Ultrafast Coherent Hole Injection at the Interface between CuSCN and Polymer PM6 Using Femtosecond Mid-Infrared Spectroscopy.

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.

Label-Free Metal-Oxide Transistor Biosensors for Metabolite Detection in Human Saliva.

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 In2 O3 /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 In2 O3 /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.

p-Type Conjugated Polymers Containing Electron-Deficient Pentacyclic Azepinedione.

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 cm2 V-1 s-1. Blends of these polymers with PC71BM 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.

Design and Piezoelectric Energy Harvesting Properties of a Ferroelectric Cyclophosphazene Salt.

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 [(PhCH2 NH)6 P3 N3 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.

On the Conformation of Dimeric Acceptors and Their Polymer Solar Cells with Efficiency over 18 .

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.

Non-invasive, ultrasensitive detection of glucose in saliva using metal oxide transistors.

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 In2O3/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 In2O3/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.

3D-printed polymer composite devices based on a ferroelectric chiral ammonium salt for high-performance piezoelectric energy harvesting.

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 {[Me3CCH(Me)NH3][BF4]} (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 P42, 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.

Interfacial Reconstructed Layer Controls the Orientation of Monolayer Transition-Metal Dichalcogenides.

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.

Understanding the Degradation of Methylenediammonium and Its Role in Phase-Stabilizing Formamidinium Lead Triiodide.

Formamidinium lead triiodide (FAPbI3) 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 (MDACl2) has been used as an additive in FAPbI3. MDA2+ has been reported as incorporated into the perovskite lattice alongside Cl-. However, the precise function and role of MDA2+ remain uncertain. Here, we grow FAPbI3 single crystals from a solution containing MDACl2 (FAPbI3-M). We demonstrate that FAPbI3-M crystals are stable against transformation to the photoinactive δ-phase for more than one year under ambient conditions. Critically, we reveal that MDA2+ is not the direct cause of the enhanced material stability. Instead, MDA2+ degrades rapidly to produce ammonium and methaniminium, which subsequently oligomerizes to yield hexamethylenetetramine (HMTA). FAPbI3 crystals grown from a solution containing HMTA (FAPbI3-H) replicate the enhanced α-phase stability of FAPbI3-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 FAPbI3-M and FAPbI3-H at ∼0.5 mol % and infer that this addition is responsible for the improved α-phase stability.

Recent Progress in Colloidal Quantum Dot Thermoelectrics.

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.

Visualization of domain structure and piezoelectric energy harvesting in a ferroelectric metal-ligand cage.

The ferroelectric behaviour of an octahedral cage [[Ni6(H2O)12(TPTA)8]·(NO3)12·36H2O] (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.

18.73% efficient and stable inverted organic photovoltaics featuring a hybrid hole-extraction layer.

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-9H-carbazol-9-yl)ethyl)phosphonic acid (Br-2PACz) between the bulk-heterojunction (BHJ) and a 7 nm-thin layer of MoO3 in inverted OPVs, and study its effects on the cell performance. We find that the Br-2PACz/MoO3 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/MoO3-based OPVs exhibit higher operational stability under continuous illumination and thermal annealing (80 °C). The T80 lifetime of OPVs featuring Br-2PACz/MoO3 - taken as the time over which the cell's PCE reduces to 80% of its initial value - increases compared to MoO3-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.

Surface Modification of Hetero-phase Nanoparticles for Low-Cost Solution-Processable High-k Dielectric Polymer Nanocomposites.

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 TiO2 and BaTiO3 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 TiO2:BaTiO3 NPs, the dielectric constant of the ensuing NC is found to be 50.2, which is comparable with the functionalized BaTiO3-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.

Ultra-Narrowband Near-Infrared Responsive J-Aggregates of Fused Quinoidal Tetracyanoindacenodithiophene.

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.

The effect of residual palladium on the performance of organic electrochemical transistors.

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.

Hitherto Unknown Solvent and Anion Pairs in Solvation Structures Reveal New Insights into High-Performance Lithium-Ion Batteries.

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.

Radiofrequency Schottky Diodes Based on p-Doped Copper(I) Thiocyanate (CuSCN).

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 C60F48 to improve the diode's operating characteristics. Rectifier circuits fabricated with the doped CuSCN/C60F48 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 VIN = ±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 C60F48. The ensuing diode technology can be used in flexible complementary circuits targeting low-energy-budget applications for the emerging internet of things device ecosystem.

Rapid and up-scalable manufacturing of gigahertz nanogap diodes.

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.

Chlorine-Infused Wide-Band Gap p-CuSCN/n-GaN Heterojunction Ultraviolet-Light Photodetectors.

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 × 1018 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 × 102% 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.