The pressing demand for sustainable energy storage solutions has spurred the burgeoning development of aqueous zinc batteries. However, kinetics-sluggish Zn2+ as the dominant charge carriers in cathodes leads to suboptimal charge-storage capacity and durability of aqueous zinc batteries. Here, we discover that an ultrathin two-dimensional polyimine membrane, featured by dual ion-transport nanochannels and rich proton-conduction groups, facilitates rapid and selective proton passing. Subsequently, a distinctive electrochemistry transition shifting from sluggish Zn2+-dominated to fast-kinetics H+-dominated Faradic reactions is achieved for high-mass-loading cathodes by using the polyimine membrane as an interfacial coating. Notably, the NaV3O8·1.5H2O cathode (10 mg cm-2) with this interfacial coating exhibits an ultrahigh areal capacity of 4.5 mAh cm-2 and a state-of-the-art energy density of 33.8 Wh m-2, along with apparently enhanced cycling stability. Additionally, we showcase the applicability of the interfacial proton-selective coating to different cathodes and aqueous electrolytes, validating its universality for developing reliable aqueous batteries.
Graphene is used as a growth template for van der Waals epitaxy of organic semiconductor (OSC) thin films. During the synthesis and transfer of chemical-vapor-deposited graphene on a target substrate, local inhomogeneities in the graphene-in particular, a nonuniform strain field in the graphene template-can easily form, causing poor morphology and crystallinity of the OSC thin films. Moreover, a strain field in graphene introduces a pseudo-electric field in the graphene. Here, the study investigates how the strain and strain-induced pseudo-electric field of a graphene template affect the self-assembly of π-conjugated organic molecules on it. Periodically strained graphene templates are fabricated by transferring graphene onto an array of nanospheres and then analyzed the growth and nucleation behavior of C60 thin films on the strained graphene templates. Both experiments and a numerical simulation demonstrated that strained graphene reduced the desorption energy between the graphene and the C60 molecules and thereby suppressed both nucleation and growth of the C60. A mechanism is proposed in which the strain-induced pseudo-electric field in graphene modulates the binding energy of organic molecules on the graphene.
For organic solar cells to be competitive, the light-absorbing molecules should simultaneously satisfy multiple key requirements, including weak-absorption charge transfer state, high dielectric constant, suitable surface energy, proper crystallinity, etc. However, the systematic design rule in molecules to achieve the abovementioned goals is rarely studied. In this work, guided by theoretical calculation, we present a rational design of non-fullerene acceptor o-BTP-eC9, with distinct photoelectric properties compared to benchmark BTP-eC9. o-BTP-eC9 based device has uplifted charge transfer state, therefore significantly reducing the energy loss by 41 meV and showing excellent power conversion efficiency of 18.7%. Moreover, the new guest acceptor o-BTP-eC9 has excellent miscibility, crystallinity, and energy level compatibility with BTP-eC9, which enables an efficiency of 19.9% (19.5% certified) in PM6:BTP-C9:o-BTP-eC9 based ternary system with enhanced operational stability.
Interest has grown in services that consume a significant amount of energy, such as large language models (LLMs), and research is being conducted worldwide on synaptic devices for neuromorphic hardware. However, various complex processes are problematic for the implementation of synaptic properties. Here, synaptic characteristics are implemented through a novel method, namely side chain control of conjugated polymers. The developed devices exhibit the characteristics of the biological brain, especially spike-timing-dependent plasticity (STDP), high-pass filtering, and long-term potentiation/depression (LTP/D). Moreover, the fabricated synaptic devices show enhanced nonvolatile characteristics, such as long retention time (≈102 s), high ratio of Gmax/Gmin, high linearity, and reliable cyclic endurance (≈103 pulses). This study presents a new pathway for next-generation neuromorphic computing by modulating conjugated polymers with side chain control, thereby achieving high-performance synaptic properties.
