Enhancing Light Outcoupling Efficiency via Anisotropic Low Refractive Index Electron Transporting Materials for Efficient Perovskite Light-Emitting Diodes.

Thanks to the extensive efforts toward optimizing perovskite crystallization properties, high-quality perovskite films with near-unity photoluminescence quantum yield are successfully achieved. However, the light outcoupling efficiency of perovskite light-emitting diodes (PeLEDs) is impeded by insufficient light extraction, which poses a challenge to the further advancement of PeLEDs. Here, an anisotropic multifunctional electron transporting material, 9,10-bis(4-(2-phenyl-1H-benzo[d]imidazole-1-yl)phenyl) anthracene (BPBiPA), with a low extraordinary refractive index (ne ) and high electron mobility is developed for fabricating high-efficiency PeLEDs. The anisotropic molecular orientations of BPBiPA can result in a low ne of 1.59 along the z-axis direction. Optical simulations show that the low ne of BPBiPA can effectively mitigate the surface plasmon polariton loss and enhance the photon extraction efficiency in waveguide mode, thereby improving the light outcoupling efficiency of PeLEDs. In addition, the high electron mobility of BPBiPA can facilitate balanced carrier injection in PeLEDs. As a result, high-efficiency green PeLEDs with a record external quantum efficiency of 32.1% and a current efficiency of 111.7 cd A-1 are obtained, which provides new inspirations for the design of electron transporting materials for high-performance PeLEDs.

Structural Engineering of Iridium(III) Phosphors with Imidazo[4,5-b]pyrazin-2-ylidene Cyclometalates for Efficient Blue Electroluminescence.

Iridium(III) complexes are particularly noted for their excellent potentials in fabrication of blue organic light-emitting diodes (OLEDs), but the severe efficiency roll-off largely hampered their practical applications. To reveal the underlying characteristics, three Ir(III) complexes, namely f-ct5c, f-ct5d, and f-ct11, bearing imidazo[4,5-b]pyrazin-2-ylidene cyclometalates are prepared and characterized in detail. Both f-ct5c and f-ct5d (also their mixture f-ct5mix) gave intensive blue emissions peaking at ≈465 nm with short radiative lifetimes of 1.76 and 2.45 µs respectively, in degassed toluene. Alternatively, f-ct11 with two 4-tert-butylphenyl substituents on each imidazo[4,5-b]pyrazin-2-ylidene entity, possessed a bluish-green emission (508 nm) together with an extended radiative lifetime of 34.3 µs in the dispersed PMMA matrix. Consequently, the resulting solution-processed OLED with f-ct11 delivered a maximum external quantum efficiency (EQEmax ) of 6.5% with serious efficiency roll-offs. In contrast, f-ct5mix based device achieved a high EQEmax of 27.2% and the EQE maintained at 23.0% of 1000 cd m-2 . Furthermore, the hyper-OLEDs with f-ct5mix as the sensitizer and v-DABNA as the terminal emitter afford narrowed emission with a considerably high EQEmax exceeding 32%, affirming the potential of f-ct5mix to serve as both the emitter and sensitizer in OLEDs.

Enhanced Horizontal Dipole Orientation by Novel Penta-Helicene Anthracene-Based Host for Efficient Blue Fluorescent OLEDs.

Due to the relatively low photoluminescence quantum yield (PLQY) and horizontal dipole orientation of doped films, anthracene-based fluorescent organic light-emitting diodes (F-OLEDs) have faced a great challenge to achieve high external quantum efficiency (EQE). Herein, a novel approach is introduced by incorporating penta-helicene into anthracene, presented as linear-shaped 3-(4-(10-phenylanthracen-9-yl)phenyl)dibenzo[c,g]phenanthrene (BABH) and 3-(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)dibenzo[c,g]phenanthrene (NABH). These blue hosts exhibit minimal intermolecular overlap of π-π stacking, effectively suppressing excimer formation, which facilitates the effective transfer of singlet energy to the fluorescent dopant for PLQY as high as 90%. Additionally, the as-obtained two hosts of BABH and NABH have effectively demonstrated major horizontal components transition dipole moments (TDM) and high thermal stability with glass transitional temperature (Tg ) surpassing 188 °C, enhancing the horizontal dipole orientation of their doped films to be 89% and 93%, respectively. The OLEDs based on BABH and NABH exhibit excellent EQE of 10.5% and 12.4% at 462 nm and device lifetime up to 90% of the initial luminance over 4500 h at 100 cd m-2 , which has firmly established them as among the most efficient blue F-OLEDs based on anthracene to date to the best knowledge. This work provides an instructive strategy to design an effective host for highly efficient and stable F-OLEDs.

