Metal-organic Interface Research Articles

In-Device Ballistic-Electron-Emission Spectroscopy for Accurately In Situ Mapping Energy Level Alignment at Metal-Organic Semiconductors Interface.

Energy level alignment at metal/organic semiconductors (OSCs) interface governs electronic processes in organic electronics devices, making its precise determination essential for understanding carrier transport behaviors and optimizing device performance. However, it is proven that accurately characterizing the energy barrier at metal/OSC interface under operational conditions remains challenging due to the technical limitations of traditional methods. Herein, through integrating highly-improved device constructions with an ingenious derivative-assisted data processing method, this study demonstrates an in-device ballistic-electron-emission spectroscopy using hot-electron transistors to accurately characterize the energy barrier at metal/OSC interface under in-operando conditions. This technique is found that a remarkable improvement in measurement accuracy, reaching up to ±0.03eV, can be achieved-surpassing previous techniques (±0.1-0.2eV). The high accuracy allows us to monitor subtle changes in energy barriers at metal/OSC interface caused by variations in the aggregation state of OSCs, a phenomenon that is theoretically possible but failed to be directly demonstrated through conventional methods. Moreover, this study makes demonstration that this technology is universally applicable to various metal/OSC interfaces consisting of electron-transporting, hole-transporting, and ambipolar OSCs. These findings manifest the great potential of this method to advance both theoretical exploration and technical applications in organic electronics.

Boosting alkyne semi-hydrogenation selectivity via metal-organic interface modulated self-supporting palladium-based catalysts

The semi-hydrogenation of alkynes is crucial in the chemical industry, yet developing catalysts with both high activity and selectivity remains challenging. In this work, we introduced a self-supported method to fabricate a palladium-based nanocatalyst by in-situ reduction of Pd(II) on copper-based coordination polymers (Cu(I)-PNS) without external reducing agents. The resulting Pd/Cu(I)-PNS catalyst demonstrated exceptional efficiency and 94.8 % selectivity for styrene in the semi-hydrogenation of phenylacetylene, with no over-hydrogenation. Our findings highlight that the metal–organic interface enhances the catalyst’s selectivity by weakening styrene adsorption due to electronic modification. Additionally, the catalyst exhibited superior stability and activity, showing potential for various alkynes. This approach offers a direct and efficient strategy for creating highly selective palladium-based nanocatalysts for industrial applications.

Dual functional bio-inspired additives reconstruct metal-organic interface stability for wearable energy storage system

Aqueous zinc-ion batteries (AZIBs) hold significant promise across wearable energy storage devices due to their superior safety and cost-effectiveness. However, the instability of the electrode/electrolyte interface leads to severe hydrogen evolution reaction (HER) and dendritic growth. Herein, a bio-inspired additive, keratin (Ker), is introduced to construct a robust interfacial layer. The hydrogen bonding donors homogenize the distribution of interfacial hydrogen bond networks and increases the electron density in Zn2+-OH interaction, stabilizing bound H2O molecules and effectively inhibiting HER. Additionally, electron transfer from the highly reactive thiol (-SH) motivates the formation of Zn-S chemical linkage, enhancing interface stability. These features endow Zn||Zn symmetric cells with an impressive cycle life, reaching up to 3364 h at 1 mA cm−2/1 mAh cm−2. The Zn||α-MnO2 and Zn||VO2 full cells also exhibit a substantial capacity retention after 1000 cycles. Incorporating multi-step laser cutting technology enables the fabrication of flexible, large-area micro-batteries with prolonged cycle life. This study presents an advanced methodology for heralding a promising pathway to improve the reversibility of aqueous energy storage systems.

The Role of Rare-Earth Atoms in the Anisotropy and Antiferromagnetic Exchange Coupling at a Hybrid Metal-Organic Interface.

Magnetic anisotropy and magnetic exchange interactions are crucial parameters that characterize the hybrid metal-organic interface, a key component of an organic spintronic device. It is shown that the incorporation of 4f RE atoms to hybrid metal-organic interfaces of CuPc/REAu2 type (RE = Gd, Ho) constitutes a feasible approach toward on-demand magnetic properties and functionalities. The GdAu2 and HoAu2 substrates differ in their magnetic anisotropy behavior. Remarkably, the HoAu2 surface promotes the inherent out-of-plane anisotropy of CuPc, owing to the match between the anisotropy axis of substrate and molecule. Furthermore, the presence of RE atoms leads to a spontaneous antiferromagnetic exchange coupling at the interface, induced by the 3d-4f superexchange interaction between the unpaired 3d electron of CuPc and the 4f electrons of the RE atoms. It is shown that 4f RE atoms with unquenched quantum orbital momentum ( ), as it is the case of Ho, induce an anisotropic interfacial exchangecoupling.

