Integration of Ultrathin Hafnium Oxide with a Clean van der Waals Interface for Two-Dimensional Sandwich Heterostructure Electronics.

Integrating high-κ dielectrics with a small equivalent oxide thickness (EOT) with two-dimensional (2D) semiconductors for low-power consumption van der Waals (vdW) heterostructure electronics remains challenging in meeting both interface quality and dielectric property requirements. Here, we demonstrate the integration of ultrathin amorphous HfOx sandwiched within vdW heterostructures by the selective thermal oxidation of HfSe2 precursors. The self-cleaning process ensures a high-quality interface with a low interface state density of 1011-1012 cm-2 eV-1. The synthesized HfOx displays excellent dielectric properties with an EOT of ∼1.5 nm, i.e., a high κ of ∼16, an ultralow leakage current of 10-6 A/cm2, and an impressively high breakdown field of 9.5 MV/cm. This facilitates low-power consumption vdW heterostructure MoS2 transistors, demonstrating steep switching with a low subthreshold swing of 61 mV/decade. This one-step integration of high-κ dielectrics into vdW sandwich heterostructures holds immense potential for developing low-power consumption 2D electronics while meeting comprehensive dielectric requirements.

Mie Magnetic Structural Colors from Short Chains of TiO2 Nanospheres.

We demonstrate distinctive structural colors within a small footprint by using a short chain of nanospheres. Rather than using high-index materials like Si (n ∼ 4), which ensure strong modal confinement, TiO2 is employed. TiO2 has an intermediate index (n ∼ 2), promoting stronger modal coupling between the magnetic dipoles of each particle. This approach enables selective engineering of the magnetic response and yields larger spectral changes compared to that of Si. Despite the lower refractive index, the absence of absorption in TiO2 also produces higher scattering intensities than Si. We develop a quasistatic analytical model that describes the dipolar modal coupling in a trimer and use it to reveal distinct magnetic field strengths in the outer or central particle depending on the polarization of incident light. These results suggest pathways to manipulate the magnetic field in chains of particles and create vibrant structural colors with simple configurations.

Mechanism Study of Molecular Trap in All-Organic Polystyrene-Based Dielectric Composite.

It is a huge challenge to explore how charge traps affect the electric breakdown of polymer-based dielectric composites. In this paper, alkane and aromatic molecules with different substituents are investigated according to DFT theoretical method. The combination of strong electron-withdrawing groups and aromatic rings can establish high electron affinity molecules. 4'-Nitro-4-dimethylaminoazobenzene (NAABZ) with a vertical electron affinity of 1.39 eV and a dipole moment of 10.15 D is introduced into polystyrene (PSt) to analyze the influence of charge traps on electric properties. Marcus charge transfer theory is applied to calculate the charge transfer rate between PSt and NAABZ. The nature of charge traps is elaborated from a dynamic perspective. The enhanced breakdown mechanism of polymers-based composites stems from the constraint of carrier mobility caused by the change in transfer rate. But the electrophile nature of high electron affinity filler can decrease the potential barriers at the metal-polymer interface. Simultaneously, the relationship between the electron affinity of fillers and the breakdown strength of polymer-based composites is nonlinear because of the presence of the inversion region. Based on the deep understanding of the molecular trap, this work provides the theoretical calculation for the design and development of high-performance polymer dielectrics.

Significantly Enhanced the Energy Density of Dielectric Composites by Sandwich Structure with Highly Insulating Mica Nanosheets.

Dielectric polymer composites exhibit great application prospects in advanced pulse power systems and electric systems. However, the decline of breakdown strength by loading of single high dielectric constant nanofiller hinders the sustained increase in energy density of the composites. Here, a sandwich-structured nanocomposite prepared with mica nanosheets as the second filler exhibits decoupled modulation of dielectric constant and breakdown strength. The traditional layered clay mineral mica is exfoliated into nanosheets and filled into polyvinylidene difluoride (PVDF), which shows a special depolarization effect in the polymer matrix. In Kelvin probe microscopy characterization and thermally stimulated depolarization current indicates that the mica nanosheets provided space charge traps for the polymer matrix and effectively suppressed the carrier motion. A sandwich structure composite material with mica nanosheets as the central layer has achieved a high energy density of 11.48 J cm-3, 2.4 times higher than the pure PVDF film. This is due to the fact that randomly oriented distribution of nanosheets in a polymer matrix provide better current blocking. This work provides an effective method to improve the energy density of dielectric polymer composites by synergistically introducing insulating nanosheets and high dielectric constant nanofillers.