Accelerating multielectron reduction at CuxO nanograins interfaces with controlled local electric field.

Regulating electron transport rate and ion concentrations in the local microenvironment of active site can overcome the slow kinetics and unfavorable thermodynamics of CO2 electroreduction. However, simultaneous optimization of both kinetics and thermodynamics is hindered by synthetic constraints and poor mechanistic understanding. Here we leverage laser-assisted manufacturing for synthesizing CuxO bipyramids with controlled tip angles and abundant nanograins, and elucidate the mechanism of the relationship between electron transport/ion concentrations and electrocatalytic performance. Potassium/OH- adsorption tests and finite element simulations corroborate the contributions from strong electric field at the sharp tip. In situ Fourier transform infrared spectrometry and differential electrochemical mass spectrometry unveil the dynamic evolution of critical *CO/*OCCOH intermediates and product profiles, complemented with theoretical calculations that elucidate the thermodynamic contributions from improved coupling at the Cu+/Cu2+ interfaces. Through modulating the electron transport and ion concentrations, we achieve high Faradaic efficiency of 81% at ~900 mA cm-2 for C2+ products via CO2RR. Similar enhancement is also observed for nitrate reduction reaction (NITRR), achieving 81.83 mg h-1 ammonia yield rate per milligram catalyst. Coupling the CO2RR and NITRR systems demonstrates the potential for valorizing flue gases and nitrate wastes, which suggests a practical approach for carbon-nitrogen cycling.

Cascading Energy Transfer for Highly Efficient Deep-Red OLED Emission with Cyclometalated [3+2+1] Iridium Complexes.

The promising cyclometalated iridium (III) complexes have been proved to possess great potential in vacuum-deposited organic light-emitting diodes (OLEDs) applications for full-color displays and white solid-state lighting sources. Herein, based on the unique bidentate ligand of dibenzo[a,c]phenazine (dbpz) group with strong conjugated effect of aromatic rings for red emission, four novel [3+2+1] coordinated iridium (III) emissive materials have been rationally designed and synthesized. The monodentate ligands of -CN and -OCN have been effectively employed to tune the deep-red emission of 628-675 nm with high photoluminescence quantum yields up to 98%. Moreover, all devices displayed deep-red color coordinates ranging from (0.675, 0.325) to (0.716, 0.284), which is close to the standard-red color coordinates of (0.708, 0.292), as recommended by International Telecommunication Union Radiocommunication (ITU-R) BT.2020. The device based on n BuIr(dbpz)CN with an exciplex cohost has exhibited maximum external quantum efficiencies of 20.7% and good stability. With n BuIr(dbpz)CN as an effective sensitizer, the n BuIr(dbpz)OCN based phosphorescent OLED devices have successfully demonstrated cascading energy transfer processes, contributing to pure red emission with maximum luminance as high as 6471 cd m-2 . Therefore, this work has been successfully demonstrated rational molecular design strategy of [3+2+1] iridium complexes to obtain highly efficient deep-red electrophosphorescent emission.

Enhancing operational stability of OLEDs based on subatomic modified thermally activated delayed fluorescence compounds.

The realization of operationally stable blue organic light-emitting diodes is a challenging issue across the field. While device optimization has been a focus to effectively prolong device lifetime, strategies based on molecular engineering of chemical structures, particularly at the subatomic level, remains little. Herein, we explore the effect of targeted deuteration on donor and/or acceptor units of thermally activated delayed fluorescence emitters and investigate the structure-property relationship between intrinsic molecular stability, based on isotopic effect, and device operational stability. We show that the deuteration of the acceptor unit is critical to enhance the photostability of thermally activated delayed fluorescence compounds and hence device lifetime in addition to that of the donor units, which is commonly neglected due to the limited availability and synthetic complexity of deuterated acceptors. Based on these isotopic analogues, we observe a gradual increase in the device operational stability and achieve the long-lifetime time to 90% of the initial luminance of 23.4 h at the luminance of 1000 cd m-2 for thermally activated delayed fluorescence-sensitized organic light-emitting diodes. We anticipate our strategic deuteration approach provides insights and demonstrates the importance on structural modification materials at a subatomic level towards prolonging the device operational stability.

