Magnetic Hyperporous Elastic Material with Excellent Fatigue Resistance and Oil Retention for Oil-Water Separation.

Oily wastewater has caused serious threats to the environment; thus, high-performance absorbing materials for effective oil-water separation technology have attracted increasing attention. Herein, we develop a magnetic, hydrophobic, and lipophilic hyperporous elastic material (HEM) templated by high internal phase emulsions (HIPE), in which free-radical polymerization of butyl acrylate (BA) and divinylbenzene (DVB) is employed in the presence of poly(dimethylsiloxane) (PDMS), lecithin surfactant, and modified Fe3O4 nanoparticles. The adoption of the emulsion template with nanoparticles as both stabilizers and cross-linkers endows the HEM with biomimetic hierarchical open-cell micropores and elastic cross-linked networks, generating an oil absorbent with outstanding mechanical stability. Compressive fatigue resistance of the HEM is demonstrated to endure 2000 mechanical cycles without plastic deformation or strength degradation. By exploiting the synergistic effect of hierarchical structures and low-surface-energy components, the resulting HEM also possesses excellent and robust hydrophobicity (water contact angle of 164°) and good oil absorption capacity, in which Fe3O4 nanoparticles lead to convenient magnetically controlled oil recyclability as well. Notably, the unique biomimetic microporous structure demonstrates superior oil retention capacity (>95% at 1000 rpm and >60% at 10,000 rpm) over the state-of-the-art porous materials for a diverse variety of oils to reduce the risk of secondary oil leakage, along with good recoverability by squeezing owing to the excellent compression resilience. These excellent performances of our HEM provide broad prospects for practical applications in oil-water separation, energy conversion, and smart soft robotics.

Adaptive decision threshold algorithm based on a sliding window to reduce BER of free-space optical communication systems.

Free-space optical communication (FSOC) systems face susceptibility to several factors, such as transmission distance, atmospheric turbulence, and alignment errors. These elements contribute to fluctuations in the signal strength reaching the receiver. The resultant signal fluctuations can result in misjudgments and an elevated bit error rate (BER). This paper proposes an adaptive decision threshold algorithm based on a sliding window (ADTSW). By estimating received signal parameters and delimiting the amplitude interval, the algorithm ensures that the decision threshold tracks signal fluctuations, thereby reducing signal misjudgment. The effectiveness of the algorithm is validated through simulations and experimentation. When the signal peak-to-peak value fluctuates, simulation results demonstrate that the proposed algorithm achieves a 1-order-of-magnitude reduction in BER compared to the traditional fixed decision threshold (FDT) method. Under the influence of weak atmospheric turbulence with different scintillation variance, both simulation and experimentation indicate a 1-order-of-magnitude reduction in BER compared to the FDT method. The ADTSW algorithm proves its capability in minimizing misjudgments, thereby effectively reducing BER and improving communication quality.

Versatile Neuromorphic Modulation and Biosensing based on N-type Small-molecule Organic Mixed Ionic-Electronic Conductors.

The ion/chemical-based modulation feature of organic mixed ionic-electronic conductors (OMIECs) are critical to advancing next generation bio-integrated neuromorphic hardware. Despite achievements with polymeric OMIECs in organic electrochemical neuronal synapse (OENS). However, small molecule OMIECs based OENS has not yet been realized. Here, for the first time, we demonstrate an effective materials design concept of combining n-type fused all-acceptor small molecule OMIECs with subtle side chain optimization that enables robustly and flexibly modulating versatile synaptic behavior and sensing neurotransmitter in solid or aqueous electrolyte, operating in accumulation modes. By judicious tuning the ending side chains, the linear oligoether and butyl chain derivative gNR-Bu exhibits higher recognition accuracy for a model artificial neural network (ANN) simulation, higher steady conductance states and more outstanding ambient stability, which is superior to the state-of-art n-type OMIECs based OENS. These superior artificial synapse characteristics of gNR-Bu can be attributed to its higher crystallinity with stronger ion bonding capacities. More impressively, we unprecedentedly realized n-type small-molecule OMIECs based OENS as a neuromorphic biosensor enabling to respond synaptic communication signals of dopamine even at sub-µM level in aqueous electrolyte. This work may open a new path of small-molecule ion-electron conductors for next-generation ANN and bioelectronics.

