Efficient Deep-Blue Light-Emitting Diodes Through Decoupling of Colloidal Perovskite Quantum Dots.

Metal halide perovskite light-emitting diodes (PeLEDs) have exceptional color purity but designs that emit deep-blue color with high efficiency have not been fully achieved and become more difficult in the thin film of confined perovskite colloidal quantum dots (PeQDs) due to particle interaction. Here it is demonstrated that electronic coupling and energy transfer in PeQDs induce redshift in the emission by PeQD film, and consequently hinder deep-blue emission. To achieve deep-blue emission by avoiding electronic coupling and energy transfer, a QD-in-organic solid solution is introduced to physically separate the QDs in the film. This physical separation of QDs reduces the interaction between them yielding a blueshift of ≈7 nm in the emission spectrum. Moreover, using a hole-transporting organic molecule with a deep-lying highest occupied molecular orbital (≈6.0 eV) as the organic matrix, the formation of exciplex emission is suppressed. As a result, an unprecedently high maximum external quantum efficiency of 6.2% at 462 nm from QD-in-organic solid solution film in PeLEDs is achieved, which satisfies the deep-blue color coordinates of CIEy < 0.06. This work suggests an important material strategy to deepen blue emission without reducing the particle size to <≈4 nm.

Engineering Symmetry Breaking in Twisted MoS2-MoSe2 Heterostructures for Optimal Thermoelectric Performance.

Engineering symmetry breaking in thermoelectric materials holds promise for achieving an optimal thermoelectric efficiency. van der Waals (vdW) layered transition metal dichalcogenides (TMDCs) provide critical opportunities for manipulating the intrinsic symmetry through in-plane symmetry breaking interlayer twists and out-of-plane symmetry breaking heterostructures. Herein, the symmetry-dependent thermoelectric properties of MoS2 and MoSe2 obtained via first-principles calculations are reported, yielding an advanced ZT of 2.96 at 700 K. The underlying mechanisms reveal that the in-plane symmetry breaking results in a lowest thermal conductivity of 1.96 W·m-1·K-1. Additionally, the electric properties can be significantly modulated through band flattening and bandgap alteration, stemming directly from the modified interlayer electronic coupling strength owing to spatial repulsion effects. In addition, out-of-plane symmetry breaking induces band splitting, leading to a decrease in the degeneracy and complex band structures. Consequently, the power factor experiences a notable enhancement from ∼1.32 to 1.71 × 10-2 W·m-1·K-2, which is attributed to the intricate spatial configuration of charge densities and the resulting intensified intralayer electronic coupling. Upon simultaneous implementation of in-plane and out-of-plane symmetry breaking, the TMDCs exhibit an indirect bandgap to direct bandgap transition compared to the pristine structure. This work demonstrates an avenue for optimizing thermoelectric performance of TMDCs through the implementation of symmetry breaking.

Properties of the iron-sulfur cluster electron transfer relay in an [FeFe]-hydrogenase that is tuned for H2 oxidation catalysis.

[FeFe]-hydrogenases catalyze the reversible oxidation of H2 from electrons and protons at an organometallic active site cofactor named the H-cluster. In addition to the H-cluster, most [FeFe]-hydrogenases possess accessory FeS cluster (F-cluster) relays that function in mediating electron transfer with catalysis. There is significant variation in the structural properties of F-cluster relays among the [FeFe]-hydrogenases; however, it is unknown how this variation relates to the electronic and thermodynamic properties, and thus the electron transfer properties, of enzymes. Clostridium pasteurianum [FeFe]-hydrogenase II (CpII) exhibits a large catalytic bias for H2 oxidation (compared to H2 production), making it a notable system for examining if F-cluster properties contribute to the overall function and efficiency of the enzyme. By applying a combination of multifrequency and potentiometric electron paramagnetic resonance, we resolved two electron paramagnetic resonance signals with distinct power- and temperature-dependent properties at g = 2.058 1.931 1.891 (F2.058) and g = 2.061 1.920 1.887 (F2.061), with assigned midpoint potentials of -140 ± 18 mV and -406 ± 12 mV versus normal hydrogen electrode, respectively. Spectral analysis revealed features consistent with spin-spin coupling between the two [4Fe-4S] F-clusters, and possible functional models are discussed that account for the contribution of coupling to the electron transfer landscape. The results signify the interplay of electronic coupling and free energy properties and parameters of the FeS clusters to the electron transfer mechanism through the relay and provide new insight as to how relays functionally complement the catalytic directionality of active sites to achieve highly efficient catalysis.

