Highly Conductive Nanocomposites with Three‐Dimensional,Compactly Interconnected Graphene Networks via a Self‐Assembly Process

Polymer‐based materials with high electrical conductivity are of considerable interest because of their wide range of applications. The construction of a 3D, compactly interconnected graphene network can offer a huge increase in the electrical conductivity of polymer composites. However, it is still a great challenge to achieve desirable 3D architectures in the polymer matrix. Here, highly conductive polymer nanocomposites with 3D compactly interconnected graphene networks are obtained using a self‐assembly process. Polystyrene (PS) and ethylene vinyl acetate (EVA) are used as polymer matrixes. The obtained PS composite film with 4.8 vol% graphene shows a high electrical conductivity of 1083.3 S/m, which is superior to that of the graphene composite prepared by a solvent mixing method. The electrical conductivity of the composites is closely related to the compact contact between graphene sheets in the 3D structures and the high reduction level of graphene sheets. The obtained EVA composite films with the 3D graphene structure not only show high electrical conductivity but also exhibit high flexibility. Importantly, the method to fabricate 3D graphene structures in polymer matrix is facile, green, low‐cost, and scalable, providing a universal route for the rational design and engineering of highly conductive polymer composites.     

Soft and Self-Adhesive Thermal Interface Materials Based on Vertically Aligned,Covalently Bonded Graphene Nanowalls for Efficient Microelectronic Cooling

Urged by the increasing power and packing densities of integrated circuits and electronic devices, efficient dissipation of excess heat from hot spot to heat sink through thermal interface materials (TIMs) is a growing demand to maintain system reliability and performance. In recent years, graphene-based TIMs received considerable interest due to the ultrahigh intrinsic thermal conductivity of graphene. However, the cooling efficiency of such TIMs is still limited by some technical difficulties, such as production-induced defects of graphene, poor alignment of graphene in the matrix, and strong phonon scattering at graphene/graphene or graphene/matrix interfaces. In this study, a 120  µ m-thick freestanding film composed of vertically aligned, covalently bonded graphene nanowalls (GNWs) is grown by mesoplasma chemical vapor deposition. After filling GNWs with silicone, the fabricated adhesive TIMs exhibit a high through-plane thermal conductivity of 20.4 W m⁻¹ K⁻¹ at a low graphene loading of 5.6 wt%. In the TIM performance test, the cooling efficiency of GNW-based TIMs is ≈ 1.5 times higher than that of state-of-the-art commercial TIMs. The TIMs achieve the desired balance between high through-plane thermal conductivity and small bond line thickness, providing superior cooling performance for suppressing the degradation of luminous properties of high-power light-emitting diode chips.     

Metal‐Free Growth of Nanographene on Silicon Oxides for Transparent Conducting Applications

Conventional methods to prepare large‐area graphene for transparent conducting electrodes involve the wet etching of the metal catalyst and the transfer of the graphene film, which can degrade the film through the creation of wrinkles, cracks, or tears. The resulting films may also be obscured by residual metal impurities and polymer contaminants. Here, it is shown that direct growth of large‐area flat nanographene films on silica can be achieved at low temperature (400 °C) by chemical vapor deposition without the use of metal catalysts. Raman spectroscopy and TEM confirm the formation of a hexagonal atomic network of sp²‐bonded carbon with a domain size of about 3–5 nm. Further spectroscopic analysis reveals the formation of SiC between the nanographene and SiO₂, indicating that SiC acts as a catalyst. The optical transmittance of the graphene films is comparable with transferred CVD graphene grown on Cu foils. Despite the fact that the electrical conductivity is an order of magnitude lower than CVD graphene grown on metals, the sheet resistance remains 1–2 orders of magnitude better than well‐reduced graphene oxides.     

Nanosized Glass Frit as an Adhesion Promoter for Ink‐Jet Printed Conductive Patterns on Glass Substrates Annealed at High Temperatures

Ink‐jet printed metal nanoparticle films have been shown to anneal at high temperatures (above 500 °C) to highly conductive metal films on glass or ceramic substrates, but they suffer from cracking and inadequate substrate adhesion. Here, we report printable conductive materials, with added nanosized glass frit that can be annealed at 500 °C to form a crack‐free dense microstructure that adheres well to glass substrates. This overcomes the previous challenges while still retaining the desired high film conductivity. Controlling the particle characteristics and dispersion behavior plays an important role in successfully incorporating the glass frit into the conductive inks.     

