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Wafer-scale transfer processes of 2D materials significantly expand their application space in scalable microelectronic devices with excellent and tunable properties through van der Waals (vdW) stacking. Unlike many 2D materials, wafer-scale transfer of MXene films for vdW contact engineering has not yet been reported. With their rich surface chemistry and tunable properties, the transfer of MXenes can enable enormous possibilities in electronic devices using interface engineering. Taking advantage of the MXene hydrophilic surface, a straightforward, green, and fast process for the transfer of MXene films at the wafer scale (4-inch) is developed. Uniform vdW stacking of several types of large-area heterojunctions including MXene/MXene (Ti 3 C 2 T x , Nb 2 CT x, and V 2 CT x ), MXene/MoS 2 , and MXene/Au is further demonstrated. Multilayer support is applied to minimize damage or deformation in the transfer process of patterned Ti 3 C 2 T x film. It allows us to fabricate thin film transistors and manipulate the MXene/MoS 2 interface through the intercalation of various 2D liquids. Particularly noteworthy is the significant enhancement of the interfacial carrier transfer efficiency by ≈2 orders of magnitude using hydrogen iodide (HI) intercalation. This finding indicates a wide range of possibilities for interface engineering by transferring MXene films and employing liquid-assisted interfacial intercalation., (© 2024 Wiley‐VCH GmbH.)

Solution-processable poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is an important polymeric conductor used extensively in organic flexible, wearable, and stretchable optoelectronics. However, further enhancing its conductivity and long-term stability while maintaining its superb mechanical properties remains challenging. Here, a novel post-treatment approach to enhance the electrical properties and stability of sub-20-nm-thin PEDOT:PSS films processed from solution is introduced. The approach involves a sequential post-treatment with HNO 3 and CsCl, resulting in a remarkable enhancement of the electrical conductivity of PEDOT:PSS films to over 5500 S cm -1 , along with improved carrier mobility. The post-treated films exhibit remarkable air stability, retaining over 85% of their initial conductivity even after 270 days of storage. Various characterization techniques, including X-ray photoelectron spectroscopy, atomic force microscopy, Raman spectroscopy, Hall effect measurements, and grazing incidence wide angle X-ray scattering, coupled with density functional theory calculations, provide insights into the structural changes and interactions responsible for these improvements. To demonstrate the potential for practical applications, the ultrathin PEDOT:PSS films are connected to an inorganic light-emitting diode with a battery, showcasing their suitability as transparent electrodes. This work presents a promising approach for enhancing the electrical conductivity of PEDOT:PSS while offering a comprehensive understanding of the underlying mechanisms that can guide further advances., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Molecular doping is commonly utilized to tune the charge transport properties of organic semiconductors. However, applying this technique to electrically dope inorganic materials like metal oxide semiconductors is challenging due to the limited availability of molecules with suitable energy levels and processing characteristics. Herein, n-type doping of zinc oxide (ZnO) films is demonstrated using 1,3-dimethylimidazolium-2-carboxylate (CO 2 -DMI), a thermally activated organic n-type dopant. Adding CO 2 -DMI into the ZnO precursor solution and processing it atop a predeposited indium oxide (InO x ) layer yield InO x /n-ZnO heterojunctions with increased electron field-effect mobility of 32.6 cm 2 V -1 s -1 compared to 18.5 cm 2 V -1 s -1 for the pristine InO x /ZnO bilayer. The improved electron transport originates from the ZnO's enhanced crystallinity, reduced hydroxyl concentrations, and fewer oxygen vacancy groups upon doping. Applying the optimally doped InO x /n-ZnO heterojunctions as the electron-transporting layers (ETLs) in organic photovoltaics (OPVs) yields cells with improved power conversion efficiency of 19.06%, up from 18.3% for devices with pristine ZnO, and 18.2% for devices featuring the undoped InO x /ZnO ETL. It is shown that the all-around improved OPV performance originates from synergistic effects associated with CO 2 -DMI doping of the thermally grown ZnO, highlighting its potential as an electronic dopant for ZnO and potentially other metal oxides., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Improving hole injection through the surface modification of indium tin oxide (ITO) with self-assembled monolayers (SAMs) is a promising method for modulating the carrier injection in organic light-emitting diodes (OLEDs). However, developing SAMs with the required characteristics remains a daunting challenge. Herein, we functionalize ITO with various phosphonic acid SAMs and evaluate the SAM-modified anodes in terms of their work function (WF), molecular distribution, coverage, and electrical conductivity. We fabricate and characterize green phosphorescent SAM-based OLEDs and compared their performance against devices based on the conventional poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) hole-injection layer. We find that the usage of [2-(3,6-diiodo-9H-carbazol-9-yl)ethyl]phosphonic acid (I-2PACz) SAM yields devices with superior performance characteristics, including a maximum luminance of ∼57,300 cd m -2 and external quantum efficiency of up to ∼17%. This improvement is attributed to synergistic factors, including the deep WF of ITO/I-2PACz (5.47 eV), the formation of larger I-2PACz molecular clusters, and the intrinsic I-2PACz dipole, that collectively enhance hole-injection.