Precisely Patterned Channels in a Vertical Organic Electrochemical Transistor with a Diazirine Photo-Crosslinker.

Organic electrochemical transistors (OECTs) rely on both efficient ionic doping/de-doping process and carrier transport in the mixed ionic-electronic channel under the modulation of gate bias. Moreover, channels that hold photopatterning capability are highly desired to minimize parasitic capacitance and simplify the fabrication process/cost. However, yielding photo-patternable channels with both precise/robust patterning capability and controllable ionic-electronic coupling is still challenging. Herein, double-end trifluoromethyl diazirines (DtFDA) with different chain lengths are introduced in the OECT channel to act as both photo-crosslinker and medium to regulate ionic-electronic transport. Specifically, high-resolution patterns with a minimum line width/gap of 2 µm are realized in p(g2T-T) or Homo-gDPP based channels by introducing DtFDA. Maximum transconductances of 68.6 mS and 81.6 mS, current on/off ratio of 106 and 107 (under a drain voltage of only ±0.1 V), are achieved in p- and n-type vertical OECTs (vOECTs), respectively, along with current densities exceeding 1 kA cm-2 and good cycling stability of more than 100,000 cycles (2000 seconds). This work provides a new and facile strategy for the fabrication of vOECT channels with high resolution and high performance via the introduction of a simple and efficient crosslinker.

Suppressing the Conductance of Single-Molecule Junctions Fabricated by sp2 C-H Bond Metalation.

High-conducting single-molecule junctions have attracted a great deal of attention, but insulating single-molecule junctions, which are critical in molecular circuits, have been less investigated due to the long-standing challenges. Herein, the in situ formation of a Au-C linker via electrical-potential-mediated sp2 C-H bond metalation of polyfluoroarenes with the assistance of scanning tunneling microscope-based break junction technique is reported. This metalation process is bias-dependent and occurs with an electropositive electrode, and the formed junction is highly oriented. Surprisingly, these polyfluoroarenes exhibit unexpected low conductance even under short molecular lengths and are superior molecular insulators. Flicker noise analysis and DFT calculations confirm that the insulating properties of polyfluoroarenes are ascribed to their multiple fluorine substituents. Our results pave a way for constructing oriented asymmetric molecular junctions and provide an efficient strategy to suppress the single-molecule conductance, which will aid in the design of molecular insulators and advance the development of self-integrating functional molecular circuits.

Ligand-mediated exciton dissociation and interparticle energy transfer on CsPbBr3 perovskite quantum dots for efficient CO2-to-CO photoreduction.

Perovskite quantum dots (PQDs) hold immense potential as photocatalysts for CO2 reduction due to their remarkable quantum properties, which facilitates the generation of multiple excitons, providing the necessary high-energy electrons for CO2 photoreduction. However, harnessing multi-excitons in PQDs for superior photocatalysis remains challenging, as achieving the concurrent dissociation of excitons and interparticle energy transfer proves elusive. This study introduces a ligand density-controlled strategy to enhance both exciton dissociation and interparticle energy transfer in CsPbBr3 PQDs. Optimized CsPbBr3 PQDs with the regulated ligand density exhibit efficient photocatalytic conversion of CO2 to CO, achieving a 2.26-fold improvement over unoptimized counterparts while maintaining chemical integrity. Multiple analytical techniques, including Kelvin probe force microscopy, temperature-dependent photoluminescence, femtosecond transient absorption spectroscopy, and density functional theory calculations, collectively affirm that the proper ligand termination promotes the charge separation and the interparticle transfer through ligand-mediated interfacial electron coupling and electronic interactions. This work reveals ligand density-dependent variations in the gas-solid photocatalytic CO2 reduction performance of CsPbBr3 PQDs, underscoring the importance of ligand engineering for enhancing quantum dot photocatalysis.

