Proton-selective coating enables fast-kinetics high-mass-loading cathodes for sustainable zinc batteries.

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.

Unveiling the Role of Side Chain for Improving Nonvolatile Characteristics of Conjugated Polymers-Based Artificial Synapse.

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.

Rational molecular and device design enables organic solar cells approaching 20% efficiency.

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.

On-water surface synthesis of electronically coupled 2D polyimide-MoS2 van der Waals heterostructure.

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.

Hexaazatriphenylene-Based Two-Dimensional Conductive Covalent Organic Framework with Anisotropic Charge Transfer.

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 1.25 S cm-1 after doping with tris(4-bromophenyl)ammoniumyl hexachloroantimonate.

Triggering the Donor-Acceptor Phase Segregation with Solid Additives Enables 16.5% Efficiency in All-Polymer Solar Cells.

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.

Vertical Phase Regulation with 1,3,5-Tribromobenzene Leads to 18.5% Efficiency Binary Organic 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.

Low-Temperature Alignment of Conjugated Polymers by Plasticizer-Aided Physical Rubbing.

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.

Achieving ideal transistor characteristics in conjugated polymer semiconductors.

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.

Balancing the Efficiency and Synthetic Accessibility of Organic Solar Cells with Isomeric Acceptor Engineering.

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.

Surface Passivation by Sulfur-Based 2D (TEA)2PbI4 for Stable and Efficient Perovskite Solar Cells.

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 ∼ 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.

Disordered Phase-Assisted Growth of Organic Semiconductor Crystals on Self-Assembled Monolayer Templates.

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.

Extremely Suppressed Energetic Disorder in a Chemically Doped Conjugated Polymer.

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.

Symmetry-Induced Ordered Assembly of a Naphthobisthiadiazole-Based Nonfused-Ring Electron Acceptor Enables Efficient Organic Solar Cells.

Nonfused-ring electron acceptors (NFREAs) have received increasing attention for use in organic solar cells (OSCs) because of their synthetic simplicity and tunable optical spectra. However, their fundamental molecular interactions and the mechanism by which they govern the property-function relations of OSCs remain elusive. Here, to investigate the effects of the structural symmetry of NFREAs, two acceptor-donor-acceptor'-donor-acceptor (A-D-A'-D-A)-type NFREAs, 2,2'-(((naphtho[1,2-c:5,6-c']bis[1,2,5]thiadiazole-5,10-diylbis(4,4-bis(2-butyloctyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene-6,2-diyl))bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (NTz-4F) and 2,2'-(((benzo[c][1,2,5]thiadiazole-4,7-diylbis(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene-6,2-diyl))bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (BT-4F), are designed and synthesized. They have different A' cores: NTz-4F has a modified centrosymmetric NTz core, whereas BT-4F has a modified axisymmetric BT core. In pristine films, the NTz-4F, which has a centrosymmetric core, shows substantially enhanced intermolecular interaction and microstructural crystalline ordering compared with BT-4F, which has an axisymmetric core. Even in blends with poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8,-dione))] (PBDB-T), NTz-4F retains its highly crystalline structure, whereas BT-4F loses crystalline packing. These changes in NTz-4F result in increased electron transport and suppressed nonradiative voltage loss, resulting in a power conversion efficiency of 9.14% for PBDB-T:NTz-4F vs 7.18% for PBDB-T:BT-4F. This work demonstrates that centrosymmetric-structured cores are promising building blocks for high-performance NFREA-based OSCs.

An Electret-Powered Skin-Attachable Auditory Sensor that Functions in Harsh Acoustic Environments.

Auditory sensors have shortcomings with respect to not only personalization with wearability and portability but also detecting a human voice clearly in a noisy environment or when a mask covers the mouth. In this work, an electret-powered and hole-patterned polymer diaphragm is exploited into a skin-attachable auditory sensor. The optimized charged electret diaphragm induces a voltage bias of >400 V against the counter electrode, which reduces the necessity of a bulky power source and enables the capacitive sensor to show high sensitivity (2.2 V Pa-1 ) with incorporation of an elastomer nanodroplet seismic mass. The sophisticated capacitive structure with low mechanical damping enables a flat frequency response (80-3000 Hz) and good linearity (50-80 dBSPL ). The hole-patterned electret diaphragms help the skin-attachable sensor detect only neck-skin vibration rather than dynamic air pressure, enabling a person's voice to be detected in a harsh acoustic environment. The sensor operates reliably even in the presence of surrounding noise and when the user is wearing a gas mask. Therefore, the sensor shows strong potential of a communication tool for disaster response and quarantine activities, and of diagnosis tool for vocal healthcare applications such as cough monitoring and voice dosimetry.

Effect of Electron-Withdrawing Chlorine Substituent on Morphological and Photovoltaic Properties of All Chlorinated D-A-Type Quinoxaline-Based Polymers.