Modulating the zinc ion flux and electric field intensity by multifunctional metal-organic complex interface layer for highly stable Zn anode

The uncontrollable growth of Zn dendrites accompanied by side reactions severely impedes the industrialized process of zinc ion electrochemical energy storage devices. Herein, we propose a practical metal-organic complex interface layer to manipulate the zinc ion flux and electric field intensity, enabling highly homogeneous zinc electrodeposition. The zinc-terephthalic acid complex (ZnPTA) with lower adsorption energy for zinc ion (−1.3 eV) builds a zincophilic interface favoring the ordered nucleation and growth of Zn. Moreover, the ZnPTA layer can serve as physical barrier to protect the newly deposited Zn from corrosion in the aqueous electrolyte. The modified Zn anode with the ZnPTA layer (ZnPTA@Zn) demonstrates excellent cycling stability more than 3000 h at 1 mA/cm2. Besides, the zinc-ion battery and zinc-ion hybrid capacitor using the ZnPTA@Zn electrode deliver outstanding cycle performance (up to 5500 cycles with high residual capacity ratio of 77.9%). This work provides a promising metal-organic complex interface design on enhancing the performance of Zn metal anode.

Ultrafast Ion Transfer of Metal-Organic Framework Interface for Highly Efficient Energy Storage.

Flexible supercapacitors are favorable for wearable electronics. However, their high-rate capability and mechanical properties are limited because of unsatisfactory ion transfer kinetics and interfacial modulus mismatch inside devices. Here, we develop a metal-organic framework interface with superior electrical and mechanical properties for supercapacitors. The interfacial mechanism facilitates ultrafast ion transfer with an energy barrier reduction of 43% compared with that of conventional transmembrane transport. It delivers high specific capacity at a wide rate range and exhibits ultrastability beyond 30000 charge-discharge cycles. Furthermore, meliorative modulus mismatch benefited from ultrathin interface design that improves mechanical properties of flexible supercapacitors. It delivers a stable energy supply under various mechanical conditions like bending and twisting status and displays ultrastable mechanical properties with performance retention of 95.5% after 10 000 bending cycles. The research paves the way for interfacial engineering for ultrastable electrochemical devices.

Charge-Transfer States at Metal–Organic Interface Limit Singlet Fission Yields: A Photonically Enhanced Pump–Probe Study

Charge-Transfer States at Metal–Organic Interface Limit Singlet Fission Yields: A Photonically Enhanced Pump–Probe Study

Directing the Selectivity of CO Electrolysis to Acetate by Constructing Metal-Organic Interfaces.

Electrochemically converting CO2 to valuable chemicals holds great promise for closing the anthropogenic carbon cycle. Owing to complex reaction pathways and shared rate-determining steps, directing the selectivity of CO2 /CO electrolysis to a specific multicarbon product is very challenging. We report here a strategy for highly selective production of acetate from CO electrolysis by constructing metal-organic interfaces. We demonstrate that the Cu-organic interfaces constructed by in situ reconstruction of Cu complexes show very impressive acetate selectivity, with a high Faradaic efficiency of 84.2 % and a carbon selectivity of 92.1 % for acetate production, in an alkaline membrane electrode assembly electrolyzer. The maximum acetate partial current density and acetate yield reach as high as 605 mA cm-2 and 63.4 %, respectively. Thorough structural characterizations, control experiments, operando Raman spectroscopy measurements, and density functional theory calculation results indicate that the Cu-organic interface creates a favorable reaction microenvironment that enhances *CO adsorption, lowers the energy barrier for C-C coupling, and facilitates the formation of CH3 COOH over other multicarbon products, thus rationalizing the selective acetate production.

Enhanced Photoacoustic Response by Synergistic Ag-Melanin Interplay at the Core of Ternary Biocompatible Hybrid Silica-Based Nanoparticles.

