ZnO and passivating surface defects of ZnO that may play the role of active sites for the adsorption of oxygen and moisture.

Overcoming the biofilm barrier by cell-like microbubbles for the treatment of biofilm-associated implant infections

Although the advent of antibiotics has significantly improved the quality of life of infected patients,bacterial infections continue to pose a serious threat to public health[1,2].According to a recent report,within the next 30 years,bacterial infections are projected to surpass cancer in terms of lethality rates,resulting in an alarming 10 million deaths annually by 2050 due to the development of bacterial resistance[3].Moreover,the formation of bacterial biofilms hampers the penetration of antibacterial agents and inhibits the host immune response,making biofilm infections extremely challenging to treat[4-7].Hence,the development of innovative antimicrobial biofilm therapeutics is imperative.

The enhancement of 21.2%-power conversion efficiency in polymer photovoltaic cells by using mixed Au nanoparticles with a wide absorption spectrum of 400 nm–1000 nm

Au nanoparticles （NPs） mixed with a majority of bone-like, rod, and cube shapes and a minority of irregu- lar spheres, which can generate a wide absorption spectrum of 400 nm-1000 nm and three localized surface plas- mon resonance peaks, respectively, at 525, 575, and 775 nrn, are introduced into the hole extraction layer poly（3,4- ethylenedioxythiophene）：poly（4-styrenesulfonate） （PEDOT：PSS） to improve optical-to-electrical conversion performances in polymer photovoltaic ceils. With the doping concentration of Au NPs optimized, the cell performance is significantly improved： the short-circuit current density and power conversion efficiency of the poly（3-hexylthiophene）： [6,6]-phenyl- C60-butyric acid methyl ester cell are increased by 20.54% and 21.2%, reaching 11.15 mA.cm-2 and 4.23%. The variations of optical, electrical, and morphology with the incorporation of Au NPs in the cells are analyzed in detail, and our results demonstrate that the cell performance improvement can be attributed to a synergistic reaction, including： 1） both the local- ized surface plasmon resonanceand scattering-induced absorption enhancement of the active layer, 2） Au doping-induced hole transport/extraction ability enhancement, and 3） large interface roughness-induced efficient exciton dissociation and hole collection.

Fluorene pendant-functionalization of poly(N-vinylcarbazole)as deep-blue fluorescent and host materials for polymer light-emitting diodes

π-Electron coupling of pendant conjugated segment inπ-stacked semiconducting polymers always causes the formation of defect trapped sites and further quenched high-band excitons,which is harmful to the performance and stability of deep-blue polymer light-emitting diodes(PLEDs).Herein,considerate of“defect”carbazole(Cz)electromers in poly(N-vinylcarbazole)(PVK),a series of fluorene units are introduced into pendant segments(PVCz-DMeF,PVCz-FMeNPh and PVCz-DFMeNPh)to suppress the strongπ-electron coupling of pendant Cz units and enhance radiative transition toward fabricating sable PLEDs.Compared to PVCz-FMeNPh and PVCz-DFMeNPh,PVCz-DMeF spin-coated films show a relatively efficient deep-blue emission,completely similar to its single pendant chromophore,confirmed an extremely weak charge-transfer and electron coupling between adjacent pendant segments.Therefore,PLEDs based on PVCz-DMeF present stable and deep-blue emission with a high color purity(0.17,0.08),associated with extremely weak defect emission at 600∼700nm(induced by carbazole electromers).Finally,PLEDs based on PVCz-DMeF/F8BT blended films(1:1)also present the high maximum luminance(Lmax)of 6261 cd/m2 and current efficiency(CE_(max))of 2.03 cd/A,confirmed slightly trapped sites formation.Therefore,precisely control the arrangement and packing model of pendant units inπ-stacked polymer is an essential prerequisite for building efficient and stable emitter for optoelectronic devices.