The choice of the chlorine (Cl) atom as an electron-withdrawing substituent in conjugated polymers leads to a higher potential in the commercialization of polymer solar cells than its fluorine counterpart because of the versatility and cost-effectiveness of the chlorination process. In addition, the population and location of Cl substituents can significantly influence the photovoltaic characteristics of polymers. In this study, three chlorinated quinoxaline-based polymers were invented to examine the numerical and positioning effects of the Cl atom on their photovoltaic characteristics. The number of Cl substituents in the reference polymer, PBCl-Qx, was adjusted to three: two Cl atoms in the benzodithiophene-type D unit and one Cl atom in the quinoxaline-type A unit. Subsequently, two more Cl atoms were selectively introduced at the 4- and 5-positions of the alkylated thiophene moieties at the 2,3-positions of the quinoxaline moiety in PBCl-Qx to obtain the additional polymers PBCl-Qx4Cl and PBCl-Qx5Cl, respectively. The conventional PBCl-Qx4Cl device exhibited a better power conversion efficiency (PCE) of 12.95% as compared to those of PBCl-Qx (12.44%) and PBCl-Qx5Cl (11.82%) devices. The highest PCE of the device with PBCl-Qx4Cl was ascribed to an enhancement in the open-circuit voltage and fill factor induced by the deeper energy level of the highest occupied molecular orbital and the favorable morphological features in its blended film with Y6.

Solution-Processable Semiconducting Conjugated Planar Network.

After the emergence of graphene in the material science field, top-down and bottom-up studies to develop semiconducting organic materials with layered structures became highly active. However, most of them have suffered from poor processability, which hampers device fabrication and frustrates practical applications. Here, we suggest an unconventional approach to fabricating semiconducting devices, which avoids the processability issue. We designed a soluble amorphous network using a solution process to form a thin film on a substrate. We then employed heat treatment to develop a flattened organic structure in the thin film, as an active layer for organic thin-film transistors (TFTs). The fabricated TFTs showed good performance in both horizontal and vertical charge transport, suggesting a versatile and useful approach for the development of organic semiconductors.

A High-Fidelity Skin-Attachable Acoustic Sensor for Realizing Auditory Electronic Skin.

Wearable auditory sensors are critical in user-friendly sound-recognition systems for smart human-machine interaction and the Internet of Things. However, previously reported wearable sensors have limited sound-sensing quality as a consequence of a poor frequency response and a narrow acoustic-pressure range. Here, a skin-attachable acoustic sensor is presented that has higher sensing accuracy in wider auditory field than human ears, with flat frequency response (15-10 000 Hz) and a good range of linearity (29-134 dBSPL ) as well as high conformality to flexible surfaces and human skin. This high sound-sensing quality is achieved by exploiting the low residual stress and high processability of polymer materials in a diaphragm structure designed using acousto-mechano-electric modeling. Thus, this acoustic sensor shows high acoustic fidelity by sensing human-audible sounds, even loud sounds and low-frequency sounds that human ears cannot detect without distorting them. The polymer-based ultrasmall (<9 mm2 ) and thin sensor maintains sound-detection quality on flexible substrates and in a wide temperature range (25 to 90 °C). The acoustic sensor shows a significant potential of auditory electronic skin, by recognizing voice successfully when the sensor attached on human skin is connected to a commercial mobile device running the latest artificial intelligence assistant.

Cactus-Spine-Inspired Sweat-Collecting Patch for Fast and Continuous Monitoring of Sweat.

A sweat sensor is expected to be the most appropriate wearable device for noninvasive healthcare monitoring. However, the practical use of sweat sensors is impeded by irregular and low sweat secretion rates. Here, a sweat-collecting patch that can collect sweat efficiently for fast and continuous healthcare monitoring is demonstrated. The patch uses cactus-spine-inspired wedge-shaped wettability-patterned channels on a hierarchical microstructured/nanostructured surface. The channel shape, in combination with the superhydrophobic/superhydrophilic surface materials, induces a unidirectional Laplace pressure that transports the sweat to the sensing area spontaneously even when the patch is aligned vertically. The patch demonstrates superior sweat-collecting efficiency and reduces the time required to fill the sensing area by transporting sweat almost without leaving it inside the channel. Therefore, a sensor based on the patch responds quickly to biochemicals in sweat, and the patch enables the continuous monitoring of changes in sweat biochemicals according to their changes in the wearer's blood.

15.3% Efficiency All-Small-Molecule Organic Solar Cells Achieved by a Locally Asymmetric F, Cl Disubstitution Strategy.

Single junction binary all-small-molecule (ASM) organic solar cells (OSCs) with power conversion efficiency (PCE) beyond 14% are achieved by using non-fullerene acceptor Y6 as the electron acceptor, but still lag behind that of polymer OSCs. Herein, an asymmetric Y6-like acceptor, BTP-FCl-FCl, is designed and synthesized to match the recently reported high performance small molecule donor BTR-Cl, and a record efficiency of 15.3% for single-junction binary ASM OSCs is achieved. BTP-FCl-FCl features a F,Cl disubstitution on the same end group affording locally asymmetric structures, and so has a lower total dipole moment, larger average electronic static potential, and lower distribution disorder than those of the globally asymmetric isomer BTP-2F-2Cl, resulting in improved charge generation and extraction. In addition, BTP-FCl-FCl based active layer presents more favorable domain size and finer phase separation contributing to the faster charge extraction, longer charge carrier lifetime, and much lower recombination rate. Therefore, compared with BTP-2F-2Cl, BTP-FCl-FCl based devices provide better performance with FF enhanced from 71.41% to 75.36% and J sc increased from 22.35 to 24.58 mA cm-2, leading to a higher PCE of 15.3%. The locally asymmetric F, Cl disubstitution on the same end group is a new strategy to achieve high performance ASM OSCs.