Photoacoustics (PA) is gaining increasing credit among biomolecular imaging methodologies by virtue of its poor invasiveness, deep penetration, high spatial resolution, and excellent endogenous contrast, without the use of any ionizing radiation. Recently, we disclosed the excellent PA response of a self-structured biocompatible nanoprobe, consisting of ternary hybrid nanoparticles with a silver core and a melanin component embedded into a silica matrix. Although preliminary evidence suggested a crucial role of the Ag sonophore and the melanin-containing nanoenvironment, whether and in what manner the PA response is controlled and affected by the self-structured hybrid nanosystems remained unclear. Because of their potential as multifunctional platforms for biomedical applications, a detailed investigation of the metal-polymer-matrix interplay underlying the PA response was undertaken to understand the physical and chemical factors determining the enhanced response and to optimize the architecture, composition, and performance of the nanoparticles for efficient imaging applications. Herein, we provide the evidence for a strong synergistic interaction between eumelanin and Ag which suggests an important role in the in situ-generated metal-organic interface. In particular, we show that a strict ratio between melanin and silver precursors and an accurate choice of metal nanoparticle dimension and the kind of metal are essential for achieving strong enhancements of the PA response. Systematic variation of the metal/melanin component is thus shown to offer the means of tuning the stability and intensity of the photoacoustic response for various biomedical and theranostic applications.

Positional and Rotational Molecular Degrees of Freedom at a Roughened Metal–Organic Interface: The Copper–Fullerene System and Its Multiple Structural Phases

Positional and Rotational Molecular Degrees of Freedom at a Roughened Metal–Organic Interface: The Copper–Fullerene System and Its Multiple Structural Phases

Role of time-dependent foreign molecules bonding in the degradation mechanism of polymer field-effect transistors in ambient conditions.

Long-standing research efforts have enabled the widespread introduction of organic field-effect transistors (OFETs) in next-generation technologies. Concurrently, environmental and operational stability is the major bottleneck in commercializing OFETs. The underpinning mechanism behind these instabilities is still elusive. Here we demonstrate the effect of ambient air on the performance of p-type polymer field-effect transistors. After exposure to ambient air, the device showed significant variations in performance parameters for around 30 days, and then relatively stable behaviour was observed. Two competing mechanisms influencing environmental stability are the diffusion of moisture and oxygen in the metal-organic interface and the active organic layer of the OFET. We measured the time-dependent contact and channel resistances to probe which mechanism is dominant. We found that the dominant role in the degradation of the device stability is the channel resistance rather than the contact resistance. Through time-dependent Fourier transform infrared (FTIR) analysis, we systematically prove that moisture and oxygen cause performance variation in OFETs. FTIR spectra revealed that water and oxygen interact with the polymer chain and perturb its conjugation, thus resulting in degraded performance of the device upon prolonged exposure to ambient air. Our results are important in addressing the environmental instability of organic devices.

Metal-Ligand Interactions and Their Roles in Controlling Nanoparticle Formation and Functions.

ConspectusFunctional nanoparticles (NPs) have been studied extensively in the past decades for their unique nanoscale properties and their promising applications in advanced nanosciences and nanotechnologies. One critical component of studying these NPs is to prepare monodisperse NPs so that their physical and chemical properties can be tuned and optimized. Solution phase reactions have provided the most reliable processes for fabricating such monodisperse NPs in which metal-ligand interactions play essential roles in the synthetic controls. These interactions are also key to stabilizing the preformed NPs for them to show the desired electronic, magnetic, photonic, and catalytic properties. In this Account, we summarize some representative organic bipolar ligands that have recently been explored to control NP formation and NP functions. These include aliphatic acids, alkylphosphonic acids, alkylamines, alkylphosphines, and alkylthiols. This ligand group covers metal-ligand interactions via covalent, coordination, and electrostatic bonds that are most commonly employed to control NP sizes, compositions, shapes, and properties. The metal-ligand bonding effects on NP nucleation rate and growth can now be more thoroughly investigated by in situ spectroscopic and theoretical studies. In general, to obtain the desired NP size and monodispersity requires rational control of the metal/ligand ratios, concentrations, and reaction temperatures in the synthetic solutions. In addition, for multicomponent NPs, the binding strength of ligands to various metal surfaces needs to be considered in order to prepare these NPs with predesigned compositions. The selective ligand binding onto certain facets of NPs is also key to anisotropic growth of NPs, as demonstrated in the synthesis of one-dimensional nanorods and nanowires. The effects of metal-ligand interactions on NP functions are discussed in two aspects, electrochemical catalysis for CO2 reduction and electronic transport across NP assemblies. We first highlight recent advances in using surface ligands to promote the electrochemical reduction of CO2. Several mechanisms are discussed, including the modification of the catalyst surface environment, electron transfer through the metal-organic interface, and stabilization of the CO2 reduction intermediates, all of which facilitate selective CO2 reduction. These strategies lead to better understanding of molecular level control of catalysis for further catalyst optimization. Metal-ligand interaction in magnetic NPs can also be used to control tunneling magnetoresistance properties across NPs in NP assemblies by tuning NP interparticle spacing and surface spin polarization. In all, metal-ligand interactions have yielded particularly promising directions for tuning CO2 reduction selectivity and for optimizing nanoelectronics, and the concepts can certainly be extended to rationalize NP engineering at atomic/molecular precision for the fabrication of sensitive functional devices that will be critical for many nanotechnological applications.