Metabolites are essential molecules involved in various metabolic processes, and their deficiencies and excessive concentrations can trigger significant physiological consequences. The detection of multiple metabolites within a non-invasively collected biofluid could facilitate early prognosis and diagnosis of severe diseases. Here, a metal oxide heterojunction transistor (HJ-TFT) sensor is developed for the label-free, rapid detection of uric acid (UA) and 25(OH)Vitamin-D3 (Vit-D3) in human saliva. The HJ-TFTs utilize a solution-processed In 2 O 3 /ZnO channel functionalized with uricase enzyme and Vit-D3 antibody for the selective detection of UA and Vit-D3, respectively. The ultra-thin tri-channel architecture facilitates strong coupling between the electrons transported along the buried In 2 O 3 /ZnO heterointerface and the electrostatic perturbations caused by the interactions between the surface-immobilized bioreceptors and target analytes. The biosensors can detect a wide range of concentrations of UA (from 500 nm to 1000 µM) and Vit-D3 (from 100 pM to 120 nm) in human saliva within 60 s. Moreover, the biosensors exhibit good linearity with the physiological concentration of metabolites and limit of detections of ≈152 nm for UA and ≈7 pM for Vit-D3 in real saliva. The specificity is demonstrated against various interfering species, including other metabolites and proteins found in saliva, further showcasing its capabilities., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Tracking the dynamics of ultrafast hole injection into copper thiocyanate (CuSCN) at the interface can be experimentally challenging. These challenges include restrictions in accessing the ultraviolet spectral range through transient electronic spectroscopy, where the absorption spectrum of CuSCN is located. Time-resolved vibrational spectroscopy solves this problem by tracking marker modes at specific frequencies and allowing direct access to dynamical information at the molecular level at donor-acceptor interfaces in real time. This study uses photoabsorber PM6 (poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)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))]) as a model system to explore and decipher the hole transfer dynamics of CuSCN using femtosecond (fs) mid-infrared (IR) spectroscopy. The time-resolved results indicate that excited PM6 exhibits a sharp vibrational mode at 1599 cm -1 attributed to the carbonyl group, matching the predicted frequency position obtained from time-dependent density functional theory (DFT) calculations. The fs mid-IR spectroscopy demonstrates a fast formation (<168 fs) and blue spectral shift of the CN stretching vibration from 2118 cm -1 for CuSCN alone to 2180 cm -1 for PM6/CuSCN, confirming the hole transfer from PM6 to CuSCN. The short interfacial distance and high frontier orbital delocalization obtained from the interfacial DFT models support a coherent and ultrafast regime for hole transfer. These results provide direct evidence for hole injection at the interface of CuSCN for the first time using femtosecond mid-IR spectroscopy and serve as a new investigative approach for interfacial chemistry and solar cell communities.

The determination of molecular conformations of oligomeric acceptors (OAs) and their impact on molecular packing are crucial for understanding the photovoltaic performance of their resulting polymer solar cells (PSCs) but have not been well studied yet. Herein, we synthesized two dimeric acceptor materials, DIBP3F-Se and DIBP3F-S, which bridged two segments of Y6-derivatives by selenophene and thiophene, respectively. Theoretical simulation and experimental 1D and 2D NMR spectroscopic studies prove that both dimers exhibit O-shaped conformations other than S- or U-shaped counter-ones. Notably, this O-shaped conformation is likely governed by a distinctive "conformational lock" mechanism, arising from the intensified intramolecular π-π interactions among their two terminal groups within the dimers. PSCs based on DIBP3F-Se deliver a maximum efficiency of 18.09 %, outperforming DIBP3F-S-based cells (16.11 %) and ranking among the highest efficiencies for OA-based PSCs. This work demonstrates a facile method to obtain OA conformations and highlights the potential of dimeric acceptors for high-performance PSCs., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Cyclophosphazenes offer a robust and easily modifiable platform for a diverse range of functional systems that have found applications in a wide variety of areas. Herein, for the first time, it reports an organophosphazene-based supramolecular ferroelectric [(PhCH 2 NH) 6 P 3 N 3 Me]I, [PMe]I. The compound crystallizes in the polar space group Pc and its thin-film sample exhibits remnant polarization of 5 µC cm -2 . Vector piezoresponse force microscopy (PFM) measurements indicated the presence of multiaxial polarization. Subsequently, flexible composites of [PMe]I are fabricated for piezoelectric energy harvesting applications using thermoplastic polyurethane (TPU) as the matrix. The highest open-circuit voltages of 13.7 V and the maximum power density of 34.60 µW cm -2 are recorded for the poled 20 wt.% [PMe]I/TPU device. To understand the molecular origins of the high performance of [PMe]I-based mechanical energy harvesting devices, piezoelectric charge tensor values are obtained from DFT calculations of the single crystal structure. These indicate that the mechanical stress-induced distortions in the [PMe]I crystals are facilitated by the high flexibility of the layered supramolecular assembly., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Transistor-based biosensors represent an emerging technology for inexpensive point-of-care testing (POCT) applications. However, the limited sensitivity of the current transistor technologies hinders their practical deployment. In this study, we developed tri-channel In 2 O 3 /ZnO heterojunction thin-film transistors (TFTs) featuring the surface-immobilized enzyme glucose oxidase to detect glucose in various biofluids. This unusual channel design facilitates strong coupling between the electrons transported along the buried In 2 O 3 /ZnO heterointerface and the electrostatic perturbations caused by the interactions between glucose and surface-immobilized glucose oxidase. The enzyme selectively binds to glucose, causing a change in charge density on the channel surface. By exploring this effect, the solid-state biosensing TFT (BioTFT) can selectively detect glucose in artificial and real saliva over a wide range of concentrations from 500 nM to 20 mM with limits of detection of ∼365 pM (artificial saliva) and ∼416 nM (real saliva) in less than 60 s. The specificity of the sensor towards glucose has been demonstrated against various interfering species in artificial saliva, further highlighting its unique capabilities. Moreover, the BioTFTs exhibited good operating stability upon storage for up to two weeks, with relative standard deviation (RSD) values ranging from 2.36% to 6.39% for 500 nM glucose concentration. Our BioTFTs are easy to manufacture with reliable operation, making them ideal for non-invasive POCT applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Semiconducting colloidal quantum dots (CQDs) represent an emerging class of thermoelectric materials for use in a wide range of future applications. CQDs combine solution processability at low temperatures with the potential for upscalable manufacturing via printing techniques. Moreover, due to their low dimensionality, CQDs exhibit quantum confinement and a high density of grain boundaries, which can be independently exploited to tune the Seebeck coefficient and thermal conductivity, respectively. This unique combination of attractive attributes makes CQDs very promising for application in emerging thermoelectric generator (TEG) technologies operating near room temperature. Herein, recent progress in CQDs for application in emerging thin-film thermoelectrics is reviewed. First, the fundamental concepts of thermoelectricity in nanostructured materials are outlined, followed by an overview of the popular synthetic methods used to produce CQDs with controllable sizes and shapes. Recent strides in CQD-based thermoelectrics are then discussed with emphasis on their application in thin-film TEGs. Finally, the current challenges and future perspectives for further enhancing the performance of CQD-based thermoelectric materials for future applications are discussed., (© 2023 Wiley-VCH GmbH.)