Enhancing Hydrogen Evolution Reaction Activity of Palladium Catalyst by Immobilization on MXene Nanosheets.

Efficient catalysts with minimal content of catalytically active noble metals are essential for the transition to the clean hydrogen economy. Catalyst supports that can immobilize and stabilize catalytic nanoparticles and facilitate the supply of electrons and reactants to the catalysts are needed. Being hydrophilic and more conductive compared with carbons, MXenes have shown promise as catalyst supports. However, the controlled assembly of their 2D sheets creates a challenge. This study established a lattice engineering approach to regulate the assembly of exfoliated Ti3C2Tx MXene nanosheets with guest cations of various sizes. The enlargement of guest cations led to a decreased interlayer interaction of MXene lamellae and increased surface accessibility, allowing intercalation of Pd nanoparticles. Stabilization of Pd nanoparticles between interlayer-expanded MXene nanosheets improved their electrocatalytic activity. The Pd-immobilized K+-intercalated MXene nanosheets (PdKMX) demonstrated exceptional electrocatalytic performance for the hydrogen evolution reaction with the lowest overpotential of 72 mV (@10 mA cm-2) and the highest turnover frequency of 1.122 s-1 (@ an overpotential of 100 mV), which were superior to those of the state-of-the-art Pd nanoparticle-based electrocatalysts. Weakening of the interlayer interaction during self-assembly with K+ ions led to fewer layers in lamellae and expansion of the MXene in the c direction during Pd anchoring, providing numerous surface-active sites and promoting mass transport. In situ spectroscopic analysis suggests that the effective interfacial electron injection from the Pd nanoparticles strongly immobilized on interlayer-expanded PdKMX may be responsible for the improved electrocatalytic performance.

Staggered Assembly of a Dimeric Au13 Cluster: Impacts on Coupling of Geometric Isomerism.

The specific states of aggregation of metal atoms in sub-nanometer-sized gold clusters are related to the different quantum confinement volumes of electrons, leading to novel optical and electronic properties. These volumes can be tuned by changing the relative positions of the gold atoms to generate isomers. Studying the isomeric gold core and the electron coupling between the basic units is fundamentally important for nanoelectronic devices and luminescence; however, appropriate cases are lacking. In this study, the structure of the first staggered di-superatomic Au25 -S was solved using single-crystal X-ray diffraction. The optical properties of Au25 -S were studied by comparing with eclipsed Au25 -E. From Au25 -E to Au25 -S, changes in the electronic structures occurred, resulting in significantly different optical absorptions originating from the coupling between the two Au13 modules. Au25 -S shows a longer electron decay lifetime of 307.7 ps before populating the lowest triplet emissive state, compared to 1.29 ps for Au25 -E. The experimental and theoretical results show that variations in the geometric isomerism lead to distinct photophysical processes owing to isomerism-dependent electronic coupling. This study offers new insights into the connection between the geometric isomerism of nanosized building blocks and the optical properties of their assemblies, opening new possibilities for constructing function-specific nanomaterials.

Kinkless Electronic Junction along 1D Electronic Channel Embedded in a Van Der Waals Layer.

Here, the formation of type-I and type-II electronic junctions with or without any structural discontinuity along a well-defined 1 nm-wide 1D electronic channel within a van der Waals layer is reported. Scanning tunneling microscopy and spectroscopy techniques are employed to investigate the atomic and electronic structure along peculiar domain walls formed on the charge-density-wave phase of 1T-TaS2 . Distinct kinds of abrupt electronic junctions with discontinuities of the band gap along the domain walls are found, some of which even do not have any structural kinks and defects. Density-functional calculations reveal a novel mechanism of the electronic junction formation; they are formed by a kinked domain wall in the layer underneath through substantial electronic interlayer coupling. This work demonstrates that the interlayer electronic coupling can be an effective control knob over nanometer-scale electronic property of 2D atomic monolayers.

The Effect of Monomer Size on Fusion and Coupling in Colloidal Quantum Dot Molecules.