Glycol Monomethyl Ether-Substituted Carbazolyl Hole-Transporting Material for Stable Inverted Perovskite Solar Cells with Efficiency of 25.52.

Organic self-assembled molecules (OSAMs) based hole transporting materials play a pivotal role in achieving highly efficient and stable inverted perovskite solar cells (IPSCs). However, the reported carbazol-based OSAMs have serious drawbacks, such as poor solubility in alcohol solution, worse matched energy arrangement with perovskite, and limited molecular species, which greatly limit the device performance. To address above problems, a novel OSAM 4-(3,6-glycol monomethyl ether-9H-carbazol-9-yl) butyl]phosphonic acid (GM-4PACz) was synthesized as hole-transporting material by introducing glycol monomethyl ether (GM) side chains at carbazolyl unit. GM groups enhance the surface energy of Indium Tin Oxide (ITO)/SAM substrate to facilitate the nucleation and growth of up perovskite film, suppress cation defects, release the residual stress at SAM/perovskite interface, and evaluate energy level for matching with perovskite. Consequently, the GM-4PACz based IPSC achieves a champion PCE of 25.52%, a respectable open-circuit voltage (VOC) of 1.21 V, a high stability, possessing 93.29% and 91.75% of their initial efficiency after aging in air for 2000 h or tracking at maximum power point for 1000 h, respectively.

150 Gbps multi-wavelength FSO transmission with 25-GHz ITU-T grid in the mid-infrared region.

The 3∼5 µm mid-infrared (mid-IR) light has several exceptional benefits in the case of adverse atmospheric conditions compared to the 1.5 µm band, so it is a promising candidate for optical carriers for free-space communication (FSO) through atmospheric channels. However, the transmission capacity in the mid-IR band is constrained in the lower range due to the immaturity of its devices. In this work, to replicate the 1.5 µm band dense wavelength division multiplexing (DWDM) technology to the 3 µm band for high-capacity transmission, we demonstrate a 12-channel 150 Gbps FSO transmission in the 3 µm band based on our developed mid-IR transmitter and receiver modules. These modules enable wavelength conversion between the 1.5 µm and 3 µm bands based on the effect of difference-frequency generation (DFG). The mid-IR transmitter effectively generates up to 12 optical channels ranging from 3.5768 µm to 3.5885 µm with a power of 6.6 dBm, and each channel carries 12.5 Gbps binary phase shift keying (BPSK) modulated data. The mid-IR receiver regenerates the 1.5 µm band DWDM signal with a power of -32.1 dBm. Relevant results of regenerated signal demodulation have been collected in detail, including bit error ratio (BER), constellation diagram, and eye diagram. The power penalties of the 6th to 8th channels selected from the regenerated signal are lower than 2.2 dB compared with back-to-back (BTB) DWDM signal at a bit error ratio (BER) of 1E-6, and other channels can also achieve good transmission quality. It is expected to further push the data capacity to the terabit-per-second level by adding more 1.5 µm band laser sources and using wider-bandwidth chirped nonlinear crystals.

Free-space transmission of picosecond-level, high-speed optical pulse streams in the 3†µm band.