Three-dimensional printing (3DP) is an emerging technology to fabricate complex architectures, necessary to realize state-of-the-art flexible and wearable electronic devices. In this regard, top-performing devices containing organic ferro- and piezoelectric compounds are desired to circumvent significant shortcomings of conventional piezoceramics, e.g. toxicity and high-temperature device processibility. Herein, we report on a 3D-printed composite of a chiral ferroelectric organic salt {[Me 3 CCH(Me)NH 3 ][BF 4 ]} (1) with a biodegradable polycaprolactone (PCL) polymer that serves as a highly efficient piezoelectric nanogenerator (PENG). The ferroelectric property of 1 originates from its polar tetragonal space group P 4 2 , verified by P - E loop measurements. The ferroelectric domain characteristics of 1 were further probed by piezoresponse force microscopy (PFM), which gave characteristic 'butterfly' and hysteresis loops. The PFM amplitude vs. drive voltage measurements gave a relatively high magnitude of the converse piezoelectric coefficient for 1. PCL polymer composites with various weight percentages (wt%) of 1 were prepared and subjected to piezoelectric energy harvesting tests, which gave a maximum open-circuit voltage of 36.2 V and a power density of 48.1 μW cm -2 for the 10 wt% 1-PCL champion device. Furthermore, a gyroid-shaped 3D-printed 10 wt% 1-PCL composite was fabricated to test its practical utility, which gave an excellent output voltage of 41 V and a power density of 56.8 μW cm -2 . These studies promise the potential of simple organic compounds for building PENG devices using advanced manufacturing technologies.

Bisthienoazepinedione (BTA) has been reported for constructing high-performing p-type conjugated polymers in organic electronics, but the ring extended version of BTA is not well explored. In this work, we report a new synthesis of a key building block to the ring expanded electron-deficient pentacyclic azepinedione (BTTA). Three copolymers of BTAA with benzodithiophene substituted by different side chains are prepared. These polymers exhibit similar energy levels and optical absorption in solution and solid state, while significant differences are revealed in their film morphologies and behavior in transistor and photovoltaic devices. The best-performing polymers in transistor devices contained alkylthienyl side chains on the BDT unit ( pBDT-BTTA-2 and pBDT-BTTA-3 ) and demonstrated maximum saturation hole mobilities of 0.027 and 0.017 cm 2 V -1 s -1 . Blends of these polymers with PC 71 BM exhibited a best photovoltaic efficiency of 6.78% for pBDT-BTTA-3 -based devices. Changing to a low band gap non-fullerene acceptor (BTP-eC9) resulted in improved efficiency of up to 13.5%. Our results are among the best device performances for BTA and BTTA-based p-type polymers and highlight the versatile applications of this electron-deficient BTTA unit., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Growing continuous monolayer films of transition-metal dichalcogenides (TMDs) without the disruption of grain boundaries is essential to realize the full potential of these materials for future electronics and optoelectronics, but it remains a formidable challenge. It is generally believed that controlling the TMDs orientations on epitaxial substrates stems from matching the atomic registry, symmetry, and penetrable van der Waals forces. Interfacial reconstruction within the exceedingly narrow substrate-epilayer gap has been anticipated. However, its role in the growth mechanism has not been intensively investigated. Here, we report the experimental conformation of an interfacial reconstructed (IR) layer within the substrate-epilayer gap. Such an IR layer profoundly impacts the orientations of nucleating TMDs domains and, thus, affects the materials' properties. These findings provide deeper insights into the buried interface that could have profound implications for the development of TMD-based electronics and optoelectronics.