The fusion step in the formation of colloidal quantum dot molecules, constructed from two core/shell quantum dots, dictates the coupling strength and hence their properties and enriched functionalities compared to monomers. Herein, studying the monomer size effect on fusion and coupling, we observe a linear relation of the fusion temperature with the inverse nanocrystal radius. This trend, similar to that in nanocrystal melting, emphasizes the role of the surface energy. The suggested fusion mechanism involves intraparticle ripening where atoms diffuse to the reactive connecting neck region. Moreover, the effect of monomer size and neck filling on the degree of electronic coupling is studied by combined atomistic-pseudopotential calculations and optical measurements, uncovering strong coupling effects in small QD dimers, leading to significant optical changes. Understanding and controlling the fusion and hence coupling effect allows tailoring the optical properties of these nanoscale structures, with potential applications in photonic and quantum technologies.

Understanding the Microscopic Origin of the Contact Resistance at the Polymer-Electrode Interface.

Contact resistance (RC) in organic devices originates from a mismatch in energy levels between injecting electrodes and organic semiconductors (OSCs). However, the microscopic effects governing charge transfer between electrodes and the OSCs have not been analyzed in detail. We fabricated transistors with different OSCs (PTB7, PCDTBT, and PTB7-Th) and electrodes (MoO3, Au, and Ag) and measured their contact resistance. Regardless of the electrodes, devices with PTB7-Th exhibit the lowest values of RC. To explain the trends observed, first-principles computations were performed on contact interfaces based on the projector operator diabatization method. Our results revealed that differences in energy levels and the electronic couplings between OSCs' highest occupied molecular orbitals and vacant states on the electrodes influence device RC. Further, based on values obtained from the first-principles, the rate of charge transfer between OSCs and electrodes is calculated and found to correlate strongly with trends in RC for devices with different OSCs. We thus show that device RC is governed by the feasibility of charge transfer at the contact interface and hence determined by energy levels and electronic coupling among orbitals and states located on OSCs and electrodes.

Highly Rectifying Water-Mediated Hydrogen Bond-Coupled Organic-Inorganic Interfaces.

Asymmetrically conducting interfaces are the building blocks of electronic devices. While p-n junction diodes made of seminal inorganic semiconductors with rectification ratios close to the theoretical limits are routinely fabricated, the analogous organic-inorganic and organic-organic interfaces are still too leaky to afford functional use. We report fabricating highly rectifying organic-inorganic interfaces by forming water-mediated hydrogen bonds between the hydrophilic surfaces of a hole-conducting polymer anode and a polycrystalline n-type metal oxide cathode. These hydrogen bonds simultaneously strengthen the anode-cathode electronic coupling, facilitate the matching between their incompatible surface structures, and passivate the detrimental surface imperfections. Compared to an analogous directly joined interface, our hydrogen-bonded Au-PEDOT:PSS-H2O-TiO2-Ti diodes demonstrate 105 times higher rectification ratios. These results illustrate the strong electronic coupling power of the hydrogen bonds on a macroscopic scale and underscore the hydrogen-bonded interfaces as the building blocks of fabricating organic electronic and optoelectronic devices. The presented interface model is anticipated to advance designing electronic devices based on the organic-organic and organic-inorganic hetero-interfaces. Described electronic implications of hydrogen bonding on the conductive polymer interfaces are anticipated to be impactful in the organic electronics and neuromorphic engineering.

Large-scale surface hopping simulation of charge transport in hexagonal molecular crystals: role of electronic coupling signs.

In large-scale surface hopping simulations with a huge number of electronic states, trivial crossings could easily lead to incorrect long-range charge transfer and induce large numerical errors. We here study the charge transport in two-dimensional hexagonal molecular crystals with a parameter-free full crossing corrected global flux surface hopping method. Fast time-step size convergence and system size independence have been realized in large systems containing thousands of molecular sites. In hexagonal systems, each molecular site has six nearest neighbours. We find that the signs of their electronic couplings have a strong impact on the charge mobility and delocalization strength. In particular, changing the signs of electronic couplings can even lead to a transition from hopping to band-like transport. In comparison, such phenomena cannot be observed in extensively studied two-dimensional square systems. This is attributed to symmetry of the electronic Hamiltonian and distribution of the energy levels. Due to its high performance, the proposed approach is promising to be applied to more realistic and complex systems for molecular design.

Enhancing Prosthetic Control through High-Fidelity Myoelectric Mapping with Molecular Anchoring Technology.