Polymers , Synapses , Polymers/chemistry , Synapses/physiology , Neuronal Plasticity/physiology , Neural Networks, Computer
Soft piezoresistive pressure sensors play an underpinning role in enabling a plethora of future Internet of Things (IoT) applications such as human-robot interaction (HRI) technologies, wearable devices, and metaverse ecosystems. Despite significant attempts to enhance the performance of these sensors, existing sensors still fall short of achieving high strain tolerance and linearity simultaneously. Herein, we present a low-cost, facile, and scalable approach to fabricating a highly strain-tolerant and linearly sensitive soft piezoresistive pressure sensor. Our design utilizes thin nanocracked gold films (NC-GFs) deposited on poly(dimethylsiloxane) (PDMS) as electrodes of the sensor. The large mismatch stress between gold (Au) and PDMS induces the formation of secondary wrinkles along the pyramidal-structured electrode under pressure; these wrinkles function as protuberances on the electrode and enable exceptional linear sensitivity of 4.2 kPa-1 over a wide pressure range. Additionally, our pressure sensor can maintain its performance even after severe mechanical deformations, including repeated stretching up to 30% strain, due to the outstanding strain tolerance of NC-GF. Our sensor's impressive sensing performance and mechanical robustness make it suitable for diverse IoT applications, as demonstrated by its use in wearable pulse monitoring devices and human-robot interaction systems.
Robotics , Wearable Electronic Devices , Humans , Ecosystem , Monitoring, Physiologic , Gold
With the commercialization of first-generation flexible mobiles and displays in the late 2010s, humanity has stepped into the age of flexible electronics. Inevitably, soft multifunctional sensors, as essential components of next-generation flexible electronics, have attracted tremendous research interest like never before. This review is dedicated to offering an overview of the latest emerging trends in soft multifunctional sensors and their accordant future research and development (R&D) directions for the coming decade. First, key characteristics and the predominant target stimuli for soft multifunctional sensors are highlighted. Second, important selection criteria for soft multifunctional sensors are introduced. Next, emerging materials/structures and trends for soft multifunctional sensors are identified. Specifically, the future R&D directions of these sensors are envisaged based on their emerging trends, namely i) decoupling of multiple stimuli, ii) data processing, iii) skin conformability, and iv) energy sources. Finally, the challenges and potential opportunities for these sensors in future are discussed, offering new insights into prospects in the fast-emerging technology.
The water surface provides a highly effective platform for the synthesis of two-dimensional polymers (2DP). In this study, we present an efficient on-water surface synthesis of crystalline monolayer 2D polyimide (2DPI) through the imidization reaction between tetra (4-aminophenyl) porphyrin (M1) and perylenetracarboxylic dianhydride (M2), resulting in excellent stability and coverage over a large area (tens of cm2). We further fabricate innovative organic-inorganic hybrid van der Waals heterostructures (vdWHs) by combining with exfoliated few-layer molybdenum sulfide (MoS2). High-resolution transmission electron microscopy (HRTEM) reveals face-to-face stacking between MoS2 and 2DPI within the vdWH. This stacking configuration facilitates remarkable charge transfer and noticeable n-type doping effects from monolayer 2DPI to MoS2, as corroborated by Raman spectroscopy, photoluminescence measurements, and field-effect transistor (FET) characterizations. Notably, the 2DPI-MoS2 vdWH exhibits an impressive electron mobility of 50 cm2/V·s, signifying a substantial improvement over pristine MoS2 (8 cm2/V·s). This study unveils the immense potential of integrating 2D polymers to enhance semiconductor device functionality through tailored vdWHs, thereby opening up exciting new avenues for exploring unique interfacial physical phenomena.
The development of covalent organic frameworks (COFs) with efficient charge transport is of immense interest for applications in optoelectronic devices. To enhance COF charge transport properties, electroactive building blocks and dopants can be used to induce extended conduction channels. However, understanding their intricate interplay remains challenging. We designed and synthesized a tailor-made COF structure with electroactive hexaazatriphenylene (HAT) core units and planar dioxin (D) linkages, denoted as HD-COF. With the support of theoretical calculations, we found that the HAT units in the HD-COF induce strong, eclipsed π-π stacking. The unique stacking of HAT units and the weak in-plane conjugation of dioxin linkages leads to efficient anisotropic charge transport. We fabricated HD-COF films to minimize the grain boundary effect of bulk COFs, which resulted in enhanced conductivity. As a result, the HD-COF films showed an electrical conductivity as high as 1.25â S cm-1 after doping with tris(4-bromophenyl)ammoniumyl hexachloroantimonate.