Formamidinium lead triiodide (FAPbI 3 ) is the leading candidate for single-junction metal-halide perovskite photovoltaics, despite the metastability of this phase. To enhance its ambient-phase stability and produce world-record photovoltaic efficiencies, methylenediammonium dichloride (MDACl 2 ) has been used as an additive in FAPbI 3 . MDA 2+ has been reported as incorporated into the perovskite lattice alongside Cl - . However, the precise function and role of MDA 2+ remain uncertain. Here, we grow FAPbI 3 single crystals from a solution containing MDACl 2 (FAPbI 3 -M). We demonstrate that FAPbI 3 -M crystals are stable against transformation to the photoinactive δ-phase for more than one year under ambient conditions. Critically, we reveal that MDA 2+ is not the direct cause of the enhanced material stability. Instead, MDA 2+ degrades rapidly to produce ammonium and methaniminium, which subsequently oligomerizes to yield hexamethylenetetramine (HMTA). FAPbI 3 crystals grown from a solution containing HMTA (FAPbI 3 -H) replicate the enhanced α-phase stability of FAPbI 3 -M. However, we further determine that HMTA is unstable in the perovskite precursor solution, where reaction with FA + is possible, leading instead to the formation of tetrahydrotriazinium (THTZ-H + ). By a combination of liquid- and solid-state NMR techniques, we show that THTZ-H + is selectively incorporated into the bulk of both FAPbI 3 -M and FAPbI 3 -H at ∼0.5 mol % and infer that this addition is responsible for the improved α-phase stability.

Developing efficient and stable organic photovoltaics (OPVs) is crucial for the technology's commercial success. However, combining these key attributes remains challenging. Herein, we incorporate the small molecule 2-((3,6-dibromo-9 H -carbazol-9-yl)ethyl)phosphonic acid (Br-2PACz) between the bulk-heterojunction (BHJ) and a 7 nm-thin layer of MoO 3 in inverted OPVs, and study its effects on the cell performance. We find that the Br-2PACz/MoO 3 hole-extraction layer (HEL) boosts the cell's power conversion efficiency (PCE) from 17.36% to 18.73% (uncertified), making them the most efficient inverted OPVs to date. The factors responsible for this improvement include enhanced charge transport, reduced carrier recombination, and favourable vertical phase separation of donor and acceptor components in the BHJ. The Br-2PACz/MoO 3 -based OPVs exhibit higher operational stability under continuous illumination and thermal annealing (80 °C). The T 80 lifetime of OPVs featuring Br-2PACz/MoO 3 - taken as the time over which the cell's PCE reduces to 80% of its initial value - increases compared to MoO 3 -only cells from 297 to 615 h upon illumination and from 731 to 1064 h upon continuous heating. Elemental analysis of the BHJs reveals the enhanced stability to originate from the partially suppressed diffusion of Mo ions into the BHJ and the favourable distribution of the donor and acceptor components induced by the Br-2PACz.

The ferroelectric behaviour of an octahedral cage [[Ni 6 (H 2 O) 12 (TPTA) 8 ]·(NO 3 ) 12 ·36H 2 O] (1) exhibiting high remnant polarization of 25.31 μC cm -2 is discovered. For the first time, clear domain structures and the characteristic electromechanical responses are demonstrated using piezoresponsive force microscopy for a thin film of 1. Owing to its mechanical energy conversion capability, polymer composites of 1 were employed as efficient piezoelectric nanogenerators.

Narrowband photoresponsive molecules are highly coveted in high-resolution imaging, sensing, and monochromatic photodetection, especially those extending into the near-infrared (NIR) spectral range. Here, a new class of J-aggregating materials based on quinoidal indacenodithiophenes (IDTs) that exhibit an ultra-narrowband (full width half maxima of 22 nm) NIR absorption peak centered at 770 nm is reported. The spectral width is readily tuned by the length of the solubilizing alkyl group, with longer chains resulting in significant spectral narrowing. The J-aggregate behavior is confirmed by a combination of excited state lifetime measurements and single-crystal X-ray diffraction measurements. Their utility as electron-transporting materials is demonstrated in both transistor and phototransistor devices, with the latter demonstrating good response at NIR wavelengths (780 nm) over a range of intensities., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

The surface modification of nanoparticles (NPs) is crucial for fabricating polymer nanocomposites (NCs) with high dielectric permittivity. Here, we systematically studied the effect of surface functionalization of TiO 2 and BaTiO 3 NPs to enhance the dielectric permittivity of polyvinylidene fluoride (PVDF) NCs by 23 and 74%, respectively, measured at a frequency of 1 kHz. To further increase the dielectric permittivity of PVDF/NPs-based NCs, we developed a new hetero-phase filler-based approach that is cost-effective and easy to implement. At a 1:3 mixing ratio of TiO 2 :BaTiO 3 NPs, the dielectric constant of the ensuing NC is found to be 50.2, which is comparable with the functionalized BaTiO 3 -based NC. The highest dielectric constant value of 76.1 measured at 1 kHz was achieved using the (3-aminopropyl)triethoxysilane (APTES)-modified hetero-phase-based PVDF composite at a volume concentration of 5%. This work is an important step toward inexpensive and easy-to-process high-k nanocomposite dielectrics.