New [3+2+1] Iridium Complexes as Effective Phosphorescent Sensitizers for Efficient Narrowband Saturated-Blue Hyper-OLEDs.

Two newly designed and synthesized [3+2+1] iridium complexes through introducing bulky trimethylsiliyl (TMS) groups are doped with a terminal emitter of v-DABNA to form an coincident overlapping spectra between the emission of these two phosphors and the absorption of v-DABNA, creating cascade resonant energy transfer for efficient triplet harvesting. To boost the color quality and efficiency, the fabricated hyper-OLEDs have been optimized to achieve a high external quantum efficiency of 31.06%, which has been among the highest efficiency results reported for phosphor sensitized saturated-blue hyper-OLEDs, and pure blue emission peak at 467 nm with the full width at half maxima (FWHM) as narrow as 18 nm and the CIEy values down to 0.097, satisfying the National Institute of Standards and Technology (NIST) requirement for saturated blue OLEDs display. Surprisingly, such hyper-OLEDs have obtained the converted lifetime (LT50 ) up to 4552 h at the brightness of 100 cd m-2 , demonstrating effective Förster resonance energy transfer (FRET) process. Therefore, employing these new bulky TMS substituent [3+2+1] iridium(III) complexes for effective sensitizers can greatly pave the way for further development of high efficiency and stable blue OLEDs in display and lighting applications.

Exploring the Core Parameters of CNC-Based Chiral Nematic Structures for Enhancing the Dissymmetry Factor of Right-Handed Circularly Polarized Luminescence.

The chiral nematic nanostructure formed from cellulose nanocrystal (CNC) self-assembly has shown great potential as a matrix for generating circularly polarized luminescent (CPL) light with a high dissymmetry factor. Exploring the relationship between the device composition and structure and the light dissymmetry factor is crucial to a common strategy for a strongly dissymmetric CPL light. In this study, we have compared the single-layered and double-layered CNC-based CPL devices with different luminophores, such as rhodamine 6G (R6G), methylene blue (MB), crystal violet (CV), and silicon quantum dots (Si QDs). We demonstrated that forming a double-layered structure of CNCs nanocomposites is a simple but effective pathway for enhancing the CPL dissymmetry factor for CNC-based CPL materials containing different luminophores. The |glum| values of double-layered CNC devices (dye@CNC5||CNC5) versus that of single-layered devices (dye@CNC5) are 3.25 times for Si QDs, 3.7 times for R6G, 3.1 times for MB, and 2.78 times for CV series. The different enhancement degrees of these CNC layers with a similar thickness may be due to the different pitch numbers in the chiral nematic liquid crystal layers whose photonic band gap (PBG) has been modified to match the emission wavelengths of dyes. Furthermore, the assembled CNC nanostructure has great tolerance to the addition of nanoparticles. Gold nanorods coated with the SiO2 layer (Au NR@SiO2) were added for enhancing the dissymmetry factor of MB in CNC composites (named MAS devices). When the strong longitudinal plasmonic band of the Au NR@SiO2 matched the emission wavelength of MB and the PBG of assembled CNC structures simultaneously, the increase in the glum factor and quantum yield of MAS composites was obtained. The good compatibility of the assembled CNC nanostructures makes it a universal platform for developing strong CPL light sources with a high dissymmetry factor.

Si/Organic Integrated Narrowband Near-Infrared Photodetector.