The utilization of mid-infrared (mid-IR) light spanning the 3-5 µm range presents notable merits over the 1.5 µm band when operating in adverse atmospheric conditions. Consequently, it emerges as a promising prospect for serving as optical carriers in free-space communication (FSO) through atmospheric channels. However, due to the insufficient performance level of devices in the mid-IR band, the capability of mid-IR communication is hindered in terms of transmission capacity and signal format. In this study, we conduct experimental investigations on the transmission of time-domain multiplexed ultra-short optical pulse streams, with a pulse width of 1.8 ps and a data rate of up to 40 Gbps at 3.6 µm, based on the difference frequency generation (DFG) effect. The mid-IR transmitter realizes an effective wavelength conversion of optical time division multiplexing (OTDM) signals from 1.5 µm to 3.6 µm, and the obtained power of the 40 Gbps mid-IR OTDM signal at the optimum temperature of 54.8 °C is 7.4 dBm. The mid-IR receiver successfully achieves the regeneration of the 40 Gbps 1.5 µm OTDM signal, and the corresponding regenerated power at the optimum temperature of 51.5 °C is -30.56 dBm. Detailed results pertaining to the demodulation of regeneration 1.5 µm OTDM signal have been acquired, encompassing parameters such as pulse waveform diagram, bit error rate (BER), and Q factor. The estimated power penalty of the 40 Gbps mid-IR OTDM transmission is 2.4 dB at a BER of 1E-6, compared with the back-to-back (BTB) transmission. Moreover, it is feasible by using chirped PPLN crystals with wider bandwidth to increase the data rate to the order of one hundred gigabits.

Near-noiseless and small-footprint phase sensitive optical parametric amplifier using AlGaAs-on-insulator waveguides.

Phase sensitive amplifiers (PSAs) based on optical parametric amplification feature near noiseless amplification, which is of considerable benefit for improving the performance of optical communication systems. Currently, the majority of research on PSAs is carried out on the basis of highly nonlinear fibers or periodically poled lithium niobite waveguides, with the impediments of being susceptible to environmental interference and requiring complex temperature control systems to maintain quasi-phase matching conditions, respectively. Here, a near-noiseless and small-footprint PSA based on dispersion-engineered AlGaAs-on-insulator (AlGaAsOI) waveguides is proposed and demonstrated theoretically. The phase-dependent gain and the phase-to-phase transfer function of the PSA are calculated to analyze its characteristics. Furthermore, we investigate in detail the effects of linear loss, nonlinear coefficient, and pump power on the PSA gain and noise figure (NF) in AlGaAsOI waveguides. The results show that a PSA based on an AlGaAsOI waveguide is feasible with a maximum phase sensitive gain of 33 dB, achieving an NF of less than 1 dB over a gain bandwidth of 245 nm with a gain of >15d B, which completely covers the S + C + L band. This investigation is worthwhile for noiseless PSAs on photonic integrated chips, which are promising for low-noise optical amplification, multifunctional photonic integrated chips, quantum communication, and spectroscopy, and as a reference for low-noise PSAs depending on the third-order nonlinearity, χ (3), of the waveguide material.

Multi-modulation compatible miniaturization system for FSO communication assisted by chirp-managed laser.

In recent years, the thriving satellite laser communication industry has been severely hindered by the limitations of incompatible modulation formats and restricted Size Weight and Power (SWaP). A multi-modulation compatible method serving for free-space optical (FSO) communication has been proposed assisted by chirp-managed laser (CML). The corresponding demonstration system has been established for realizing free-switching between intensity (OOK) and phase modulation (RZ-DPSK). The feasibility and performance of system have been evaluated sufficiently when loading with 2.5 and 5 Gbps data streams, respectively. Additionally, a control-group system has been operated utilizing Mach-Zehnder modulator (MZM) for comparison between CML-based and MZM-based compatibility solutions. The OOK receiving sensitivities of CML-based system are -47.02 dBm@2.5 Gbps and -46.12 dBm@5 Gbps at BER of 1×10-3 which are 0.62 dB and 1.11 dB higher than that of MZM; the receiving sensitivities of RZ-DPSK are -50.12 dBm@2.5 Gbps and -47.03 dBm@5 Gbps which are 0.79 dB and 0.47 dB higher than that of MZM respectively. Meanwhile, CML-based transmitter abandoned the traditional modulator and its complicated supporting devices which can effectively contribute to the reduction of SWaP. The CML-based system has been proven to have the compatibility between intensity and phase modulation while also possesses a miniaturized design. It may provide fresh thinking to achieve a practical miniaturization system for satisfying the requirements of space optical network in future.