Organic electrochemical transistors are a promising technology for bioelectronic devices, with applications in neuromorphic computing and healthcare. The active component enabling an organic electrochemical transistor is the organic mixed ionic-electronic conductor whose optimization is critical for realizing high-performing devices. In this study, the influence of purity and molecular weight is examined for a p-type polythiophene and an n-type naphthalene diimide-based polymer in improving the performance and safety of organic electrochemical transistors. Our preparative GPC purification reduced the Pd content in the polymers and improved their organic electrochemical transistor mobility by ~60% and 80% for the p- and n-type materials, respectively. These findings demonstrate the paramount importance of removing residual Pd, which was concluded to be more critical than optimization of a polymer's molecular weight, to improve organic electrochemical transistor performance and that there is readily available improvement in performance and stability of many of the reported organic mixed ionic-electronic conductors., (© 2022. The Author(s).)

Solvent-solvent and solvent-anion pairings in battery electrolytes have been identified for the first time by nuclear magnetic resonance spectroscopy. These hitherto unknown interactions are enabled by the hydrogen bonding induced by the strong Lewis acid Li + , and exist between the electron-deficient hydrogen (δ + H) present in the solvent molecules and either other solvent molecules or negatively-charged anions. Complementary with the well-established strong but short-ranged Coulombic interactions between cation and solvent molecules, such weaker but longer-ranged hydrogen-bonding casts the formation of an extended liquid structure in electrolytes that is influenced by their components (solvents, additives, salts, and concentration), which in turn dictates the ion transport within bulk electrolytes and across the electrolyte-electrode interfaces. The discovery of this new inter-component force completes the picture of how electrolyte components interact and arrange themselves, sets the foundation to design better electrolytes on the fundamental level, and probes battery performances., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Schottky diodes based on inexpensive materials that can be processed using simple manufacturing methods are of particular importance for the next generation of flexible electronics. Although a number of high-frequency n-type diodes and rectifiers have been demonstrated, the progress with p-type diodes is lagging behind, mainly due to the intrinsically low conductivities of existing p-type semiconducting materials that are compatible with low-temperature, flexible, substrate-friendly processes. Herein, we report on CuSCN Schottky diodes, where the semiconductor is processed from solution, featuring coplanar Al-Au nanogap electrodes (<15 nm), patterned via adhesion lithography. The abundant CuSCN material is doped with the molecular p-type dopant fluorofullerene C 60 F 48 to improve the diode's operating characteristics. Rectifier circuits fabricated with the doped CuSCN/C 60 F 48 diodes exhibit a 30-fold increase in the cutoff frequency as compared to pristine CuSCN diodes (from 140 kHz to 4 MHz), while they are able to deliver output voltages of >100 mV for a V IN = ±5 V at the commercially relevant frequency of 13.56 MHz. The enhanced diode and circuit performance is attributed to the improved charge transport across CuSCN induced by C 60 F 48 . The ensuing diode technology can be used in flexible complementary circuits targeting low-energy-budget applications for the emerging internet of things device ecosystem.

Bismuth containing hybrid molecular ferroelectrics are receiving tremendous attention in recent years owing to their stable and non-toxic composition. However, these perovskite-like structures are primarily limited to ammonium cations. Herein, we report a new phosphonium based discrete perovskite-like hybrid ferroelectric with a formula [Me(Ph) 3 P] 3 [Bi 2 Br 9 ] (MTPBB) and its mechanical energy harvesting capability. The Polarization-Electric field (P-E) measurements resulted in a well-defined ferroelectric hysteresis loop with a remnant polarization value of 2.1 μC cm -2 . Piezoresponse force microscopy experiments enabled visualization of the ferroelectric domain structure and evaluation of the piezoelectric strain coefficient (d 33 ) for an MTPBB single crystal and thin film sample. Furthermore, flexible devices incorporating MTPBB in polydimethylsiloxane (PDMS) matrix at various concentrations were fabricated and explored for their mechanical energy harvesting properties. The champion device with 20 wt % of MTPBB in PDMS rendered a maximum peak-to-peak open-circuit voltage of 22.9 V and a maximum power density of 7 μW cm -2 at an optimal load of 4 MΩ. Moreover, the potential of MTPBB-based devices in low power electronics was demonstrated by storing the harvested energy in various electrolytic capacitors., (© 2022 Wiley-VCH GmbH.)

The massive deployment of fifth generation and internet of things technologies requires precise and high-throughput fabrication techniques for the mass production of radio frequency electronics. We use printable indium-gallium-zinc-oxide semiconductor in spontaneously formed self-aligned <10 nm nanogaps and flash-lamp annealing to demonstrate rapid manufacturing of nanogap Schottky diodes over arbitrary size substrates operating in 5 G frequencies. These diodes combine low junction capacitance with low turn-on voltage while exhibiting cut-off frequencies (intrinsic) of >100 GHz. Rectifier circuits constructed with these co-planar diodes can operate at ~47 GHz (extrinsic), making them the fastest large-area electronic devices demonstrated to date., (© 2022. The Author(s).)