Integration of an Axially Continuous Graphene with Functional Metals for High-Temperature Electrical Conductors

Demands for effective high-temperature electrical conductors continue to increase with the rapid adoption of electric vehicles. However, the use of conventional copper-based conductors is limited to relatively low temperatures due to their poor oxidation resistance and microstructural instability. Here, a highly conductive and thermally stable nickel-graphene-copper (NiGCu) wire that combines the advantages of graphene and its metallic components is developed. The NiGCu wire consists of a conductive copper core, an oxidation-resistant nickel shell, and axially continuous graphene embedded between them. The experiments on 10–80 µm diameter NiGCu wires demonstrate substantial enhancements in electrical properties and thermal stability across a variety of metrics. For instance, the smallest NiGCu wires have a 61.2% higher current density limit, 307.6% higher conductivity, and an order of magnitude smaller change in resistivity compared to conventional Ni-coated Cu counterparts after annealing at 650 °C. By performing both innovative experiments and simulations using different sizes of NiGCu wires, the diffusion coefficients of metals are quantified, for the first time to the best knowledge, through continuous graphene. These results indicate that the dramatic improvement in thermo-electrical properties is enabled by the embedded graphene layer which reduces Ni Cu interdiffusion by ≈10⁴ times at 550 °C and 650 °C.     

Large-Scale Synthesis of Graphene Films by Joule-Heating-Induced Chemical Vapor Deposition

We report large-area synthesis of few-layer graphene films by chemical vapor deposition (CVD) in a cold-wall reactor. The key feature of this method is that the catalytic metal layers on the SiO₂/Si substrates are self-heated to high growth temperature (900°C to 1000°C) by high-current Joule heating. Synthesis of high-quality graphene films, whose structural and electrical characteristics are comparable to those grown by hot-wall CVD systems, was confirmed by transmission electron microscopy images, Raman spectra, and current–voltage analysis. Optical transmittance spectra of the graphene films allowed us to estimate the number of graphene layers, which revealed that high-temperature exposure of Ni thin layers to a carbon precursor (CH₄) was critical in determining the number of graphene layers. In particular, exposure to CH₄ for 20 s produces very thin graphene films with an optical transmittance of 93%, corresponding to an average layer number of three and a sheet resistance of ~600 Ω/square.     

Stress relaxation and thermal evolution of film properties in amorphous carbon

A model for the stress relaxation of amorphous carbon films containing high concentrations of fourfold coordinated carbon is presented. The onset of stress relaxation in these materials occurs following thermal annealing at temperatures as low as 100°C, and near full stress relaxation occurs after annealing at 600°C. The stress relaxation is modeled by a series of first order chemical reactions which lead to a conversion of some fourfold coordinated carbon atoms into threefold coordinated carbon atoms. The distribution of activation energies for this process is derived from the experimental measurements of stress relaxation and is found to range from 1 eV to over 3 eV. Permanent increases in the electrical conductivity of the carbon films are also found following thermal annealing. The electrical conductivity is found to be exponentially proportional to the number of additional threefold atoms which are created upon annealing, with the increase in threefold atom concentration being deduced from the stress relaxation model. This indicates that the increase in electrical conductivity and the stress relaxation originate from the same fourfold to threefold conversion process and that electrical transport through these films is dominated by a hopping conduction process.     

Impact of Morphology on Printed Contact Performance in Carbon Nanotube Thin‐Film Transistors

Silver nanoparticles (NPs) are the most widely used conductive material throughout the printed electronics space due to their high conductivity and low cost. However, when interfacing with other prominent printed materials, such as semiconducting carbon nanotubes (CNTs) in thin‐film transistors (TFTs), silver is suboptimal when compared to more expensive or less conductive materials. Consequently, there would be significant value to improving the interface of printed silver to CNT films. In this work, the impact of nanostructure morphology on the electrical properties of printed silver and nanotube junctions in CNT‐TFTs is investigated. Three distinct silver morphologies (NPs, nanoflakes – NFs, and nanowires – NWs) are explored with top‐ and bottom‐contact configurations for each. The NF morphology in a top‐contact configuration is found to yield the best electrical interface to CNTs, resulting in an average contact resistance of 1.2 MΩ ? µm. Beyond electrical performance, several trade‐offs in morphology selection are revealed, including print resolution and process temperature. While NF inks produce the best interfaces, NP inks produce the smallest features, and NW inks are compatible with low processing temperatures (<80 °C). These results outline the trade‐offs between silver contact morphologies in CNT‐TFTs and show that contact morphology selection can be tailored for specific applications.     