150 Gbit/s 1 km high-sensitivity FSO communication outfield demonstration based on a soliton microcomb.

A high-sensitivity and large-capacity free space optical (FSO) communication scheme based on the soliton microcomb (SMC) is proposed. Using ultra-large bandwidth stabilized SMC with a frequency interval of 48.97 GHz as the laser source, 60 optical wavelengths modulated by 2.5 Gbit/s 16-Pulse position modulation (PPM) are transmitted in parallel. A corresponding outfield high-sensitivity 150 Gbit/s FSO communication experiment based on the SMC was carried out with 1 km space distance. Our experimental results show that the best sensitivity of the single comb wavelength which has higher OSNR can reach -52.62 dBm, and the difference is only 1.38 dB from the theoretical limit under the BER of 1 × 10-3 without forward error correction (FEC). In addition, at BER of 1 × 10-3, 16-PPM has a higher received sensitivity of 6.73dB and 3.72dB compared to on-off keying (OOK) and differential phase shift keying (DPSK) respectively. Meanwhile, taking the advantage of multi-channel SMC, 60 × 2.5 Gbit/s can achieve 150 Gbit/s large-capacity free-space transmission. For comparison, commercially available single-wavelength laser based FSO communication system have also been performed in the outfield. The outfield experimental results demonstrated the feasibility of high-sensitivity, large-capacity PPM FSO communication based on SMCs and provided a new perspective for the future development of large-capacity, long-haul FSO communication.

Recent progress in creating complex and multiplexed surface-grafted macromolecular architectures.

Surface-grafted macromolecules, including polymers, DNA, peptides, etc., are versatile modifications to tailor the interfacial functions in a wide range of fields. In this review, we aim to provide an overview of the most recent progress in engineering surface-grafted chains for the creation of complex and multiplexed surface architectures over micro- to macro-scopic areas. A brief introduction to surface grafting is given first. Then the fabrication of complex surface architectures is summarized with a focus on controlled chain conformations, grafting densities and three-dimensional structures. Furthermore, recent advances are highlighted for the generation of multiplexed arrays with designed chemical composition in both horizontal and vertical dimensions. The applications of such complicated macromolecular architectures are then briefly discussed. Finally, some perspective outlooks for future studies and challenges are suggested. We hope that this review will be helpful to those just entering this field and those in the field requiring quick access to useful reference information about the progress in the properties, processing, performance, and applications of functional surface-grafted architectures.

Doubly Covariance Matrix Reconstruction Based Blind Beamforming for Coherent Signals.

This paper proposes a beamforming method in the presence of coherent multipath arrivals at the array. The proposed method avoids the prior knowledge or estimation of the directions of arrival (DOAs) of the direct path signal and the multipath signals. The interferences are divided into two groups based on their powers and the interference-plus-noise covariance matrix (INCM) is reconstructed through the doubly covariance matrix reconstruction concept. The composite steering vector (CSV) that accounts for the direct path signal and multipath signals is estimated as the principal eigenvector of the sample covariance matrix with interferences and noise removed. The optimal weight vector is finally computed using the INCM and the CSV. The proposed method involves no spatial smoothing and avoids reduction in the degree of freedom. Simulation results demonstrate the improved performance of the proposed method.

Windowless Observation of Evaporation-Induced Coarsening of Au-Pt Nanoparticles in Polymer Nanoreactors.