Achieving Significantly Boosted Dielectric Energy Density of Polymer Film via Introducing a Bumpy Gold/Polymethylsilsesquioxane Granular Blocking Layer.

Polymer dielectrics are the key materials for pulsed energy storage systems, but their low energy densities greatly restrict the applications in integrated electronic devices. Herein, a unique bumpy granular interlayer consisting of gold nanoparticles (Au NPs) and polymethyksesquioxane (PMSQ) microspheres is introduced into a poly(vinylidene fluoride) (PVDF) film, forming trilayered PVDF-Au/PMSQ-PVDF films. Interestingly, the Au/PMSQ interlayer arouses a dielectric enhancement of 47% and an ultrahigh breakdown strength of 704 MV m-1, which reaches 153% of pure PVDF. It is revealed that the greatly enhanced breakdown strength originated from the Coulomb-blockade effect of Au NPs and the excellent insulating properties of PMSQ microspheres with a special molecular-scale organic-inorganic hybrid structure. Benefiting from the concurrently enhanced dielectric and breakdown performances, an outstanding energy density of 22.42 J cm-3 with an efficiency of 67.1%, which reaches 249% of that of the pure PVDF, is achieved. It is further confirmed that this design strategy is also applicable to linear dielectric polymer polyethyleneimine. The composites exhibit an energy density of 8.91 J cm-3 with a high efficiency of ≈95%. This work offers a novel and efficient strategy for concurrently enhancing the dielectric and breakdown performances of polymers toward pulsed power applications.

Multifunctional Applications Enabled by Fluorination of Hexagonal Boron Nitride.

2D materials exhibit exceptional properties as compared to their macroscopic counterparts, with promising applications in nearly every area of science and technology. To unlock further functionality, the chemical functionalization of 2D structures is a powerful technique that enables tunability and new properties within these materials. Here, the successful effort to chemically functionalize hexagonal boron nitride (hBN), a chemically inert 2D ceramic with weak interlayer forces, using a gas-phase fluorination process is exploited. The fluorine functionalization guides interlayer expansion and increased polar surface charges on the hBN sheets resulting in a number of vastly improved applications. Specifically, the F-hBN exhibits enhanced dispersibility and thermal conductivity at higher temperatures by more than 75% offering exceptional performance as a thermofluid additive. Dispersion of low volumes of F-hBN in lubricating oils also offers marked improvements in lubrication and wear resistance for steel tribological contacts decreasing friction by 31% and wear by 71%. Additionally, incorporating numerous negatively charged fluorine atoms on hBN induces a permanent dipole moment, demonstrating its applicability in microelectronic device applications. The findings suggest that anchoring chemical functionalities to hBN moieties improves a variety of properties for h-BN, making it suitable for numerous other applications such as fillers or reinforcement agents and developing high-performance composite structures.

Synthesis of low-k SiONC thin films by plasma-assisted molecular layer deposition with tetraisocyanatesilane and phloroglucinol.

Low-k SiONC thin films with excellent thermal stabilities were deposited using plasma-assisted molecular layer deposition (PA-MLD) with a tetraisocyanatesilane (Si(NCO)4) precursor, N2plasma, and phloroglucinol (C6H3(OH)3). By adjusting the order of the N2plasma exposure steps within the PA-MLD process, we successfully developed a deposition technique that allows accurate control of thickness at the Ångström level via self-limiting reactions. The thicknesses of the thin films were measured through spectroscopic ellipsometry (SE). By tuning the N2plasma power, we facilitated the formation of -NH2sites for phloroglucinol adsorption, achieving a growth per cycle of 0.18 Å cycle-1with 300 W of N2plasma power. Consequently, the thickness of the films increased linearly with each additional cycle. Moreover, the organic linkers within the film formed stable bonds through surface reactions, resulting in a negligible decrease in thickness of approximately -11% even upon exposure to a high annealing temperature of 600 °C. This observation was confirmed by SE, distinguishing the as-prepared film from previously reported low-k films that fail to maintain their thickness under similar conditions. X-ray photoelectron spectroscopy (XPS) and current-voltage (I-V) and capacitance-voltage (C-V) measurement were conducted to evaluate the composition, insulating properties, and dielectric constant according to the deposition and annealing conditions. XPS results revealed that as the plasma power increased from 200 to 300 W, the C/Si ratio increased from 0.37 to 0.67, decreasing the dielectric constant from 3.46 to 3.12. Furthermore, there was no significant difference in the composition before and after annealing, and the hysteresis decreased from 0.58 to 0.19 V owing to defect healing, while maintaining the leakage current density, breakdown field, and dielectric constant. The low dielectric constant, accurate thickness control, and excellent thermal stability of this MLD SiONC thin film enable its application as an interlayer dielectric in back-end-of-line process.