Electrical conductivity and photoluminescence of diamond films grown by downstream microwave plasma CVD

Electrical conductivity measurements and photoluminescence (PL) were used to study the effects that sample distance from the plasma during growth has on the carrier transport properties of undoped CVD diamond. The films were grown by downstream microwave plasma chemical vapor deposition at distances from 0.5 to 2.0 cm from the edge of plasma glow. Electrical conductivity measurements were performed between room temperature and 1000° C and then complimented with Raman spectroscopy and PL studies in an attempt to gain a better understanding of the CVD growth process and the resulting electrical and optical properties of the diamond films. Room temperature electrical conductivity was found to vary by over 5 orders of magnitude with increasing growth distance from the plasma, while only moderate changes were observed in the luminescence spectra.     

Maintaining Cytocompatibility of Biopolymers Through a Graphene Layer for Electrical Stimulation of Nerve Cells

Here, the utility of large‐area graphene as a flexible, biocompatible electrode to stimulate cell growth is demonstrated. Chemical vapor deposition allows the production of highly crystalline, single, double, or few‐layered graphene on copper substrates. The subsequent transfer to a biopolymer support, such as polylactic acid (PLA) or polylactic‐co‐glycolic acid (PLGA) copolymers, provides a unique electrode structure retaining the flexibility and surface properties of the underlying materials with a conductive graphene layer sufficient to enable electrical communication with excitable cells. The growth and compatibility of PC‐12 cells on these graphene‐biopolymer (GPB) electrodes is influenced more by the underlying polymer than the presence of graphene, demonstrating that the characteristics influencing biocompatibility have been retained after graphene modification. Differentiation of these cells into neural phenotypes is enhanced using electrical stimulation through the graphene conductive layer, confirming that the conductivity of graphene is sufficient to electrically communicate with cells grown on the surface. The process described herein demonstrates that non‐conducting, flexible biopolymer surfaces can be easily coated with graphene without changing the biocompatibility of the materials. This could be used to create electrodes from non‐conducting materials with optimized cell compatibility with graphene providing electrical properties suitable for stimulation of cells without greatly changing the surface properties.     

Interconnected Graphene Networks with Uniform Geometry for Flexible Conductors

Controllable construction of graphene into specific architectures at macroscopic scales is crucial for practical applications of graphene. An approach of macroscopic and conductive interconnected graphene networks with controllable patterns, pore, and skeleton sizes via chemical vapor deposition is reported here. Specifically, the pore and skeleton sizes of 3D controllable graphene (3D‐CG) architectures can be tuned from 10 to 50 μm and the orientation angles of building blocks can be designed as 45° and 90°. The electrical conductivity and density of 3D‐CGs are measured at 60–80 S cm^?1 and ≈3.6 mg cm^?3, respectively. The properties of 3D‐CGs as flexible conductors and supercapacitor electrodes are reported, to explore the potential application in wearable devices and energy store.     

Integration of Stiff Graphene and Tough Silk for the Design and Fabrication of Versatile Electronic Materials

The production of structural and functional materials with enhanced mechanical properties through the integration of soft and hard components is a common approach to Nature's material design. However, directly mimicking these optimized design routes in the lab for practical applications remains challenging. For example, graphene and silk are two materials with complementary mechanical properties that feature ultrahigh stiffness and toughness, respectively. Yet, no simple and controllable approach is developed to homogeneously integrate these two components into functional composites, mainly due to the hydrophobicity and chemical inertness of graphene. In this study, well‐dispersed and highly stable graphene/silk fibroin (SF) suspension systems are developed, which are suitable for processing to fabricate polymorphic materials, such as films, fibers, and coatings. The obtained graphene/SF nanocomposites maintain the electronic advantages of graphene, and they also allow tailorable mechanical performance to form including ultrahigh stretchable (with a strain to failure to 611 ± 85%), or high strength (339 MPa) and high stiffness (7.4 GPa) material systems. More remarkably, the electrical resistances of these graphene/SF materials are sensitive to material deformation, body movement, as well as humidity and chemical environmental changes. These unique features promise their utility as wearable sensors, smart textiles, intelligent skins, and human–machine interfaces.     