All-polymer solar cells have attracted considerable research interest due to their superior morphological stabilities, stretchability, and mechanical durability. However, the morphology optimization of the all-polymer bulk heterojunctions remains challenging due to the two long conjugated polymer chains, limiting its power conversion efficiency. Herein, we focus on the donor-acceptor phase segregation of an all-polymer active layer composed of PM6/PY-IT, a state-of-the-art all-polymer combination, by the introduction of volatile solid additives. Especially with 1,3-dibromo-5-chlorobenzene (DBCl) as the processing additive, we could effectively tune the miscibility between PM6 and PY-IT and thus optimize the phase segregation of the polymer donor and acceptor. Due to the synergetic effects on the favorable phase segregation and desired donor-acceptor distribution, the DBCl-treated devices feature the evident improvement of charge transport and collection, accompanied by the suppressed trap-assisted charge recombination. We consequently achieved a champion device efficiency of 16.5% (16.4% averaged), which is a 13% improvement compared with the control device without DBCl (14.6%). Our results highlight the importance of altering the miscibility of the polymer donor-acceptor pairs for practical applications of high-performance all-polymer solar cells.
The sequential deposition method assists the vertical phase distribution in the photoactive layer of organic solar cells, enhancing power conversion efficiencies. With this film coating approach, the morphology of both layers can be fine-tuned with high boiling solvent additives, as frequently applied in one-step casting films. However, introducing liquid additives can compromise the morphological stability of the devices due to the solvent residuals. Herein, 1,3,5-tribromobenzene (TBB) with high volatility and low cost, is used as a solid additive in the acceptor solution and combined thermal annealing to regulate the vertical phase in organic solar cells composed of D18-Cl/L8-BO. Compared to the control cells, the devices treated with TBB and those that underwent additional thermal processing exhibit increased exciton generation rate, charge carrier mobility, charge carrier lifetime, and reduced bimolecular charge recombination. As a result, the TBB-treated organic solar cells achieve a champion power conversion efficiency of 18.5% (18.1% averaged), one of the highest efficiencies in binary organic solar cells with open circuit voltage exceeding 900 mV. This study ascribes the advanced device performance to the gradient-distributed donor-acceptor concentrations in the vertical direction. The findings provide guidelines for optimizing the morphology of the sequentially deposited top layer to achieve high-performance organic solar cells.
Despite dramatic improvements in the electronic characteristics of organic semiconductors, the low operational stability of organic field-effect transistors (OFETs) hinders their direct use in practical applications. Although the literature contains numerous reports on the effects of water on the operational stability of OFETs, the underlying mechanisms of trap generation induced by water remain unclear. Here, a protonation-induced trap generation of organic semiconductors is proposed as a possible origin of the operational instability in organic field-effect transistors. Spectroscopic and electronic investigation techniques combined with simulations reveal that the direct protonation of organic semiconductors by water during operation may be responsible for the trap generation induced by bias stress; this phenomenon is independent of the trap generation at an insulator surface. In addition, the same feature occurred in small-bandgap polymers with fused thiophene rings irrespective of their crystalline ordering, implying the generality of protonation induced trap generation in various polymer semiconductors with a small bandgap. The finding of the trap-generation process provides new perspectives for achieving greater operational stability of organic field-effect transistors.
Rubbing-induced alignment of conjugated polymers is systematically investigated in terms of intra- and inter-molecular interaction. Various polymer films with a broad range of polymer chain rigidity are rubbed, and the degree of polymer chain alignment is quantitatively characterized. The rubbing technique effectively aligns crystalline domains in conjugated polymer films when the temperature approaches the critical rubbing temperature ( T r c $T_{\mathrm{r}}^{\mathrm{c}}$ ), at which the rearrangement and the slip of polymer chains are possible. A polymer with significant intra-/inter-molecular interactions exhibits higher T r c $T_{\mathrm{r}}^{\mathrm{c}}$ , though quantitative analysis reveals an intermediately aligned state at temperature Tr ' lower than T r c $T_{\mathrm{r}}^{\mathrm{c}}$ . This state originates from polymer chain aggregation in an amorphous domain. The intermediately aligned state can be controlled by plasticizer, which enables low-temperature alignment of high-mobility polymer film by reducing Tr ' to near 100 °C, increases the crystallinity, and improves the alignment effect at this state comparable to that of the completely aligned state obtained at extremely high temperatures.