Myoelectric control utilizes electrical signals generated from the voluntary contraction of remaining muscles in an amputee's stump to operate a prosthesis. Precise and agile control requires low-level myoelectric signals (below 10% of maximum voluntary contraction, MVC) from weak muscle contractions such as phantom finger or wrist movements, but imbalanced calcium concentration in atrophic skin can distort the signals. This is due to poor ionic-electronic coupling between skin and electrode, which often causes excessive muscle contraction, fatigue, and discomfort during delicate tasks. To overcome this challenge, a new strategy called molecular anchoring is developed to drive hydrophobic molecular effectively interact with and embed into stratum corneum for high coupling regions between ionic fluxes and electronic currents. The use of hydrophobic poly(N-vinyl caprolactam) gel has resulted in an interface impedance of 20 kΩ, which is 1/100 of a commercial acrylic-based electrode, allowing the detection of ultralow myoelectric signals (≈1.5% MVC) that approach human limits. With this molecular anchoring technology, amputees operate a prosthesis with greater dexterity, as phantom finger and wrist movements are predicted with 97.6% accuracy. This strategy provides the potential for a comfortable human-machine interface when amputees accomplish day-to-day tasks through precise and dexterous myoelectric control.

Etheno-bridged Azaacene Spiro Dimers.

We present the synthesis of two sets of spiro-connected azaacene dimers. Their geometry and electronic coupling are critically determined by a secondary linker, i. e., an etheno- and an ethano-bridge. The core fragment of the etheno-bridged dimer corresponds to a conformationally locked cis-stilbene. Optoelectronic properties, single crystal X-ray structures and stability with respect to oxidation of the conjugated and non-conjugated dimers are reported and compared. The conjugated dimers exhibit smaller optical gaps and bathochromically shifted absorption maxima, but are prone to unexpected oxygen addition, dearomatizing one of the azaacene substituents.

Dual-Atom Support Boosts Nickel-Catalyzed Urea Electrooxidation.

Nickel-based catalysts have been regarded as one of the most promising electrocatalysts for urea oxidation reaction (UOR), however, their activity is largely limited by the inevitable self-oxidation reaction of Ni species (NSOR) during the UOR. Here, we proposed an interface chemistry modulation strategy to trigger the occurrence of UOR before the NSOR via constructing a 2D/2D heterostructure that consists of ultrathin NiO anchored Ru-Co dual-atom support (Ru-Co DAS/NiO). Operando spectroscopic characterizations confirm this unique triggering mechanism on the surface of Ru-Co DAS/NiO. Consequently, the fabricated catalyst exhibits outstanding UOR activity with a low potential of 1.288 V at 10 mA cm-2 and remarkable long-term durability for more than 330 h operation. DFT calculations and spectroscopic characterizations demonstrate that the favorable electronic structure induced by this unique heterointerface endows the catalyst energetically more favorable for the UOR than the NSOR.

In-situ decoration of tin sulfide on Niobium carbide MXene with robust electronic coupling for improved sodium storage performance.

Tin sulfide (SnS) has been considered as one of the most promising sodium storage materials because of its excellent electrochemical activity, low cost, and low-dimensional structure. However, owing to the serious volume change upon discharging/charging and poor electronic conductivity, the SnS-based electrodes often suffer from electrode pulverization and sluggish reaction kinetics, thus resulting in serious capacity fading and degraded rate capability. In this work, SnS nanoparticles uniformly distributed on the surface of the layered Niobium carbide MXene (SnS/Nb2CTx) were fabricated through a facile solvothermal approach followed by calcination, endowing the SnS/Nb2CTx with a three-dimensional interconnected framework as well as fast charge transfer. Benefitting from the excellent electronic/ionic conductivity, efficient buffering matrix, abundant active sites, and high sodium storage activity inherited from the structure design, the robust electronic coupling between SnS nanoparticle and Nb2CTx MXene results in excellent electrochemical output, which demonstrates superior reversible capacities of 479.6 (0.1 A/g up to 100 cycles) and 278.9 mAh/g (0.5 A/g up to 500 cycles) upon sodium storage, respectively. The excellent electrochemical performance manifests the promise of the combination of metal sulfides with Nb2CTx MXene to fabricate high-performance electrodes for sodium storage.