Hybrid devices based on a heterojunction between inorganic and organic semiconductors have offered a means to combine the advantages of both classes of materials in optoelectronic devices, but, in practice, the performance of such devices has often been disappointing. Here, it is demonstrated that charge generation in hybrid inorganic-organic heterojunctions consisting of copper thiocyanate (CuSCN) and a variety of molecular acceptors (ITIC, IT-4F, Y6, PC 70 BM, C 70 , C 60 ) proceeds via emissive charge-transfer (CT) states analogous to those found at all-organic heterojunctions. Importantly, contrary to what has been observed at previous organic-inorganic heterojunctions, the dissociation of the CT-exciton and subsequent charge separation is efficient, allowing the fabrication of planar photovoltaic devices with very low non-radiative voltage losses (0.21 ±  0.02 V). It is shown that such low non-radiative recombination enables the fabrication of simple and cost-effective near-IR (NIR) detectors with extremely low dark current (4 pA cm -2 ) and noise spectral density (3 fA Hz -1/2 ) at no external bias, leading to specific detectivities at NIR wavelengths of just under 10 13 Jones, close to the performance of commercial silicon photodetectors. It is believed that this work demonstrates the possibility for hybrid heterojunctions to exploit the unique properties of both inorganic and organic semiconductors for high-performance opto-electronic devices., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Organic semiconductor nanoparticles (NPs) composed of an electron donor/acceptor (D/A) semiconductor blend have recently emerged as an efficient class of hydrogen-evolution photocatalysts. It is demonstrated that using conjugated polymers functionalized with (oligo)ethylene glycol side chains in NP photocatalysts can greatly enhance their H 2 -evolution efficiency compared to their nonglycolated analogues. The strategy is broadly applicable to a range of structurally diverse conjugated polymers. Transient spectroscopic studies show that glycolation facilitates charge generation even in the absence of a D/A heterojunction, and further suppresses both geminate and nongeminate charge recombination in D/A NPs. This results in a high yield of photogenerated charges with lifetimes long enough to efficiently drive ascorbic acid oxidation, which is correlated with greatly enhanced H 2 -evolution rates in the glycolated NPs. Glycolation increases the relative permittivity of the semiconductors and facilitates water uptake. Together, these effects may increase the high-frequency relative permittivity inside the NPs sufficiently, to cause the observed suppression of exciton and charge recombination responsible for the high photocatalytic activities of the glycolated NPs., (© 2021 Wiley-VCH GmbH.)

The low carrier mobility of organic semiconductors and the high parasitic resistance and capacitance often encountered in conventional organic Schottky diodes hinder their deployment in emerging radio frequency (RF) electronics. Here, these limitations are overcome by combining self-aligned asymmetric nanogap electrodes (≈25 nm) produced by adhesion lithography, with a high mobility organic semiconductor, and RF Schottky diodes able to operate in the 5G frequency spectrum are demonstrated. C 16 IDT-BT is used, as the high hole mobility polymer, and the impact of p-doping on the diode performance is studied. Pristine C 16 IDT-BT-based diodes exhibit maximum intrinsic and extrinsic cutoff frequencies (f C ) of >100 and 6 GHz, respectively. This extraordinary performance is attributed to the planar nature of the nanogap channel and the diode's small junction capacitance (<2 pF). Doping of C 16 IDT-BT with the molecular p-dopant C 60 F 48 improves the diode's performance further by reducing the series resistance resulting to intrinsic and extrinsic f C of >100 and ≈14 GHz respectively, while the DC output voltage of an RF rectifier circuit increases by a tenfold. Our work highlights the importance of the planar nanogap architecture and paves the way for the use of organic Schottky diodes in large-area RF electronics of the future., (© 2022 Wiley-VCH GmbH.)

Copper thiocyanate (CuSCN) is a p-type semiconductor that exhibits hole-transport and wide-band gap (∼3.9 eV) characteristics. However, the conductivity of CuSCN is not sufficiently high, which limits its potential application in optoelectronic devices. Herein, CuSCN thin films were exposed to chlorine using a dry etching system to enhance their electrical properties, yielding a maximum hole concentration of 3 × 10 18 cm -3 . The p-type CuSCN layer was then deposited onto an n-type gallium nitride (GaN) layer to form a prototypical ultraviolet-based photodetector. X-ray photoelectron spectroscopy further demonstrated the interface electronic structures of the heterojunction, confirming a favorable alignment for holes and electrons transport. The ensuing p-CuSCN/n-GaN heterojunction photodetector exhibited a turn-on voltage of 2.3 V, a responsivity of 1.35 A/W at -1 V, and an external quantum efficiency of 5.14 × 10 2 % under illumination with ultraviolet light (peak wavelength of 330 nm). The work opens a new pathway for making a plethora of hybrid optoelectronic devices of inorganic and organic nature by using p-type CuSCN as the hole injection layer.

If perovskite solar cells (PSCs) with high power conversion efficiencies (PCEs) are to be commercialized, they must achieve long-term stability, which is usually assessed with accelerated degradation tests. One of the persistent obstacles for PSCs has been successfully passing the damp-heat test (85°C and 85% relative humidity), which is the standard for verifying the stability of commercial photovoltaic (PV) modules. We fabricated damp heat-stable PSCs by tailoring the dimensional fragments of two-dimensional perovskite layers formed at room temperature with oleylammonium iodide molecules; these layers passivate the perovskite surface at the electron-selective contact. The resulting inverted PSCs deliver a 24.3% PCE and retain >95% of their initial value after >1000 hours at damp-heat test conditions, thereby meeting one of the critical industrial stability standards for PV modules.