Organic thin-film transistors (OTFTs) with ideal behavior are highly desired, because nonideal devices may overestimate the intrinsic property and yield inferior performance in applications. In reality, most polymer OTFTs reported in the literature do not exhibit ideal characteristics. Supported by a structure-property relationship study of several low-disorder conjugated polymers, here, we present an empirical selection rule for polymer candidates for textbook-like OTFTs with high reliability factors (100% for ideal transistors). The successful candidates should have low energetic disorder along their backbones and form thin films with spatially uniform energetic landscapes. We demonstrate that these requirements are satisfied in the semicrystalline polymer PffBT4T-2DT, which exhibits a reliability factor (~100%) that is exceptionally high for polymer devices, rendering it an ideal candidate for OTFT applications. Our findings broaden the selection of polymer semiconductors with textbook-like OTFT characteristics and would shed light upon the molecular design criteria for next-generation polymer semiconductors.
With the continuous development of organic semiconductor materials and on-going improvement of device technology, the power conversion efficiencies (PCEs) of organic solar cells (OSCs) have surpassed the threshold of 19%. Now, the low production cost of organic photovoltaic materials and devices have become an imperative demand for its practical application and future commercialization. Herein, the feasibility of simplified synthesis for cost-effective small-molecule acceptors via end-cap isomeric engineering is demonstrated, and two constitutional isomers, BTP-m-4Cl and BTP-o-4Cl, are synthesized and compared in parallel. These two non-fullerene acceptors (NFAs) have very similar optoelectronic properties but nonuniform morphological and crystallographic characteristics. Consequently, the OSCs composed of PM6:BTP-m-4Cl realize PCE of 17.2%, higher than that of the OSCs with PM6:BTP-o-4Cl (≈16%). When ternary OSCs are fabricated with PM6:BTP-m-4Cl:BTP-o-4Cl, the averaged PCE value reaches 17.95%, presenting outstanding photovoltaic performance. Most excitingly, the figure of merit (FOM) values of PM6:BTP-m-4Cl, PM6:BTP-o-4Cl, and PM6:BTP-m-4Cl:BTP-o-4Cl based devices are 0.190, 0.178, and 0.202 respectively. The FOM values of these systems are all among the top ones of the current high-efficiency OSC systems, revealing high cost-effectiveness of the two NFAs. This work provides a general but accessible strategy to minimize the efficiency-cost gap and promises the economic prospects of OSCs.
Perovskite solar cells (PSCs) with superior performance have been recognized as a potential candidate in photovoltaic technologies. However, defects in the active perovskite layer induce nonradiative recombination which restricts the performance and stability of PSCs. The construction of a thiophene-based 2D structure is one of the significant approaches for surface passivation of hybrid PSCs that may combine the benefits of the stability of 2D perovskite with the high performance of three-dimensional (3D) perovskite. Here, a sulfur-rich spacer cation 2-thiopheneethylamine iodide (TEAI) is synthesized as a passivation agent for the construction of a three-dimensional/two-dimensional (3D/2D) perovskite bilayer structure. TEAI-treated PSCs possess a much higher efficiency (20.06%) compared to the 3D perovskite (MA0.9FA0.1PbI3) devices (17.42%). Time-resolved photoluminescence and femtosecond transient absorption spectroscopy are employed to investigate the effect of surface passivation on the charge carrier dynamics of the 3D perovskite. Additionally, the stability test of TEAI-treated perovskite devices reveals significant improvement in humid (RH â¼ 46%) and thermal stability as the sulfur-based 2D (TEA)2PbI4 material self-assembles on the 3D surface, making the perovskite surface hydrophobic. Our findings provide a reliable approach to improve device stability and performance successively, paving the way for industrialization of PSCs.
In the last decade, soft acoustic/vibration sensors have gained tremendous research interest due to their unique ability to detect broadband acoustic/vibration stimuli, potentializing futuristic applications including voice biometrics, voice-controlled human-machine-interfaces, electronic skin, and skin-mountable healthcare devices. Importantly, to benefit most from these sensors, it is inevitable to use machine learning (ML) to process their output signals; with ML, a more accurate and efficient interpretation of original data is possible. This paper is dedicated to offering an overview of recent advances empowering the development of soft acoustic/vibration sensors and their signal processing using ML. First, the key performance parameters of the sensors are discussed. Second, popular transduction mechanisms for the sensors are addressed, followed by an in-depth overview of each type, covering materials used, structural designs, and sensing performances. Third, potential applications of the sensors are elaborated and fourth, a thorough discussion on ML is conducted, exploring different types of ML, specific ML algorithms suitable for processing acoustic/vibration signals, and current trends in ML-assisted applications. Finally, the challenges and potential opportunities in soft acoustic/vibration sensor and ML research are revealed to offer new insights into future prospects in these fields.