Water-Soluble Reversible Photo-Cross-Linking Polymer Dielectrics.

Effective recycling of mixed materials requires the separation of the different components without the need for toxic solvents. One approach involves utilizing a water-soluble coating with reversible photo-cross-linkers, making it robust until end of life where it can then be dissolved in water after de-cross-linking. Here, a novel coumarin methacrylate monomer and its nitroxide-mediated copolymerization to create poly((methacrylic acid)-co-(styrene sulfonate)-co-(coumarin methacrylate)) for water-soluble thin films are reported. Under exposure to light, the coumarin functional groups produce reversible [2+2] cycloadditions which cross-link the resulting polymer films, making them no longer water soluble. Characterization of reversible cross-linking behavior is reported through changes in contact angle and in situ rheological characterization. The resulting polymers are successfully integrated into metal-insulator-metal capacitors, demonstrating the potential use for water-soluble reversible photo-cross-linkable dielectric materials for organic electronics.

Constructing Novel High Dielectric Constant Polyimides Containing Dipolar Pendant Groups with Enhanced Orientational Polarization.

Polymer dielectrics with high dielectric constant are urgently demanded for potential electrical and pulsed power applications. The design of polymers with side chains containing dipolar groups is considered an effective method for preparing materials with a high dielectric constant and low loss. This study synthesizes and comprehensively compare the dielectric properties of novel polyimides with side chains containing urea (BU-PI), carbamate (BC-PI), and sulfonyl (BS-PI) functional groups. The novel polyimides exhibit relatively high dielectric constant and low dielectric loss values due to the enhanced orientational polarization and suppressed dipole-dipole interactions of dipolar groups. In particular, BU-PI containing urea pendant groups presents the highest dielectric constant of 6.14 and reasonably low dielectric loss value of 0.0097. The strong γ transitions with low activation energies derived from dielectric spectroscopy measurements have been further evaluated to demonstrate the enhanced free rotational motion of urea pendant dipoles. In energy storage applications, BU-PI achieves a discharged energy density of 6.92 J cm-3 and a charge-discharge efficiency above 83% at 500 MV m-1. This study demonstrates that urea group, as dipolar pendant group, can provide polymers with better dielectric properties than the most commonly used sulfonyl groups.

Interfacial Charge Transport Enhancement of Liquid-Crystalline Polymer Transistors Enabled by Ionic Polyurethane Dielectric.

In organic field-effect transistors (OFETs) using disordered organic semiconductors, interface traps that hinder efficient charge transport, stability, and device performance are inevitable. Benchmark poly(9,9-dioctylfuorene-co-bithiophene) (F8T2) liquid-crystalline polymer semiconductor has been extensively investigated for organic electronic devices due to its promising combination of charge transport and light emission properties. This study demonstrates that high-capacitance single-layered ionic polyurethane (PU) dielectrics enable enhanced charge transport in F8T2 OFETs. The ionic PU dielectrics are composed of a mild blending of PU ionogel and PU solution, thereby forming a solid-state film with robust interfacial characteristics with semiconductor layer and gate electrode in OFETs and measuring high capacitance values above 10 µF cm-2 owing to the combined dipole polarization and electric double layer formation. The optimized fabricated ionic PU-gated OFETs exhibit a low-voltage operation at -3 V with a remarkable hole mobility of over 5 cm2 V-1 s-1 (average = 2.50 ± 1.18 cm2 V-1 s-1), which is the highest mobility achieved so far for liquid-crystalline F8T2 OFETs. This device also provides excellent bias-stable characteristics in ambient air, exhibiting a negligible threshold voltage shift of -0.03 V in the transfer curves after extended bias stress, with a reduced trap density.