Novel Cu Nanowires/Graphene as the Back Contact for CdTe Solar Cells

Cu‐nanowire‐doped graphene (Cu NWs/graphene) is successfully incorporated as the back contact in thin‐film CdTe solar cells. 1D, single‐crystal Cu nanowires (NWs) are prepared by a hydrothermal method at 160 °C and 3D, highly crystalline graphene is obtained by ambient‐pressure CVD at 1000 °C. The Cu NWs/graphene back contact is obtained from fully mixing the Cu nanowires and graphene with poly(vinylidene fluoride) (PVDF) and N‐methyl pyrrolidinone (NMP), and then annealing at 185 °C for solidification. The back contact possesses a high electrical conductivity of 16.7 S cm^?1 and a carrier mobility of 16.2 cm² V^?1 s^?1. The efficiency of solar cells with Cu NWs/graphene achieved is up to 12.1%, higher than that of cells with traditional back contacts using Cu‐particle‐doped graphite (10.5%) or Cu thin films (9.1%). This indicates that the Cu NWs/graphene back contact improves the hole collection ability of CdTe cells due to the percolating network, with the super‐high aspect ratio of the Cu nanowires offering enormous electrical transport routes to connect the individual graphene sheets. The cells with Cu NWs/graphene also exhibit an excellent thermal stability, because they can supply an active Cu diffusion source to form an stable intermediate layer of CuTe between the CdTe layer and the back contact.     

Fabrication of flexible conductive graphene/Ag/Al-doped zinc oxide multilayer films for application in flexible organic light-emitting diodes

Graphene/Ag/Al-doped zinc oxide (AZO) multilayer films were fabricated by using chemical vapor deposition and magnetron sputtering methods. The electrical and optical properties of the transparent conductive graphene/Ag/AZO films were investigated. The graphene/Ag/AZO film can maintain high conductivity and transmittance without obvious degradation during bending test. A green flexible organic light emitting diode with a structure of graphene/Ag/AZO/N,N-diphenyl-N,N-bis(1-napthyl)-1,1-biphenyl-4,4-diamine/tris(8-hydroxyquinoline) aluminum(III)/lithium fluoride/Al exhibited a stable green emission and light-emitting efficiency during the cycle bending test. The multilayer films hold promise for application in flexible optoelectronic devices.     

Microsphere Structure Composite Phase Change Material with Anti-Leakage,Self-Sensing,and Photothermal Conversion Properties for Thermal Energy Harvesting and Multi-Functional Sensor

The low thermal conductivity and liquid melt leakage of phase change materials are long-standing bottlenecks for efficient and safe thermal energy harvesting. Although high thermal conductivity materials combined with phase change materials can address the thermal conductivity problem, ensuring no leakage and no reduction in latent heat in the meantime remains challenging. Here, a strategy to synthesize microsphere-structured phase change composites by encapsulating phase change materials in graphene via emulsion polymerization (no additional emulsifier) and chemical reduction is proposed. Multiple graphene sheets are connected to construct an efficient thermally conductive (increase 58.5 times in thermal conductivity) and electrically conductive network. The composite microspheres exhibit no leakage (<0.5%) and superior phase transition behavior after 1500 heating-cooling cycles, and sense external environments such as temperature changes and water drops falling, allowing them to be engineered into devices for temperature monitoring. In addition, it converts electrical energy into thermal energy to achieve rapid temperature increases. The incorporation of polydopamine improves the photothermal efficiency of the phase change microspheres and senses light irradiation, offering a promising route to extend the single source of thermal energy. This method provides new insight into the photothermal integration and intelligent sensing of phase-change materials.     