The Soft-Strain Effect Enabled High-Performance Flexible Pressure Sensor and Its Application in Monitoring Pulse Waves

Flexible and wearable pressure sensors attached to human skin are effective and convenient in accurate and real-time tracking of various physiological signals for disease diagnosis and health assessment.Conventional flexible pressure sensors are constructed using compressible dielectric or conductive layers,which are electrically sensitive to external mechanical stimulation.However,saturated deformation under large compression significantly restrains the detection range and sensitivity of such sensors.Here,we report a novel type of flexible pressure sensor to overcome the compression saturation of the sensing layer by softstrain ffect,enabling an utra-high sensitivity of~636 kPa^(-1) and a wide detection range from 0.1 kPa to 56 kPa.In addition,the cyclic loading-unloading test reveals the excellent stability of the sensor,which maintains its signal detection after 10.000 cycles of 10 kPa compression.The sensor is capable of monitoring arterial pulse waves from both deep tissue and distal parts,such as digital arteries and dorsal pedal arteries,which can be used for blood pressure estimation by pulse transit time at the same artery branch.

Aggregation-induced delayed electrochemiluminescence of organic dots in aqueous media

Full utilization of the excited species at both singlet states(1R*)and triplet states(3R*)is crucial to improving electrochemiluminescence(ECL)efficiency but is challenging for organic luminescent materials.Here,an aggregation-induced delayed ECL(AIDECL)active organic dot(OD)containing a benzophenone acceptor and dimethylacridine donor is reported,which shows high ECL efficiency via reverse intersystem crossing(RISC)of non-emissive 3R*to emissive 1R*,overcoming the spin-forbidden radiative decay from 3R*.By introducing dual donor-acceptor pairs into luminophores,it is found that nonradiative pathway could be further suppressed via enhanced intermolecular weak interactions,and multiple spin-up conversion channels could be activated.As a consequence,the obtained OD enjoys a 6.8-fold higher ECL efficiency relative to the control AIDECL-active OD.Single-crystal studies and theoretical calculations reveal that the enhanced AIDECL behaviors come from the acceleration of both radiative transition and RISC.This work represents a major step towards purely organic,high-efficiency ECL dyes and a direction for the design of next-generation ECL dyes at the molecular level.

Construction and electrical control of ultrahigh-density organic memory arrays at cr yog enic temperature

Investigation into the structural and magnetic properties of organic molecules at cryogenic temperature is beneficial for reducing molec-ular vibration and stabilizing magnetization,and is of great im-portance for constructing novel spintronics devices of better perfor-mance and scaling the device size down to nanoscale.In order to explore the possibility of fabricating molecule-based memory chips of ultrahigh density,two-dimensional close-packed molecular arrays with carboxylic acid molecules were constructed in the current work and the magnetic properties in a low-temperature scanning tunnel-ing microscope were also investigated.The results demonstrated that each nonmagnetic molecule can be controllably and independently switched into a stable spin-carrying state at 4 K by applying a voltage pulse with atomic resolution.Benefiting from the small size of a single molecule as the basic storage bit,the two-dimensional molecular ar-rays allowing controllable electrical manipulations on each molecule can behave as a platform of memory chip with an ultrahigh storage density of∼320 terabytes(Tb)(or∼2500 terabits)per square inch.This work highlights the potential and advantage of employing or-ganic molecules in developing future cryogenic information storage techniques and devices at nanoscale.

Recent Advances in Tumor Microenvironment Hydrogen Peroxide-Responsive Materials for Cancer Photodynamic Therapy

Photodynamic therapy(PDT),as one of the noninvasive clinical cancer phototherapies,suffers from the key drawback associated with hypoxia at the tumor microenvironment(TME),which plays an important role in protecting tumor cells from damage caused by common treatments.High concentration of hydrogen peroxide(H2O2),one of the hallmarks of TME,has been recognized as a double-edged sword,posing both challenges,and opportunities for cancer therapy.The promising perspectives,strategies,and approaches for enhanced tumor therapies,including PDT,have been developed based on the fast advances in H2O2-enabled theranostic nanomedicine.In this review,we outline the latest advances in H2O2-responsive materials,including organic and inorganic materials for enhanced PDT.Finally,the challenges and opportunities for further research on H2O2-responsive anticancer agents are envisioned.