A Green High-k Dielectric from Modified Carboxymethyl Cellulose-Based with Dextrin.

Many crucial components inside electronic devices are made from non-renewable, non-biodegradable, and potentially toxic materials, leading to environmental damage. Finding alternative green dielectric materials is mandatory to align with global sustainable goals. Carboxymethyl cellulose (CMC) is a bio-polymer derived from cellulose and has outstanding properties. Herein, citric acid, dextrin, and CMC based hydrogels are prepared, which are biocompatible and biodegradable and exhibit rubber-like mechanical properties, with Young modulus values of 0.89 MPa. Hence, thin film CMC-based hydrogel is explored as a suitable green high-k dielectric candidate for operation at low voltages, demonstrating a high dielectric constant of up to 78. These fabricated transistors reveal stable high capacitance (2090 nF cm-2) for ≈±3 V operation. Using a polyelectrolyte-type approach and poly-(2-vinyl anthracene) (PVAn) surface modification, this study demonstrates a thin dielectric layer (d ≈30 nm) with a small voltage threshold (Vth ≈-0.8 V), moderate transconductance (gm ≈65 nS), and high ON-OFF ratio (≈105). Furthermore, the dielectric layer exhibits stable performance under bias stress of ± 3.5 V and 100 cycles of switching tests. The modified CMC-based hydrogel demonstrates desirable performance as a green dielectric for low-voltage operation, further highlighting its biocompatibility.

Optimizing Capacitive Pressure Sensor Geometry: A Design of Experiments Approach with a Computer-Generated Model.

This study presents a comprehensive investigation into the design and optimization of capacitive pressure sensors (CPSs) for their integration into capacitive touch buttons in electronic applications. Using the Finite Element Method (FEM), various geometries of dielectric layers were meticulously modeled and analyzed for their capacitive and sensitivity parameters. The flexible elastomer polydimethylsiloxane (PDMS) is used as a diaphragm, and polyvinylidene fluoride (PVDF) is a flexible material that acts as a dielectric medium. The Design of Experiment (DoE) techniques, aided by statistical analysis, were employed to identify the optimal geometric shapes of the CPS model. From the prediction using the DoE approach, it is observed that the cylindrical-shaped dielectric medium has better sensitivity. Using this optimal configuration, the CPS was further examined across a range of dielectric layer thicknesses to determine the capacitance, stored electrical energy, displacement, and stress levels at uniform pressures ranging from 0 to 200 kPa. Employing a 0.1 mm dielectric layer thickness yields heightened sensitivity and capacitance values, which is consistent with theoretical efforts. At a pressure of 200 kPa, the sensor achieves a maximum capacitance of 33.3 pF, with a total stored electric energy of 15.9 × 10-12 J and 0.468 pF/Pa of sensitivity for 0.1 dielectric thickness. These findings underscore the efficacy of the proposed CPS model for integration into capacitive touch buttons in electronic devices and e-skin applications, thereby offering promising advancements in sensor technology.

Ultrahigh Energy Storage in 2D High-κ Perovskites.

Dielectric capacitors have greater power densities than batteries, and, unlike batteries, they do not utilize chemical reactions during cycling. Thus, they can become ideal, safe energy storage devices. However, dielectric capacitors yield rather low energy densities compared with other energy storage devices such as batteries and supercapacitors. Here, we present a rational approach for designing ultrahigh energy storage capacitors using two-dimensional (2D) high-κ dielectric perovskites (Ca2Nam-3NbmO3m+1; m = 3-6). Individual Ca2Nam-3NbmO3m+1 nanosheets exhibit an ultrahigh dielectric strength (638-1195 MV m-1) even in the monolayer form, which exceeds those of conventional dielectric materials. Multilayer stacked nanosheet capacitors exhibit ultrahigh energy densities (174-272 J cm-3), high efficiencies (>90%), excellent reliability (>107 cycles), and temperature stability (-50-300 °C); the maximum energy density is much higher than those of conventional dielectric materials and even comparable to those of lithium-ion batteries. Enhancing the energy density may make dielectric capacitors more competitive with batteries.

Anisotropic Semicrystalline Homopolymer Dielectrics for High-Temperature Capacitive Energy Storage.