Spectrally selective narrowband photodetection is critical for near-infrared (NIR) imaging applications, such as for communicationand night-vision utilities. It is a long-standing challenge for detectors based on silicon, to achieve narrowband photodetection without integrating any optical filters. Here, this work demonstrates a NIR nanograting Si/organic (PBDBT-DTBT:BTP-4F) heterojunction photodetector (PD), which for the first time obtains the full-width-at-half-maximum (FWHM) of only 26 nm and fast response of 74 µs at 895 nm. The response peak can be successfully tailored from 895 to 977 nm. The sharp and narrow response NIR peak is inherently attributed to the coherent overlapping between the NIR transmission spectrum of organic layer and diffraction enhanced absorption peak of patterned nanograting Si substrates. The finite difference time domain (FDTD) physics calculation confirms the resonant enhancement peaks, which is well consistent with the experiment results. Meanwhile, the relative characterization indicates that the introduction of the organic film can promote carrier transfer and charge collection, facilitating efficient photocurrent generation. This new device design strategy opens up a new window in developing low-cost sensitive NIR narrowband detection.

Ultrafast Charge Transfer 2D MoS2 /Organic Heterojunction for Sensitive Photodetector.

The 2D MoS2 with superior optoelectronic properties such as high charge mobility and broadband photoresponse has attracted broad research interests in photodetectors (PD). However, due to the atomic thin layer of 2D MoS2 , its pure photodetectors usually suffer from inevitable drawbacks such as large dark current, and intrinsically slow response time. Herein, a new organic material BTP-4F with high mobility is successfully stacked with 2D MoS2 film to form an integrated 2D MoS2 /organic P-N heterojunction, facilitating efficient charge transfer as well as significantly suppressed dark current. As a result, the as-obtained 2D MoS2 /organic (PD) has exhibited excellent response and fast response time of 332/274 µs. The analysis validated photogenerated electron transition from this monolayer MoS2 to subsequent BTP-4F film, whereas the transited electron is originated from the A- exciton of 2D MoS2 by temperature-dependent photoluminescent analysis. The ultrafast charge transfer time of ≈0.24 ps measured by time-resolved transient absorption spectrum is beneficial for efficient electron-hole pair separation, greatly contributing to the obtained fast photoresponse time of 332/274 µs. This work can open a promising window to acquire low-cost and high-speed (PD).

Low-voltage-modulated perovskite/organic dual-band photodetectors for visible and near-infrared imaging.

Visible and near-infrared (NIR) light dual-band photodetectors (PDs) have potential applications in signal detection, bioimaging, optical communications and safety monitoring. Herein, we report an ultrafast perovskite/organic heterojunction dual-mode PD with a voltage-modulated photoresponse range in visible and NIR spectra. The PD, comprising a perovskite layer to absorb visible light (500-810 nm) and an organic bulk heterojunction layer for NIR light absorption (810-950 nm), exhibited a switchable spectral response in the visible or NIR bands. The voltage-modulated visible and NIR photoresponses of the PD were attributable to controlled charge photogeneration in perovskite and organic blend thin films under different bias polarities. The device exhibited peak responsivities of 93.5 and 102.2 mA/W in the visible and NIR bands, respectively; a high detectivity of 4.3 × 109 Jones (at forward bias of 0.7 V and incident 625 nm light) and 1.6 × 1012 Jones (at reverse bias of -1.5 V and incident 900 nm light); a fast microsecond response time; and a wide dynamic range (>120 dB) both in the visible mode and NIR mode. Also, this voltage-modulated dual-band PD shows promising applications in visible light and NIR imaging, which is proven by demonstrating a PD array with 25 pixels (5 × 5).

Exploiting extraordinary topological optical forces at bound states in the continuum.

Polarization singularities and topological vortices in photonic crystal slabs centered at bound states in the continuum (BICs) can be attributed to zero amplitude of polarization vectors. We show that such topological features are also observed in optical forces within the vicinity of BIC, around which the force vectors wind in the momentum space. The topological force carries force topological charge and can be used for trapping and repelling nanoparticles. By tailoring asymmetry of the photonic crystal slab, topological force will contain spinning behavior and shifted force zeros, which can lead to three-dimensional asymmetric trapping. Several off-Γ BICs generate multiple force zeros with various force distribution patterns. Our findings introduce the concepts of topology to optical force around BICs and create opportunities to realize optical force vortices and enhanced reversible forces for manipulating nanoparticles and fluid flow.

Hybrid modeling of perovskite light-emitting diodes with nanostructured emissive layers.