Improved Performance of Organic Thermoelectric Generators Through Interfacial Energetics.

The interfacial energetics are known to play a crucial role in organic diodes, transistors, and sensors. Designing the metal-organic interface has been a tool to optimize the performance of organic (opto)electronic devices, but this is not reported for organic thermoelectrics. In this work, it is demonstrated that the electrical power of organic thermoelectric generators (OTEGs) is also strongly dependent on the metal-organic interfacial energetics. Without changing the thermoelectric figure of merit (ZT) of polythiophene-based conducting polymers, the generated power of an OTEG can vary by three orders of magnitude simply by tuning the work function of the metal contact to reach above 1000µWcm-2 . The effective Seebeck coefficient (Seff ) of a metal/polymer/metal single leg OTEG includes an interfacial contribution (Vinter /ΔT) in addition to the intrinsic bulk Seebeck coefficient of the polythiophenes, such that Seff =S + Vinter /ΔT varies from 22.7µVK-1 [9.4µVK-1 ] with Al to 50.5µVK-1 [26.3µVK-1 ] with Pt for poly(3,4-ethylenedioxythiophene):p-toluenesulfonate [poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)]. Spectroscopic techniques are used to reveal a redox interfacial reaction affecting locally the doping level of the polymer at the vicinity of the metal-organic interface and conclude that the energetics at the metal-polymer interface provides a new strategy to enhance the performance of OTEGs.

Organic interfacial engineering of gold nanowires for selective glycerol electrooxidation

The selective electrochemical conversion of glycerol into value-added products is a green and sustainable strategy for the biomass utilization. In this work, Au nanowires (Au-NW) modified with polyethyleneimine (PEI) molecule (Au-NW@PEI) is obtained by an up-bottom post-modification approach. Physical characterization, molecular dynamics simulation and density functional theory demonstrate that the loose-packed PEI monolayer firmly and uniformly distribute on the Au-NW surface due to the strong Au-N interaction. Electrochemical experiments and product analysis display that PEI modification significantly enhance the electro-activity of Au-NW for the glycerol electro-oxidation reaction (GEOR) due to the electronic effect. Meanwhile, the steric hindrance and electrostatic effect of PEI layer make the optimizing adsorption of intermediates possible. Therefore, the selectivity of C3 product glyceric acid over Au-NW@PEI is increased by nearly 20%. The work thus indicates that the rational design of metal-organic interface can effectively elevate the electro-activity and selectivity of Au nanostructures, which may have wide application in biomass development.

Hydrogenation of crotonaldehyde over ligand-capped Ir catalysts: Metal-organic interface boosts both activity and selectivity

Hydrogenation of crotonaldehyde over ligand-capped Ir catalysts: Metal-organic interface boosts both activity and selectivity

Tuning the carrier injection barrier of hybrid metal-organic interfaces on rare earth-gold surface compounds.

Magnetic hybrid metal-organic interfaces possess a great potential in areas such as organic spintronics and quantum information processing. However, tuning their carrier injection barriers on-demand is fundamental for the implementation in technological devices. We have prepared hybrid metal-organic interfaces by the adsorption of copper phthalocyanine CuPc on REAu2 surfaces (RE = Gd, Ho and Yb) and studied their growth, electrostatics and electronic structure. CuPc exhibits a long-range commensurability and a vacuum level pinning of the molecular energy levels. We observe a significant effect of the RE valence of the substrate on the carrier injection barrier of the hybrid metal-organic interface. CuPc adsorbed on trivalent RE-based surfaces (HoAu2 and GdAu2) exhibits molecular level energies that may allow injection carriers significantly closer to an ambipolar injection behavior than in the divalent case (YbAu2).

When Molecular Dimerization Induces Magnetic Bi‐Stability at the Metal–Organic Interface

Abstract2D metal–organic frameworks have been recently proposed as a flexible platform for realizing new functional materials including quantum phases. Here, we present a method to create metal‐organic dimer complexes by on‐surface assembly on a metal substrate using low‐temperature scanning tunneling microscopy (STM) and spectroscopy (STS). We demonstrate that a dimer of Mn‐Phthalocyanine (MnPc)2 on a Ag(111) surface can be switched between two stable configurations upon a small conformational change controlled by STM manipulation. By means of density‐functional theory calculations, it is found that the two conformations correspond to an antiferromagnetic (AFM) and a ferromagnetic (FM) state respectively. Directly coordinated Mn atoms of the dimer lead to an AFM‐coupling whereas indirectly coordinated (shifted) Mn atoms lead to a FM‐coupling. Rarely seen in a molecular‐dimers with transition‐metal atoms, the FM‐AFM‐FM transition is thus readily on‐surface accessible. Furthermore, the two configurations of the switch are easily identified by their Kondo states, opening interesting routes in terms of both, writing (FM versus AFM states) and reading. These results pave the experimental route toward dimer‐based materials with complex magnetic structures of potential interest for application in spintronics, logics and computing.