High-temperature dielectric polymers are in high demand for powering applications in extreme environments. Here, we have developed high-temperature homopolymer dielectrics with anisotropy by leveraging the hierarchical structure in semicrystalline polymers. The lamellae have been aligned parallel to the surface in the dielectric films. This structural arrangement resembles the horizontal alignment of nanosheet fillers in polymer nanocomposites and nanosheet-like lamellae in block copolymers, which has been proven to provide the optimal topological structure for electrical energy storage. The unique ordering of lamellae in our dielectric films endue a significantly increased breakdown strength and a reduced leakage current compared to amorphous films. This novel approach of enhancing the capacitive energy storage properties by controlled orientation of lamellae in homopolymer offers a new perspective for the design of high-temperature polymer dielectrics.

Enabling Polymer Single Crystals to Be High-Performance Dielectric.

Semicrystalline polymer dielectrics (SPDs) are highly sought-after state-of-the-art dielectric materials. As the disorder in SPDs degrades their electrical properties, homogeneously ordered SPDs are desired. However, complex crystallization behaviors of polymers make such homogeneity elusive. Polymer lamellar single crystals (PLSCs), the most regularly-ordered form of SPDs possible under mild crystallizing conditions, are ideal platforms for understanding and developing high-performance dielectric materials. Here, a typical and widely used SPD, polyethylene (PE) is selected as the model material. We successfully obtained, large, uniform, and high-quality PE PLSCs and devised a non-destructive strategy to construct PE PLSC-based vertical capacitors. These nanometer-thick capacitors exhibit exceptional dielectric properties, with a high breakdown strength of 6.95 MV/cm and a low dielectric constant of 2.14±0.07, that outperform the properties of any existing neat PE. This work provides novel insights into exploring the performance possibility of ordered SPDs and reveals the PLSCs as potential high-performance dielectric materials.

On the Working Mechanisms of Molecules-Based Van der Waals Dielectrics.

Sb2 O3 molecules offer unprecedented opportunities for the integration of a van der Waals (vdW) dielectric and a 2D vdW semiconductor. However, the working mechanisms underlying molecules-based vdW dielectrics remain unclear. Here, the working mechanisms of Sb2 O3 and two Sb2 O3 -like molecules (As2 O3 and Bi2 O3 ) as dielectrics are systematically investigated by combining first-principles calculations and gate leakage current theories. It is revealed that molecules-based vdW dielectrics have a considerable advantage over conventional dielectric materials: defects hardly affect their insulating properties. This shows that it is unnecessary to synthesize high-quality crystals in practical applications, which has been a long-standing challenge for conventional dielectric materials. Further analysis reveals that a large thermionic-emission current renders Sb2 O3 difficult to simultaneously satisfy the requirements of dielectric layers in p-MOS and n-MOS, which hinders its application for complementary metal-oxide-semiconductor (CMOS) devices. Remarkably, it is found that As2 O3 can serve as a dielectric for both p-MOS and n-MOS. This work not only lays a theoretical foundation for the application of molecules-based vdW dielectrics, but also offers an unprecedentedly competitive dielectric (i.e., As2 O3 ) for 2D vdW semiconductors-based CMOS devices, thus having profound implications for future semiconductor industry.

Interfacial Interaction Enables Enhanced Mobility in Hybrid Perovskite-Conjugated Polymer Transistors with High-k Fluorinated Polymer Dielectrics.

The charge carrier mobility of organic field-effect transistors (OFETs) has been remarkably improved through several engineering approaches and techniques by targeting pivotal parts. Herein, an ultrathin perovskite channel layer that boosts the field-effect mobility of conjugated polymer OFETs by forming perovskite-conjugated polymer hybrid semiconducting channel is introduced. The optimized lead-iodide-based perovskite-conjugated polymer hybrid channel transistors show enhanced hole mobility of over 4 cm2  V-1  s-1 (average = 2.10 cm2  V-1  s-1 ) with high reproducibility using a benchmark poly(3-hexylthiophene) (P3HT) polymer and employing high-k fluorinated polymer dielectrics. A significant hole carrier mobility enhancement of ≈200-400% in benzo[1,2-b:4,5:b']dithiophene (BDT)-based conjugated polymers is also demonstrated by exploring certain interactive groups with perovskite. This significant enhancement in the transistor performance is attributed to the increased charge carrier density in the hybrid semiconducting channel and the perovskite-polymer interactions. The findings of this paper demonstrate an exceptional engineering approach for carrier mobility enhancement in hybrid perovskite-conjugated-polymer-based electronic devices.