Perovskite light-emitting diodes (PeLEDs) have attracted much attention due to their superior performance. When a bottleneck of energy conversion efficiency is achieved with materials engineering, nanostructure incorporation proves to be a feasible approach to further improve device efficiencies via light extraction enhancement. The finite-difference time-domain simulation is widely used for optical analysis of nanostructured optoelectronic devices, but reliable modeling of PeLEDs with nanostructured emissive layers remains unmet due to the difficulty of locating dipole light sources. Herein we established a hybrid process for modeling light emission behaviors of such nanostructured PeLEDs by calibrating light source distribution through electrical simulations. This hybrid modeling method serves as a universal tool for structure optimization of light-emitting diodes with nanostructured emissive layers.

Artificial neuromorphic cognitive skins based on distributed biaxially stretchable elastomeric synaptic transistors.

Cephalopod (e.g., squid, octopus, etc.) skin is a soft cognitive organ capable of elastic deformation, visualizing, stealth, and camouflaging through complex biological processes of sensing, recognition, neurologic processing, and actuation in a noncentralized, distributed manner. However, none of the existing artificial skin devices have shown distributed neuromorphic processing and cognition capabilities similar to those of a cephalopod skin. Thus, the creation of an elastic, biaxially stretchy device with embedded, distributed neurologic and cognitive functions mimicking a cephalopod skin can play a pivotal role in emerging robotics, wearables, skin prosthetics, bioelectronics, etc. This paper introduces artificial neuromorphic cognitive skins based on arrayed, biaxially stretchable synaptic transistors constructed entirely out of elastomeric materials. Systematic investigation of the synaptic characteristics such as the excitatory postsynaptic current, paired-pulse facilitation index of the biaxially stretchable synaptic transistor under various levels of biaxial mechanical strain sets the operational foundation for stretchy distributed synapse arrays and neuromorphic cognitive skin devices. The biaxially stretchy arrays here achieved neuromorphic cognitive functions, including image memorization, long-term memorization, fault tolerance, programming, and erasing functions under 30% biaxial mechanical strain. The stretchy neuromorphic imaging sensory skin devices showed stable neuromorphic pattern reinforcement performance under both biaxial and nonuniform local deformation.

Unravelling Alkali-Metal-Assisted Domain Distribution of Quasi-2D Perovskites for Cascade Energy Transfer toward Efficient Blue Light-Emitting Diodes.

Solution processable quasi-2D (Q-2D) perovskite materials are emerging as a promising candidate for blue light source in full-color display applications due to their good color saturation property, high brightness, and spectral tunability. Herein, an efficient energy cascade channel is developed by introducing sodium bromide (NaBr) in phenyl-butylammonium (PBA)-containing mixed-halide Q-2D perovskites for a blue perovskite light-emitting diode (PeLED). The incorporation of alkali metal contributes to the nucleation and growth of Q-2D perovskites into graded distribution of domains with different layer number . The study of excitation dynamics by transient absorption (TA) spectroscopy confirms that NaBr induces more Q-2D perovskite phases with small n number, providing a graded energy cascade pathway to facilitate more efficient energy transfer processes. In addition, the nonradiative recombination within the Q-2D perovskites is significantly suppressed upon Na+ incorporation, as validated by the trap density estimation. Consequently, the optimized blue PeLEDs manifest a peak external quantum efficiency (EQE) of 7.0% emitting at 486 nm with a maximum luminance of 1699 cd m-2 . It is anticipated that these findings will improve the understanding of alkali-metal-assisted optimization of Q-2D perovskites and pave the way toward high-performance blue PeLEDs.

Fluorescent concentrator based MISO-NOMA for visible light communications.

The experimental realization of multiple-input single-output (MISO) in visible light communication (VLC) has always been difficult due to dynamic channels, complex alignment, and limited capacity. We designed a quantum dot (QD) fluorescent concentrator combined with power domain multiplexing of a non-orthogonal multiple access (NOMA) scheme to provide an estimation-free MISO system. The system supports a large detection area of over 4 cm2 and a sum rate up to 120 Mbps over 2.3-m free space, providing a promising connection for the Internet of things (IoT). The concentrator was further implemented in an underwater environment under insufficient incident power. A record data rate of 120 Mbps has been achieved in a 1.5-m underwater MISO system, with a mean bit error rate of 3.24 × 10-3, which is below the forward error correction criterion.