Recent efforts in the field of organic photodetectors (OPD) have been focused on extending broadband detection into the near-infrared (NIR) region. Here, two blends of an ultralow bandgap push-pull polymer TQ-T combined with state-of-the-art non-fullerene acceptors, IEICO-4F and Y6, are compared to obtain OPDs for sensing in the NIR beyond 1100 nm, which is the cut off for benchmark Si photodiodes. It is observed that the TQ-T:IEICO-4F device has a superior IR responsivity (0.03 AW -1 at 1200 nm and -2 V bias) and can detect infrared light up to 1800 nm, while the TQ-T:Y6 blend shows a lower responsivity of 0.01 AW -1 . Device physics analyses are tied with spectroscopic and morphological studies to link the superior performance of TQ-T:IEICO-4F OPD to its faster charge separation as well as more favorable donor-acceptor domains mixing. In the polymer blend with Y6, the formation of large agglomerates that exceed the exciton diffusion length, which leads to high charge recombination, is observed. An application of these devices as biometric sensors for real-time heart rate monitoring via photoplethysmography, utilizing infrared light, is demonstrated., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

A facile solvothermal synthesis approach for chemical composition control in ternary Bi-S-I systems is reported by simply controlling the sulfide concentration. We demonstrate the application of these bismuth-based ternary mixed-anion compounds as high capacity anode materials in rechargeable batteries. Cells utilising Bi 13 S 18 I 2 achieved an initial capacity value of 807 mA h g -1 , while those with BiSI/Bi 13 S 18 I 2 a value of 1087 mA h g -1 in lithium-ion battery systems.

Solution-processed metal halide perovskite (MHP) single crystals (SCs) are in high demand for a growing number of printed electronic applications due to their superior optoelectronic properties compared to polycrystalline thin films. There is an urgent need to make SC fabrication facile, scalable, and compatible with the printed electronic manufacturing infrastructure. Here, a universal cosolvent evaporation (CSE) strategy is presented by which perovskite SCs and arrays are produced directly on substrates via printing and coating methods within minutes at room temperature from drying droplets. The CSE strategy successfully guides the supersaturation via controlled drying of droplets to suppress all crystallization pathways but one, and is shown to produce SCs of a wide variety of 3D, 2D, and mixed-cation/halide perovskites with consistency. This approach works with commonly used precursors and solvents, making it universal. Importantly, the SC consumes the precursor in the droplet, which enables the large-scale fabrication of SC arrays with minimal residue. Direct on-chip fabrication of 3D and 2D perovskite photodetector devices with outstanding performance is demonstrated. The approach shows that any MHP SC can now be manufactured on substrates using precision printing and scalable, high-throughput coating methods., (© 2022 Wiley-VCH GmbH.)

Electronic doping in organic materials has remained an elusive concept for several decades. It drew considerable attention in the early days in the quest for organic materials with high electrical conductivity, paving the way for the pioneering work on pristine organic semiconductors (OSCs) and their eventual use in a plethora of applications. Despite this early trend, however, recent strides in the field of organic electronics have been made hand in hand with the development and use of dopants to the point that are now ubiquitous. Here, we give an overview of all important advances in the area of doping of organic semiconductors and their applications. We first review the relevant literature with particular focus on the physical processes involved, discussing established mechanisms but also newly proposed theories. We then continue with a comprehensive summary of the most widely studied dopants to date, placing particular emphasis on the chemical strategies toward the synthesis of molecules with improved functionality. The processing routes toward doped organic films and the important doping-processing-nanostructure relationships, are also discussed. We conclude the review by highlighting how doping can enhance the operating characteristics of various organic devices.

We demonstrate proof-of-concept refractive-index structures with large refractive-index-gradient profiles, using a micro-contact photothermal annealing (μCPA) process to pattern organic/inorganic hybrid materials comprising titanium oxide hydrate within a poly(vinyl alcohol) binder. A significant refractive index modulation of up to Δ n ≈ +0.05 can be achieved with μCPA within less than a second of pulsed lamp exposure, which promises the potential for a high throughput fabrication process of photonic structures with a polymer-based system.

Solid-state transistor sensors that can detect biomolecules in real time are highly attractive for emerging bioanalytical applications. However, combining upscalable manufacturing with the required performance remains challenging. Here, an alternative biosensor transistor concept is developed, which relies on a solution-processed In 2 O 3 /ZnO semiconducting heterojunction featuring a geometrically engineered tri-channel architecture for the rapid, real-time detection of important biomolecules. The sensor combines a high electron mobility channel, attributed to the electronic properties of the In 2 O 3 /ZnO heterointerface, in close proximity to a sensing surface featuring tethered analyte receptors. The unusual tri-channel design enables strong coupling between the buried electron channel and electrostatic perturbations occurring during receptor-analyte interactions allowing for robust, real-time detection of biomolecules down to attomolar (am) concentrations. The experimental findings are corroborated by extensive device simulations, highlighting the unique advantages of the heterojunction tri-channel design. By functionalizing the surface of the geometrically engineered channel with severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) antibody receptors, real-time detection of the SARS-CoV-2 spike S1 protein down to am concentrations is demonstrated in under 2 min in physiological relevant conditions., (© 2021 Wiley-VCH GmbH.)