Alternating [1.1.1]Propellane-(Meth)Acrylate Copolymers: A New Class of Dielectrics with High Energy Density for Film Capacitors.

Polymer dielectrics with high energy density are of urgent demand in electric and electronic devices, but the tradeoff between dielectric constant and breakdown strength is still unsolved. Herein, the synthesis and molar mass control of three alternating [1.1.1]propellane-(meth)acrylate copolymers, denoted as P-MA, P-MMA, and P-EA, respectively, are reported. These copolymers exhibit high thermal stability and are semi-crystalline with varied glass transition temperatures and melting temperatures. The rigid bicyclo[1.1.1]pentane units in the polymer backbone promote the orientational polarization of the polar ester groups, thus enhancing the dielectric constants of these polymers, which are 4.50 for P-EA, 4.55 for P-MA, and 5.11 for P-MMA at 10 Hz and room temperature, respectively. Moreover, the high breakdown strength is ensured by the non-conjugated nature of bicyclo[1.1.1]pentane unit. As a result, these copolymers show extraordinary energy storage performance; P-MA exhibits a discharge energy density of 9.73 J cm-3 at 750 MV m-1 and ambient temperature. This work provides a new type of promising candidates as polymer dielectrics for film capacitors, and offers an efficient strategy to improve the dielectric and energy storage properties by introducing rigid non-conjugated bicyclo[1.1.1]pentane unit into the polymer backbone.

Highly Flexible Dielectric Films from Solution Processable Covalent Organic Frameworks.

Covalent organic frameworks (COFs) are known to be a promising class of materials for a wide range of applications, yet their poor solution processability limits their utility in many areas. Here we report a pore engineering method using hydrophilic side chains to improve the processability of hydrazone and ß-ketoenamine-linked COFs and the production of flexible, crystalline films. Mechanical measurements of the free-standing COF films of COF-PEO-3 (hydrazone-linked) and TFP-PEO-3 (ß-ketoenamine-linked), revealed a Young's modulus of 391.7 MPa and 1034.7 MPa, respectively. The solubility and excellent mechanical properties enabled the use of these COFs in dielectric devices. Specifically, the TFP-PEO-3 film-based dielectric capacitors display simultaneously high dielectric constant and breakdown strength, resulting in a discharged energy density of 11.22 J cm-3 . This work offers a general approach for producing solution processable COFs and mechanically flexible COF-based films, which hold great potential for use in energy storage and flexible electronics applications.

Phase-Controlled Synthesis and Quasi-Static Dielectric Resonances in Silver Iron Sulfide (AgFeS2 ) Nanocrystals.

Ternary metal-chalcogenide semiconductor nanocrystals are an attractive class of materials due to their tunable optoelectronic properties that result from a wide range of compositional flexibility and structural diversity. Here, the phase-controlled synthesis of colloidal silver iron sulfide (AgFeS2 ) nanocrystals is reported and their resonant light-matter interactions are investigated. The product composition can be shifted selectively from tetragonal to orthorhombic by simply adjusting the coordinating ligand concentration, while keeping the other reaction parameters unchanged. The results show that excess ligands impact precursor reactivity, and consequently the nanocrystal growth rate, thus deterministically dictating the resulting crystal structure. Moreover, it is demonstrated that the strong ultraviolet-visible extinction peak exhibited by AgFeS2 nanocrystals is a consequence of a quasi-static dielectric resonance (DR), analogous to the optical response observed in CuFeS2 nanocrystals. Spectroscopic studies and computational calculations confirm that a negative permittivity at ultraviolet/visible frequencies arises due to the electronic structure of these intermediate-band (IB) semiconductor nanocrystals, resulting in a DR consisting of resonant valence-band-to-intermediate-band excitations, as opposed to the well-known localized surface plasmon resonance response typically observed in metallic nanostructures. Overall, these results expand the current library of an underexplored class of IB semiconductors with unique optical properties, and also enrich the understanding of DRs in ternary metal-iron-sulfide nanomaterials.