Achieving high mobility and bias stability is a challenging obstacle in the advancement of organic thin-film transistors (OTFTs). To this end, the fabrication of high-quality organic semiconductor (OSC) thin films is critical for OTFTs. Self-assembled monolayers (SAMs) have been used as growth templates for high-crystalline OSC thin films. Despite significant research progress in the growth of OSC on SAMs, a detailed understanding of the growth mechanism of the OSC thin films on a SAM template is lacking, which has limited its use. In this study, the effects of the structure (thickness and molecular packing) of SAM on the nucleation and growth behavior of the OSC thin films were investigated. We found that disordered SAM molecules assisted in the surface diffusion of the OSC molecules and resulted in a small nucleation density and large grain size of the OSC thin films. Moreover, a thick SAM with disordered SAM molecules on the top was found to be beneficial for the high mobility and bias stability of the OTFTs.
Neuromorphic computing based on two-dimensional transition-metal dichalcogenides (2D TMDs) has attracted significant attention recently due to their extraordinary properties generated by the atomic-thick layered structure. This study presents sulfur-defect-assisted MoS2 artificial synaptic devices fabricated by a simple sputtering process, followed by a precise sulfur (S) vacancy-engineering process. While the as-sputtered MoS2 film does not show synaptic behavior, the S vacancy-controlled MoS2 film exhibits excellent synapse with remarkable nonvolatile memory characteristics such as a high switching ratio (â¼103), a large memory window, and long retention time (â¼104 s) in addition to synaptic functions such as paired-pulse facilitation (PPF) and long-term potentiation (LTP)/depression (LTD). The synaptic device working mechanism of Schottky barrier height modulation by redistributing S vacancies was systemically analyzed by electrical, physical, and microscopy characterizations. The presented MoS2 synaptic device, based on the precise defect engineering of sputtered MoS2, is a facile, low-cost, complementary metal-oxide semiconductor (CMOS)-compatible, and scalable method and provides a procedural guideline for the design of practical 2D TMD-based neuromorphic computing.
The rapid growth of the electronics industry and proliferation of electronic materials and telecommunications technologies has led to the release of a massive amount of untreated electronic waste (e-waste) into the environment. Consequently, catastrophic environmental damage at the microbiome level and serious human health diseases threaten the natural fate of the planet. Currently, the demand for wearable electronics for applications in personalized medicine, electronic skins (e-skins), and health monitoring is substantial and growing. Therefore, "green" characteristics such as biodegradability, self-healing, and biocompatibility ensure the future application of wearable electronics and e-skins in biomedical engineering and bioanalytical sciences. Leveraging the biodegradability, sustainability, and biocompatibility of natural materials will dramatically influence the fabrication of environmentally friendly e-skins and wearable electronics. Here, the molecular and structural characteristics of biological skins and artificial e-skins are discussed. The focus then turns to the biodegradable materials, including natural and synthetic-polymer-based materials, and their recent applications in the development of biodegradable e-skin in wearable sensors, robotics, and human-machine interfaces (HMIs). Finally, the main challenges and outlook regarding the preparation and application of biodegradable e-skins are critically discussed in a near-future scenario, which is expected to lead to the next generation of biodegradable e-skins.
Robotics , Wearable Electronic Devices , Humans , Skin , Electronics , Biomedical Engineering
Chemical doping can be used to tune the optoelectronic properties of conjugated polymers (CPs), extending their applications as conducting materials. Unfortunately, chemically doped CP films containing excess dopants exhibit an increase in energetic disorder upon structural alteration, and Coulomb interactions between charge carriers and dopants also affect such disorder. The increase in energetic disorder leads to a broadening of the density of states, which consequently impedes efficient charge transport in chemically doped CPs. However, the molecular origins that are inherently resistant to such incidental increase of energetic disorder in chemically doped CPs have not been sufficiently explored. Here, it is discovered that energetic disorder in chemically doped CPs can be suppressed to a level close to the theoretical limit. Indacenodithiophene-co-benzothiadiazole (IDTBT) doped with triethyloxonium hexachloroantimonate (OA) exhibits disorder-free charge-transport characteristics and band-like transport behavior with astonishing carrier mobility as a result of reinforced 1D intramolecular transport. Molecular structure of IDTBT provides a capability to lower the energetic disorder that generally arises from the inclusion of heterogeneous dopants. The results suggest the possibilities of implementing disorder-free CPs that exhibit excellent charge transport characteristics in the chemically doped state and satisfy a prerequisite for their availability in the industry.