There is a growing demand to attain organic materials with high electron mobility, μ e , as current reliable reported values are significantly lower than those exhibited by their hole mobility counterparts. Here, it is shown that a well-known nonfullerene-acceptor commonly used in organic solar cells, that is, BTP-4F (aka Y6), enables solution-processed organic thin-film transistors (OTFT) with a μ e as high as 2.4 cm 2  V -1  s -1 . This value is comparable to those of state-of-the-art n-type OTFTs, opening up a plethora of new possibilities for this class of materials in the field of organic electronics. Such efficient charge transport is linked to a readily achievable highly ordered crystalline phase, whose peculiar structural properties are thoroughly discussed. This work proves that structurally ordered nonfullerene acceptors can exhibit intrinsically high mobility and introduces a new approach in the quest of high μ e organic materials, as well as new guidelines for future materials design., (© 2021 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Neuromorphic computing has the potential to address the inherent limitations of conventional integrated circuit technology, ranging from perception, pattern recognition, to memory and decision-making ( Acc. Chem. Res. 2019, 52 (4), 964-974) ( Nature 2004, 431 (7010), 796-803) ( Nat. Nanotechnol. 2013, 8 (1), 13-24). Despite their low power consumption ( Nano Lett. 2016, 16 (11), 6724-6732), traditional two-terminal memristors can perform only a single function while lacking heterosynaptic plasticity ( Nanotechnology 2013, 24 (38), 382001). Inspired by the unconditioned reflex, multiterminal memristive transistors (memtransistor) were developed to realize complex functions, such as multiterminal modulation and heterosynaptic plasticity ( Nature 2018, 554, (7693), 500-504). Here we combine a hybrid metal halide perovskite with an organic conjugated polymer to form heterojunction transistors that are responsive to both electrical and optical stimuli. We show that the synergistic effects of photoinduced ion migration in the perovskite and electronic transport in the polymer layers can be exploited to realize memristive functions. The device combines reversible, nonvolatile conductance modulation with large switching current ratios, high endurance, and long retention times. Using in situ scanning Kelvin probe microscopy and variable-temperature charge transport measurement, we correlate the collective effects of bias-induced and photoinduced ion migration with the heterosynaptic behavior observed in this hybrid memtransistor. The hybrid heterojunction channel concept is expected to be applicable to other material combinations making it a promising platform for deployment in innovative neuromorphic devices of the future.

High-voltage lithium-ion batteries (LIBs) enabled by high-voltage electrolytes can effectively boost energy density and power density, which are critical requirements to achieve long travel distances, fast-charging, and reliable safety performance for electric vehicles. However, operating these batteries beyond the typical conditions of LIBs (4.3 V vs Li/Li + ) leads to severe electrolyte decomposition, while interfacial side reactions remain elusive. These critical issues have become a bottleneck for developing electrolytes for applications in extreme conditions. Herein, an additive-free electrolyte is presented that affords high stability at high voltage (4.5 V vs Li/Li + ), lithium-dendrite-free features upon fast-charging operations (e.g., 162 mAh g -1 at 3 C), and superior long-term battery performance at low temperature. More importantly, a new solvation structure-related interfacial model is presented, incorporating molecular-scale interactions between the lithium-ion, anion, and solvents at the electrolyte-electrode interfaces to help interpret battery performance. This report is a pioneering study that explores the dynamic mutual-interaction interfacial behaviors on the lithium layered oxide cathode and graphite anode simultaneously in the battery. This interfacial model enables new insights into electrode performances that differ from the known solid electrolyte interphase approach to be revealed, and sets new guidelines for the design of versatile electrolytes for metal-ion batteries., (© 2021 Wiley-VCH GmbH.)

Self-assembled monolayers (SAMs) based on Br-2PACz ([2-(3,6-dibromo-9H-carbazol-9-yl)ethyl]phosphonic acid) 2PACz ([2-(9H-Carbazol-9-yl)ethyl]phosphonic acid) and MeO-2PACz ([2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid) molecules were investigated as hole-extracting interlayers in organic photovoltaics (OPVs). The highest occupied molecular orbital (HOMO) energies of these SAMs were measured at -6.01 and -5.30 eV for Br-2PACz and MeO-2PACz, respectively, and found to induce significant changes in the work function (WF) of indium-tin-oxide (ITO) electrodes upon chemical functionalization. OPV cells based on PM6 (poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)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)]) : BTP-eC9 : PC 71 BM ([6,6]-phenyl-C71-butyric acid methyl ester) using ITO/Br-2PACz anodes exhibited a maximum power conversion efficiency (PCE) of 18.4 %, outperforming devices with ITO/MeO-2PACz (14.5 %) and ITO/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT : PSS) (17.5 %). The higher PCE was found to originate from the much higher WF of ITO/Br-2PACz (-5.81 eV) compared to ITO/MeO-2PACz (4.58 eV) and ITO/PEDOT : PSS (4.9 eV), resulting in lower interface resistance, improved hole transport/extraction, lower trap-assisted recombination, and longer carrier lifetimes. Importantly, the ITO/Br-2PACz electrode was chemically stable, and after removal of the SAM it could be recycled and reused to construct fresh OPVs with equally impressive performance., (© 2021 Wiley-VCH GmbH.)

Electronic doping of organic semiconductors is essential for their usage in highly efficient optoelectronic devices. Although molecular and metal complex-based dopants have already enabled significant progress of devices based on organic semiconductors, there remains a need for clean, efficient and low-cost dopants if a widespread transition towards larger-area organic electronic devices is to occur. Here we report dimethyl sulfoxide adducts as p-dopants that fulfil these conditions for a range of organic semiconductors. These adduct-based dopants are compatible with both solution and vapour-phase processing. We explore the doping mechanism and use the knowledge we gain to 'decouple' the dopants from the choice of counterion. We demonstrate that asymmetric p-doping is possible using solution processing routes, and demonstrate its use in metal halide perovskite solar cells, organic thin-film transistors and organic light-emitting diodes, which showcases the versatility of this doping approach., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)