Recent progress of flexible and wearable strain sensors for human-motion monitoring

With the rapid development of human artificial intelligence and the inevitably expanding markets, the past two decades have witnessed an urgent demand for the flexible and wearable devices, especially the flexible strain sensors. Flexible strain sensors, incorporated the merits of stretchability, high sensitivity and skin-mountable,are emerging as an extremely charming domain in virtue of their promising applications in artificial intelligent realms, human-machine systems and health-care devices. In this review, we concentrate on the transduction mechanisms, building blocks of flexible physical sensors, subsequently property optimization in terms of device structures and sensing materials in the direction of practical applications. Perspectives on the existing challenges are also highlighted in the end.

Matrix Effect on Polydiarylfluorenes Electrospun Hybrid Microfibers: From Morphology Tuning to High Explosive Detection Efficiency

Precisely optimizing the morphology of functional hybrid polymeric systems is crucial to improve its photophysical property and further extend their optoelectronic applications. The physic-chemical property of polymeric matrix in electrospinning (ES) processing is a key factor to dominate the condensed structure of these hybrid microstructures and further improve its functionality. Herein, we set a flexible poly(ethylene oxide) (PEO) as the matrix to obtain a series of polydiarylfluorenes (including PHDPF, PODPF and PNDPF) electrospun hybrid microfibers with a robust deep-blue emission. Significantly different from the rough morphology of their poly(N-vinylcarbazole) (PVK) ES hybrid fibers, polydiarylfluorenes/PEO ES fibers showed a smooth morphology and small size with a diameter of 1∼2 µm. Besides, there is a relatively weak phase separation under rapid solvent evaporation during the ES processing, associated with the hydrogen-bonded-assisted network of PEO in ES fibers. These relative “homogeneous” ES fibers present efficient deep-blue emission (PLQY>50%), due to weak interchain aggregation. More interestingly, low fraction of planar (β) conformation appears in the uniform PODPF/PEO ES fibers, induced by the external traction force in ES processing. Meanwhile, PNDPF/PEO ES fibers present a highest sensitivity than those of other ES fibers, associated with the smallest diameter and large surface area. Finally, compared to PODPF/PVK fibers and PODPF/PEO amorphous ES fibers, PODPF/PEO ES fibers obtained from DCE solution exhibit an excellent quenching behavior toward a saturated DNT vapor, mainly due to the synergistic effect of small size, weak separation, β-conformation formation and high deep-blue emission efficiency.

Rapid inactivation of multidrug-resistant bacteria and enhancement of osteoinduction via titania nanotubes grafted with polyguanidines

The rapid in situ inhibition of bacterial contamination and subsequent infection without inducing drug resistance is highly vital for the successful implantation and long-term service of titanium(Ti)-based orthopedic implants.However,the instability and potential cytotoxicity of current coatings have deterred their clinical practice.In this study,anodic oxidized titania nanotubes(TNT)were modified with antibacterial polyhexamethylene guanidine(PG)with the assistance of 3,4-dihydroxyphenylacetic acid.Interestingly,the prepared TNT-PG coating exhibited superior in vitro antibacterial activity than flat Ti-PG coating and effectively killed typical pathogens such as Escherichia coli and superbug methicillinresistant Staphylococcus aureus with above 4-log reduction(>99.99%killed)in only 5 min.TNT-PG coating also exerted excellent hemocompatibility with red blood cells and nontoxicity toward mouse pre-osteoblasts(MC3 T3-E1)in 1 week of coculture.In addition,the efficient in vivo anti-infective property of this coating was observed in a rat subcutaneous infection model.More importantly,TNT-PG coating improved the expression of alkaline phosphatase and enhanced the extracellular matrix mineralization of pre-osteoblasts,denoting its osteoinductive capacity.This versatile TNT-PG coating with excellent antibacterial activity and biocompatibility could be a promising candidate for advanced orthopedic implant applications.