The interactions between nanoparticles and solvents play a critical role in the formation of complex, metastable nanostructures. However, direct observation of such interactions with high spatial and temporal resolution is challenging with conventional liquid-cell transmission electron microscopy (TEM) experiments. Here, a windowless system consisting of polymer nanoreactors deposited via scanning probe block copolymer lithography (SPBCL) on an amorphous carbon film is used to investigate the coarsening of ultrafine (1-3 nm) Au-Pt bimetallic nanoparticles as a function of solvent evaporation. In such reactors, homogeneous Au-Pt nanoparticles are synthesized from metal-ion precursors in situ under electron irradiation. The nonuniform evaporation of the thin polymer film not only concentrates the nanoparticles but also accelerates the coalescence kinetics at the receding polymer edges. Qualitative analysis of the particle forces influencing coalescence suggests that capillary dragging by the polymer edges plays a significant role in accelerating this process. Taken together, this work (1) provides fundamental insight into the role of solvents in the chemistry and coarsening behavior of nanoparticles during the synthesis of polyelemental nanostructures, (2) provides insight into how particles form via the SPBCL process, and (3) shows how SPBCL-generated domes, instead of liquid cells, can be used to study nanoparticle formation. More generally, it shows why conventional models of particle coarsening, which do not take into account solvent evaporation, cannot be used to describe what is occurring in thin film, liquid-based syntheses of nanostructures.

Structural Evolution of Three-Component Nanoparticles in Polymer Nanoreactors.

Recent developments in scanning probe block copolymer lithography (SPBCL) enable the confinement of multiple metal precursors in a polymer nanoreactor and their subsequent transformation into a single multimetallic heterostructured nanoparticle through thermal annealing. However, the process by which multimetallic nanoparticles form in SPBCL-patterned nanoreactors remains unclear. Here, we utilize the combination of PEO-b-P2VP and Au, Ag, and Cu salts as a model three-component system to investigate this process. The data suggest that the formation of single-component Au, Ag, or Cu nanoparticles within polymer nanoreactors consists of two stages: (I) nucleation, growth, and coarsening of the particles to yield a single particle in each reactor; (II) continued particle growth by depletion of the remaining precursor in the reactor until the particle reaches a stable size. Also, different aggregation rates are observed for single-component particle formation (Au > Ag > Cu). This behavior is also observed for two-component systems, where nucleation sites have greater Au content than the other metals. This information can be used to trap nanoparticles with kinetic structures. High-temperature treatment ultimately facilitates the structural evolution of the kinetic particle into a particle with a fixed structure. Therefore, with multicomponent systems, a third stage that involves elemental redistribution within the particle must be part of the description of the synthetic process. This work not only provides a glimpse at the mechanism underlying multicomponent nanoparticle formation in SPBCL-generated nanoreactors but also illustrates, for the first time, the utility of SPBCL as a platform for controlling the architectural evolution of multimetallic nanoparticles in general.

Large-Area Patterning of Metal Nanostructures by Dip-Pen Nanodisplacement Lithography for Optical Applications.

Au nanostructures are remarkably important in a wide variety of fields for decades. The fabrication of Au nanostructures typically requires time-consuming and expensive electron-beam lithography (EBL) that operates in vacuum. To address this challenge, this paper reports the development of massive dip-pen nanodisplacement lithography (DNL) as a desktop fabrication tool, which allows high-throughput and rational design of arbitrary Au nanopatterns in ambient condition. Large-area (1 cm2 ) and uniform (<10% variation) Au nanostructures as small as 70 nm are readily fabricated, with a throughput 100-fold higher than that of conventional EBL. As a proof-of-concept of the applications in the opitcal field, we fabricate discrete Au nanorod arrays that show significant plasmonic resonance in the visible range, and interconnected Au nanomeshes that are used for transparent conductive electrode of solar cells.

Size-tunable, highly sensitive microelectrode arrays enabled by polymer pen lithography.

By combining polymer pen lithography (PPL) patterning with in situ polymerization, we report a straightforward and bottom-up approach for bench-top fabrication of microelectrode arrays (MEAs) with well-controlled dimensions. The as-fabricated MEAs can be used to electrodeposit prussian blue in situ and work as a biosensor for H2O2 with a detection limit as low as 5 nM at a sensitivity of 0.7 A cm-2 M-1.

The Structural Fate of Individual Multicomponent Metal-Oxide Nanoparticles in Polymer Nanoreactors.