Interface magnetism in Fe/Alq3 bilayer; interface resolved nuclear resonance scattering studies

This work provides a better understanding and behavior of the metal–organic interface magnetism, which plays a crucial role in organic spin-valve devices. Interface magnetism and topological structure of Fe on organic semiconductor film Tris(8-hydroxyquinolinato) aluminium (Alq3) have been studied and compared with Fe film deposited directly on Si (100) substrate. To get information of the diffused Fe layer at the Fe/ Alq3 interface, grazing incident nuclear resonance scattering (GINRS) measurements are made depth selective by introducing a 95% enriched thin 57Fe layer at the interface and producing x-ray standing wave within the layered structure. Compared with Fe growth on Si substrate, where film exhibits a hyperfine field value of ∼ 32 T (Bulk Fe), a thick Fe- Alq3 interface has been found with reduced electron density and hyperfine fields providing evidence of deep penetration of Fe atoms into Alq3 film. Due to the soft nature of Alq3, Fe moments relax in the film plane. At the same time, Fe on Si has resultant ∼ 43° out of plane orientation of Fe moments at the interface due to stressed and rough Fe layer near Si. Evolution of magnetism at Fe-Alq3 Interface is monitored using in-situ magneto-optical Kerr effect (MOKE) during growth of Fe on Alq3 surface and small-angle x-ray scattering (SAXS) measurements. It is found that the Fe atom tries to organize into clusters to minimize their surface/interface energy. The origin of the 24 Å thick magnetic dead layer at the interface is attributed to the small Fe clusters of paramagnetic or superparamagnetic nature. Present work provides an understanding of interfacial magnetism at metal–organic interfaces and the topological study using the GI-NRS technique, which is made depth selective to probe magnetism of the diffused ferromagnetic layer, which is otherwise difficult for lab-based techniques.

Experimental and Computational Studies on Octyl Hydroxamic Acid as an Environmentally Friendly Inhibitor of Cobalt Chemical Mechanical Polishing.

Octyl hydroxamic acid (OHA) was investigated as an inhibitor in H2O2-based alkaline silica dispersions for the polishing of cobalt (Co) films for interconnect applications. A combination of experiments and density functional theory (DFT) was used to investigate the inhibition effect and the mechanism of OHA on the Co surface. On the basis of the experiments, it can be proven that OHA has an inhibition effect on Co, which came from the inhibition of the cathodic reaction. The X-ray photoelectron spectroscopy (XPS) experiments show that the adsorption of OHA weakened the oxidation of the Co surface and protected the Co surface from corrosion. On the basis of the calculations, it can be proven that the OHAketone (ion) is most likely to react with the Co surface, and it can adsorb on the Co surface by Co-O bonds. This study provides important microscopic insights for understanding the corrosion protection of Co interconnect metals and helps to explain the corrosion inhibition mechanism of the organic-metal interface during the CMP process.

Metal-organic framework interface engineering for highly efficient oxygen evolution reaction

Metal-organic frameworks (MOFs) with intrinsically porous structures and well-dispersed metal sites are promising candidates for the oxygen evolution reaction (OER). However, the practical applications of MOFs for OER are significantly constrained due to their poor charge transfer property and insufficient inherent activity. Herein, we utilized caffeic acid as a bridging agent to covalently bond FeNi-MOF with NiMoO4 in order to tune the charge transfer properties for efficient OER. The optimized organic-inorganic heterocatalyst demonstrates superior OER performance with a low overpotential of 256 mV at a current density of 10 mA cm−2 and long-term stability, outperforming the benchmark IrO2 catalyst and single counterparts. Both experimental and theoretical results indicate that electrons can be transferred from FeNi-MOF to NiMoO4 via a caffeic acid bridging agent, which improves not only the electrical conductivity but also the adsorption capacity of OH– intermediates on MOFs. Therefore, the enhanced OER activity of the heterocatalyst is attributed to the synergistic effects of the multi-components. This study paves the way for the rational design of MOFs-based heterostructures towards efficient electrocatalytic oxygen evolution.