Unveiling the Effects of Interchain Hydrogen Bonds on Solution Gelation and Mechanical Properties of Diarylfluorene-Based Semiconductor Polymers

The intrinsically rigid and limited strain of most conjugated polymers has encouraged us to optimize the extensible properties of conjugated polymers.Herein,learning from the hydrogen bonds in glucose,which were facilitated to the toughness enhancement of cellulose,we introduced interchain hydrogen bonds to polydiarylfluorene by amide-containing side chains.Through tuning the copolymerization ratio,we systematically investigated their influence on the hierarchical condensed structures,rheology behavior,tensile performances,and optoelectronic properties of conjugated polymers.Compared to the reference copolymers with a low ratio of amide units,copolymers with 30%and 40%amide units present a feature of the shearthinning process that resembled the non-Newtonian fluid,which was enabled by the interchain dynamic hydrogen bonds.Besides,we developed a practical and universal method for measuring the intrinsic mechanical properties of conjugated polymers.We demonstrated the significant impact of hydrogen bonds in solution gelation,material crystallization,and thin film stretchability.Impressively,the breaking elongation for P4 was even up to~30%,which confirmed the partially enhanced film ductility and toughness due to the increased amide groups.Furthermore,polymer light-emitting devices(PLEDs)based on these copolymers presented comparable performances and stable electroluminescence(EL).Thin films of these copolymers also exhibited random laser emission with the threshold as low as 0.52μJ/cm^(2),suggesting the wide prospective application in the field of flexible optoelectronic devices.

Enhancement of morphological and emission stability of deep-blue small molecular emitter via a universal side-chain coupling strategy for optoelectronic device

Film morphology of emissive layers is crucial to the performance and stability of solution-processable organic light-emitting diodes(OLEDs). Compared to the interpenetration of conjugated polymer chain,small molecular emitter with a flexible side chain always presents easily aggregation upon external treatment, and caused π-electronic coupling, which is undesirable for the efficiency and stability of deep-blue OLEDs. Herein, we proposed a side-chain coupling strategy to enhance the film morphological an emission stability of solution-processable small molecular deep-blue emitter. In contrary to “parent” MC8 TPA,the crosslinkable styryl and vinyl units were introduced as ended unit at the side-chain of Cm TPA and OEYTPA. Interestingly, Cm TPA and OEYTPA films present a relatively stable morphology and uniform deep-blue emission after thermal annealing(160 ℃) in the atmosphere, different to the discontinuous MC8 TPA annealed film. Besides, compared to the Cm TPA and OEYTPA ones, serious polaron formation in the MC8 TPA annealed film also negative to the deep-blue emission, according to transient absorption analysis. Therefore, both Cm TPA and OEYTPA annealed film obtained at 140 ℃ present an excellent deep-blue ASE behavior with a 445 nm, but absence for MC8 TPA ones, associated with the disruption of annealed films. Finally, enhancement of device performance based on Cm TPA and OEYTPA film(~40%)after thermal annealing with a similar performance curves also confirmed the assumption above. Therefore, these results also supported the effectiveness of our side-chain coupling strategy for optoelectronic applications.

Electrospun Supramolecular Hybrid Microfibers from Conjugated Polymers:Color Transformation and Conductivity Evolution

A type of novel electrospun supramolecular hybrid microfibers comprising poly(9-(4-(octyloxy)-phenyl)-2,7-fluoren-9-ol)(PPFOH)and poly(A/-vinylcarbazole)(PVK)are successfully prepared for intriguing multi-color emission properties.The supramolecular tunable PPFOH aggregation in PVK matrix endows the complex with a smart energy transfer behavior to obtain the multi-color emissions.In stark contrast to PVK fibers,the emission color of PPFOH/PVK fibers with an efficient dispersion of PPFOH fluorophores at a proper dope ratio can be tuned in a wide spectrum of blue(0.1%),sky blue(0.5%),nearly white(1%),cyan(2%),green(5%)and yellow(10%).Besides,conductive behaviors of the microfiber were demonstrated in accompany with the increment of the doping ratio of PPFOH to PVK.Successful fabrication of polymer light-emitting diode(PLED)based on the blended electrospun fiber provided a further evidence of its excellent electrical property for potential applications in optoelectronic devices.