Multicomponent nanoparticles can be synthesized with either homogeneous or phase-segregated architectures depending on the synthesis conditions and elements incorporated. To understand the parameters that determine their structural fate, multicomponent metal-oxide nanoparticles consisting of combinations of Co, Ni, and Cu were synthesized by using scanning probe block copolymer lithography and characterized using correlated electron microscopy. These studies revealed that the miscibility, ratio of the metallic components, and the synthesis temperature determine the crystal structure and architecture of the nanoparticles. A Co-Ni-O system forms a rock salt structure largely owing to the miscibility of CoO and NiO, while Cu-Ni-O, which has large miscibility gaps, forms either homogeneous oxides, heterojunctions, or alloys depending on the annealing temperature and composition. Moreover, a higher-ordered structure, Co-Ni-Cu-O, was found to follow the behavior of lower ordered systems.

Biomimicking Nano-Micro Binary Polymer Brushes for Smart Cell Orientation and Adhesion Control.

A new biomimetic surface named nano-micro binary polymer brushes is fabricated by large-area bench-top dip-pen nanodisplacement lithography technique. It is composed of gelatin-modified poly(glycidyl methacrylate) nanolines which are spaced by microstripes of poly(N-isopropylacrylamide). Cells are not only adhered and oriented well on the re-used surface, but also detachable from the surface with well-preserved extracellular matrix and aligned morphology.

Liquid-Phase Beam Pen Lithography.

Beam pen lithography (BPL) in the liquid phase is evaluated. The effect of tip-substrate gap and aperture size on patterning performance is systematically investigated. As a proof-of-concept experiment, nanoarrays of nucleotides are synthesized using BPL in an organic medium, pointing toward the potential of using liquid phase BPL to perform localized photochemical reactions that require a liquid medium.

Concurrent Covalent and Supramolecular Polymerization.

Covalent and supramolecular polymerizations, both of which offer their own unique advantages, have emerged as popular strategies for making artificial materials. Herein, we describe a concurrent covalent and supramolecular polymerization strategy-namely, one which utilizes 1) a bis-azide-functionalized diazaperopyrenium dication that undergoes polymeriation covalently with a bis-alkyne-functionalized biphenyl derivative in one dimension as a result of a rapid and efficient ß-cyclodextrin(CD)-accelerated, cucurbit[6]uril(CB)-templated azide-alkyne cycloaddition, while 2) the aromatic core of the dication is able to dimerize in a criss-cross fashion by dint of π-π interactions, enabling simultaneous supramolecular assembly, resulting in an extended polymer network in an orthogonal dimension.

Tip-Directed Synthesis of Multimetallic Nanoparticles.

Alloy nanoparticles are important in many fields, including catalysis, plasmonics, and electronics, due to the chemical and physical properties that arise from the interactions between their components. Typically, alloy nanoparticles are made by solution-based synthesis; however, scanning-probe-based methods offer the ability to make and position such structures on surfaces with nanometer-scale resolution. In particular, scanning probe block copolymer lithography (SPBCL), which combines elements of block copolymer lithography with scanning probe techniques, allows one to synthesize nanoparticles with control over particle diameter in the 2-50 nm range. Thus far, single-element structures have been studied in detail, but, in principle, one could make a wide variety of multicomponent systems by controlling the composition of the polymer ink, polymer feature size, and metal precursor concentrations. Indeed, it is possible to use this approach to synthesize alloy nanoparticles comprised of combinations of Au, Ag, Pd, Ni, Co, and Pt. Here, such structures have been made with diameters deliberately tailored in the 10-20 nm range and characterized by STEM and EDS for structural and elemental composition. The catalytic activity of one class of AuPd alloy nanoparticles made via this method was evaluated with respect to the reduction of 4-nitrophenol with NaBH4. In addition to being the first catalytic studies of particles made by SPBCL, these proof-of-concept experiments demonstrate the potential for SPBCL as a new method for studying the fundamental science and potential applications of alloy nanoparticles in areas such as heterogeneous catalysis.