The role of various components in Ru-NiCo alloys in boosting the performance of overall water splitting.

Understanding the synergistic mechanism of multi-component alloys is crucial and challenging for overall water splitting. Herein, Ru-NiCo0.5-600 °C and Ru-Ni0.75Co with excellent electrocatalytic activity are designed and synthesized. The Ru-NiCo0.5-600 °C alloy exhibits remarkable HER activity with an overpotential of 42, 77 and 93 mV at 10 mA cm-2 in alkaline, acidic and neutral conditions, and the Ru-Ni0.75Co electrocatalyst presents outstanding OER activity with an overpotential of 176 mV at 10 mA cm-2 in 1.0 M KOH. The Ru-NiCo0.5-600 °C ||Ru-Ni0.75Co cell requires only 1.48 and 1.69 V to reach 10 and 100 mA cm-2 towards overall water splitting. A series of experiments reveal that the strong electronic coupling among Ru, Ni and Co regulates the electronic structure and enhances the intrinsic catalytic activity and stability of the as-synthesized Ru-NiCo electrocatalysts. Systematic experimental and theoretical results prove that Ni atoms act as the active sites of dissociating water, while Ru and Co are respectively the active centers of proton and hydroxyl adsorption for HER and OER. Our work provides a new perspective for profoundly understanding the synergistic effect of multi-component alloys towards water splitting.

Stable Cuprous Hydroxide Nanostructures by Organic Ligand Functionalization.

Copper compounds have been extensively investigated for diverse applications. However, studies of cuprous hydroxide (CuOH) have been scarce due to structural metastability. Herein, a facile, wet-chemistry procedure is reported for the preparation of stable CuOH nanostructures via deliberate functionalization with select organic ligands, such as acetylene and mercapto derivatives. The resulting nanostructures are found to exhibit a nanoribbon morphology consisting of small nanocrystals embedded within a largely amorphous nanosheet-like scaffold. The acetylene derivatives are found to anchor onto the CuOH forming CuC linkages, whereas CuS interfacial bonds are formed with the mercapto ligands. Effective electronic coupling occurs at the ligand-core interface in the former, in contrast to mostly non-conjugated interfacial bonds in the latter, as manifested in spectroscopic measurements and confirmed in theoretical studies based on first principles calculations. Notably, the acetylene-capped CuOH nanostructures exhibit markedly enhanced photodynamic activity in the inhibition of bacteria growth, as compared to the mercapto-capped counterparts due to a reduced material bandgap and effective photocatalytic generation of reactive oxygen species. Results from this study demonstrate that deliberate structural engineering with select organic ligands is an effective strategy in the stabilization and functionalization of CuOH nanostructures, a critical first step in exploring their diverse applications.

Sodium titanium phosphate nanocube decorated on tablet-like carbon for robust sodium storage performance at low temperature.

Sodium-ion batteries, featuring resource abundance and similar working mechanisms to lithium-ion batteries, have gained extensive interest in both scientific exploration and industrial applications. However, the extremely sluggish reaction kinetics of charge carrier (Na+) at subzero temperatures significantly reduces their specific capacities and cycling life. Herein, this study presents a novel hybrid structure with sodium titanium phosphate (NaTi2(PO4)3, NTP) nanocube in-situ decorated on tablet-like carbon (NTP/C), which manifests superior sodium storage performances at low temperatures. At even -25 °C, a stable cycling with a specific capacity of 94.3 mAh/g can still be maintained after 200 cycles at 0.5 A/g, delivering a high capacity retention of 91.5 % compared with that at room temperature, along with an excellent rate capability. Generally, the superionic conductor structure, flat voltage plateaus, as well as the conductive carbonaceous framework can efficiently facilitate the charge transfer, accelerate the diffusion of Na+, and decrease the electrochemical polarization. Moreover, further investigations on diffusion kinetics, solid electrolyte interface layer, and the interaction between NTP and carbonaceous skeleton reveal its high Na+ diffusion coefficient, robust solid electrolyte interface, and strong electronic interaction, thus contributing to the superior capacity retentions at subzero temperatures.