Homogeneous permeation and oriented crystallization in nanostructured mesopores for efficient and stable printable mesoscopic perovskite solar cells

The low-cost and scalable printable mesoporous perovskite solar cells(p-MPSCs) face significant challenges in regulating perovskite crystal growth due to their nanoscale mesoporous scaffold structure, which limits the improvement of device power conversion efficiency(PCE). In particular, the most commonly used solvents, N,N-dimethylformamide(DMF) and dimethyl sulfoxide(DMSO), have a single chemical interaction with the precursor components and high volatility, which is insufficient to self-regulate the perovskite crystallization process, leading to explosive nucleation and limited growth within mesoporous scaffolds. Here, we report a mixed solvent system composed of methylamine formaldehyde(MAFa)-based ionic liquid and acetonitrile(ACN) with the strong C=O–Pb coordination and N–H···I hydrogen bonding with perovskite components. We found that the mixed solvent system is beneficial for the precursor solution to homogeneously penetrate into the mesoporous scaffold,and the strong C=O–Pb coordination and N–H···I hydrogen bonding interaction can promote the oriented growth of perovskite crystals. This synergistic effect increased the PCE of the p-MPSCs from 17.50% to 19.21%, which is one of the highest records for p-MPSC in recent years. Additionally, the devices exhibit positive environmental stability, retaining over 90% of the original PCE after 1,200 h of aging under AM 1.5 illumination conditions at 55 ℃ and 55% humidity.

Spatial compartmentalization of metal nanoparticles within metal-organic frameworks for tandem reaction

Fabrication of multifunctional catalysts has always been the pursuit of synthetic chemists due to their efficiency,cost-effectiveness,and environmental friendliness.However,it is difficult to control multi-step reactions in one-pot,especially the spatial compartmentalization of incompatible active sites.Herein,we constructed metal-organic framework(MOF)composites which regulate the location distribution of metal nanoparticles according to the reaction path and coupled with the diffusion of substrates to achieve tandem reaction.The designed UiO-66-Pt-Au catalyst showed good activity and selectivity in hydrosilylation-hydrogenation tandem reaction,because the uniform microporous structures can control the diffusion path of reactants and intermediates,and Pt and Au nanoparticles were arranged in core-shell spatial distribution in UiO-66.By contrast,the low selectivity of catalysts with random deposition and physical mixture demonstrated the significance of artificial control to the spatial compartmentalization of active sites in tandem catalytic reactions,which provides a powerful approach for designing high-performance and multifunctional heterogeneous catalysts.

The Key Role of Subtle Substitution for a High-Performance Ester-Modified Oligothiophene-Based Polymer Used in Photovoltaic Cells

In organic solar cells (OSCs), developing high-performing easily synthesized photoactive materials is essential for pursuing cost- effective balance. Herein, we have designed and synthesized a pair of wide-band-gap polymers (PBDE4T-0F and PBDE4T-2F), using the low synthesis cost dicarboxylic ester-substituted quaterthiophene as the building block. Despite the minor change of molecular structure for polymer PBDE4T-xF, the fluorine substituent in polymer PBDE4T-2F greatly enhances its interchain aggregation. The higher aggregation tendency of ester-modified polymer in solution is beneficial for reducing both the aggregate size and π-π stacking distance of blend film, which contribute to the highly efficient exciton dissociation and symmetric charge transport. An impressive power-conversion efficiency (PCE) of 16.1% is achieved for the PBDE4T-2F:BTP-eC9-based device, while its counterpart only delivers a PCE of 5.8% with distinctly lower short-circuit current density (J_(sc)) and fill factor. Notably, the aggregation effect of donor polymer has also been found to be associated with the energy level shifts, and thus the variation of charge transfer energy and voltage losses for blend system. The results suggest that simultaneously reduced voltage loss and increased J_(sc) can be expected by further finely tuning the aggregation behavior of the ester-modified oligothiophene-based donor polymer.