Double Cascading Charge Transfer at Integrated Perovskite/Organic Bulk Heterojunctions for Extended Near-Infrared Photoresponse and Enhanced Photocurrent.

Nowadays, nearly 48.7% near-infrared (NIR) irradiation (>800 nm) of the full solar spectrum has actually not been fully utilized since the state-of-the-art perovskite film usually can only absorb the most UV-vis sunlight radiation. Herein, high efficiency integrated Cs0.15 FA0.85 PbI3 perovskite/organic bulk (PC61 BM:D18:Y6) heterojunction solar cells with enhanced low energy photon harvest until 931 nm and a high maintained open circuit voltage of 1.04 V is successfully obtained. In particular, the favorable double cascading charge transfer paths pave an interesting possibility to spatially separate electrons upon visible light excitation and holes upon NIR photon absorption simultaneously at interfaces, significantly suppressing non-radiative bimolecular recombination and reaching the photocurrent density as high as 27.48 mA cm-2 and power conversion efficiency of 20.31%. Besides, the strong hydrophobicity of the ternary organic film has effectively prevented ambient humidity penetration and improves the stability of the perovskite in the continuous aging test (humidity > 60%) compared with the control device. This work has opened a significantly new window to improve the NIR light harvest for next generation highly efficient solar cells with full spectrum response.

Fine Emission Tuning from Near-Ultraviolet to Saturated Blue with Rationally Designed Carbene-Based [3 + 2 + 1] Iridium(III) Complexes.

We designed and synthesized a new class of six phosphorescent [3 + 2 + 1] iridium(III) complexes [(pbib)Ir(C^C)CN] bearing a tridentate 1,3-bis(1-butylimidazolin-2-ylidene) phenyl N-heterocyclic carbene (NHC)-based pincer ligand (pbib), bidentate imidazole-based NHC ligands (C^C), and a monodentate cyano group and investigated their photophysical, electrochemical, and thermal stabilities and electroluminescent properties. The extended π-conjugation of the imidazole-based C^C ligand is found to be the key to fine-tune the emission energies from ultraviolet blue (λ = 378 nm) to saturated blue (λ = 482 nm), as shown by electrochemical and photophysical studies, which is also revealed by the density functional theory (DFT) and time-dependent DFT calculations. Vacuum-deposited organic light-emitting diode devices have been fabricated with these newly synthesized emitters and exhibited the best external quantum efficiency of 6.4% and Commission International de L'Éclairage (CIE) coordinates of (0.163, 0.096), where the CIE y is very similar to the National Television System Committee standard blue CIE (x, y) coordinates of (0.149, 0.085). These results indicate that the novel [3 + 2 + 1] coordinated iridium(III) complexes [(pbib)Ir(C^C)CN], having a saturated blue emission, not only could alleviate the photodegradation of the emitters when compared to [(pbib)Ir(pmi)CN] but also provide new design strategies of saturated-blue-emitting iridium(III) complexes.

Freestanding and Sandwich MXene-Based Cathode with Suppressed Lithium Polysulfides Shuttle for Flexible Lithium-Sulfur Batteries.

Flexible lithium-sulfur (Li-S) batteries with high mechanical compliance and energy density are highly desired. This manuscript reported that large-area freestanding MXene (Ti3C2Tx) film has been obtained through a scalable drop-casting method, significantly improving adhesion to the sulfur layer under the continuously bent. Titanium oxide anchored on holey Ti3C2Tx (TiO2/H-Ti3C2Tx) was also produced by the well-controlled oxidation of few-layer Ti3C2Tx, which greatly facilitates lithium ion transport as well as prevents the shuttling of lithium polysulfides. Therefore, the obtained sandwich electrode has demonstrated a high capacity of 740 mAh g-1 at 2 C and a high capacity retention of 81% at 1 C after 500 cycles. Flexible Li-S batteries based on this sandwich electrode have a capacity retention as high as 95% after bending 500 times. This work provides effective design strategies of MXene for flexible batteries and wearable electronics.