Flexible organic electrochemical transistors for chemical and biological sensing

Chemical and biological sensing play important roles in healthcare,environmental science,food-safety tests,and medical applications.Flexible organic electrochemical transistors(OECTs)have shown great promise in the field of chemical and biological sensing,owing to their superior sensitivity,high biocompatibility,low cost,and light weight.Herein,we summarize recent progress in the fabrication of flexible OECTs and their applications in chemical and biological sensing.We start with a brief introduction to the working principle,configuration,and sensing mechanism of the flexible OECT-based sensors.Then,we focus on the fabrication of flexible OECT-based sensors,including material selection and structural engineering of the components in OECTs:the substrate,electrodes,electrolyte,and channel.Particularly,the gate modification is discussed extensively.Then,the applications of OECT-based sensors in chemical and biological sensing are reviewed in detail.Especially,the array-based and integrated OECT sensors are also introduced.Finally,we present the conclusions and remaining challenges in the field of flexible OECT-based sensing.Our timely review will deepen the understanding of the flexible OECT-based sensors and promote the further development of the fast-growing field of flexible sensing.

Doping induced morphology,crystal structure,and upconversion luminescence evolution:from Na_(3)ScF_(6):Yb/Er/Y to NaYF_(4):Yb/Er/Sc nanocrystals

Impurity doping not only provides a fundamental approach to impart unique electronic,magnetic and optical properties to target nanomaterials,but also has critical influence on nucleation and growth of many functional nanocrystals.In the current study,Y^(3+)and Sc^(3+)were adopted to tune the shape,size,and upconversion luminescence properties of Na_(3)ScF_(6):Yb/Er and NaYF_(4):Yb/Er samples,respectively.When Y^(3+)doping concentration was lower than 10 mol%,the size and shape of Na_(3)ScF_(6):Yb/Er(18/2)nanoparticles gradually changed from~18 nm rhombus to 36 nm spheres.Subsequently,the coexistence of Na_(3)ScF_(6):Yb/Er and NaYF_(4):Yb/Er nanoparticles was observed during 20 mol%-50 mol%Y^(3+)doping,and finally NaYF_(4):Yb/Er nanoparticles became the only product at>60 mol%Y^(3+)doping where the role of Sc^(3+)turned into dopant and the size of nanocrystals decreased from~30 to 20 nm gradually.Both Y^(3+)and Sc^(3+)ions doping could enhance the upconversion luminescence intensity of Na_(3)ScF_(6):Yb/Er and NaYF_(4):Yb/Er samples,for which possible mechanism was proposed from the perspective of crystal structure.Finally,the upconversion luminescence details were disclosed.

A universal ionic liquid solvent for non-halide lead sources in perovskite solar cells

Replacing lead iodide(PbI_(2))with suitable non-halides lead source has been found to be an effective method to control crystallization and fabricate high-performance perovskite solar cells(PSCs).However,the solubility of non-halide lead sources is highly limited by traditional solvents due to the chemical interaction limitation.Here,we report a series of non-halide lead sources(e.g.,lead acetate(PbAc_(2)),lead sulfate(PbSO_(4)),lead carbonate(PbCO_(3)),lead nitrate(Pb(NO_(3))_(2)),lead formate(Pb(HCOO)_(2))and lead oxalate(PbC_(2)O_(4)))can be well dissolved in an ionic liquid solvent methylammonium acetate(MAAc).We found that the universal strong coordination of C=O with lead ion(Pb^(2+))and the formation of hydrogen bonds were observed in perovskite precursor solution.This allows the dissolution of non-halide lead salts and is able to produce perovskite film with smooth,compact,and full coverage crystal grain.The power conversion efficiency(PCE)of 14.48%,19.21%,and 20.13%in PSCs based on PbSO_(4),PbAc_(2),and PbCO_(3) was achieved,respectively,in the absence of any additives and passivation agents.This study demonstrates the universality of ionic liquid for the preparation of PSCs based on nonhalides lead sources.