Highly Conductive Porous Graphene/Ceramic Composites for Heat Transfer and Thermal Energy Storage

A novel architecture of 3D graphene growth on porous Al₂O₃ ceramics is proposed for thermal management using ambient pressure chemical vapor deposition. The formation mechanism of graphene is attributed to the carbothermic reduction occurring at the Al₂O₃ surface to initialize the nucleation and growth of graphene. The graphene films are coated on insulating anodic aluminum oxide (AAO) templates and porous Al₂O₃ ceramic substrates. The graphene coated AAO possesses one‐dimensional isolated graphene tubes, which can act as the media for directional thermal transport. The graphene/Al₂O₃ composite (G‐Al₂O₃) contains an interconnected macroporous graphene framework with an extremely low sheet electrical resistance down to 0.11 Ω sq^?1 and thermal conductivity with 8.28 W m^?1 K^?1. The G‐Al₂O₃ provides enormous conductive pathways for electronic and heat transfer, suitable for application as heat sinks. Such a porous composite is also attractive as a highly thermally conductive reservoir to hold phase change materials (stearic acid) for thermal energy storage. This work displays the great potential of CVD direct growth of graphene on dielectric porous substrates for thermal conduction and electronic applications.     

Hierarchical Domain Structure and Extremely Large Wall Current in Epitaxial BiFeO3 Thin Films

Erasable electrical conductive domain walls in an insulating ferroelectric matrix provide novel functionalities for applications in logic and memory devices. The crux of such success requires sufficiently high wall currents to drive high‐speed and high‐power nanodevices. This work provides an appealing strategy to increase the current by two orders of magnitude through the careful selection of current flowing paths along the charged walls. The dense walls come into form through the hierarchical evolution of the 71°, 109°, and 180° domains of epitaxial BiFeO₃ films in a planar‐geometry ferroelectric resistance‐switching memory cell. The engineered films grown on SrTiO₃ and GdScO₃ substrates allow the observation of detailed local configurations and the evolution of the different domain types using vector piezo‐force microscopy. The higher local electrical conductivity near the charged domain walls is identified by conductive atomic‐force microscopy. It is shown that 180° domain reversal proceeds by three‐step 71° rotations of the pristine domains. Surprisingly, a maximum current of ≈300 nA is observed for current paths along charge‐uncompensated head‐to‐head hierarchical domain walls connecting the two electrodes on the film surface. Furthermore, the achievable current level can be conveniently controlled by varying the relative directions of the initial polarization and the applied field.     

Improving Graphene Diffusion Barriers via Stacking Multiple Layers and Grain Size Engineering

It is shown that the performance of graphene diffusion barriers can be enhanced by stacking multiple layers of graphene and increasing grain size. The focus is on large‐area barriers of graphene grown by chemical vapor deposition (CVD) in the context of passivating an underlying Cu substrate from oxidation in air at 200 °C and use imaging Raman spectroscopy as a tool to temporally and spatially map the barrier performance and to guide barrier design. At 200 °C in air, Cu oxidation proceeds in multiple regimes: first slowly via transport through atomic‐scale grain boundary defects inherent to CVD‐graphene and then more rapidly as the graphene itself degrades and new defects are formed. In the initial regime, the graphene passivates better than previously reported. Whereas oxidation through single sheets primarily occurs through grain boundaries, oxidation through multiple sheets is spatially confined to their intersection. Performance further increases with grain‐size. The degradation of the graphene itself at 200 °C ultimately limits high temperature but suggests superior low temperature barrier performance. This study is expected to improve the understanding of mass transport through CVD‐graphene materials and lead to improved large area graphene materials for barrier applications.     

Humidity‐Driven Mechanical and Electrical Response of Graphene/Cloisite Hybrid Films

Humidity‐driven and electrically responsive graphene/cloisite hybrid films are obtained by casting water dispersions of graphene oxide and cloisite Na⁺. Coupling hydrophilicity and a high water vapor barrier in a homogenous film enables to realize humidity‐driven actuators which exploit the water gradient generated across the film section under asymmetric exposure to humidity. The hybrid films are self‐standing, flexible, and exhibit fast humidity‐triggered bidirectional bending up to 75°, which is tuned by varying the relative amount of the two components. Up to 60% of the bending angle can be preserved at the steady state, providing a large and reliable response to humidity. Moreover, thermal treatment results in the reduction of graphene oxide, endowing the films with humidity‐dependent electrical conductivity, which increases from 1.5 × 10^?6 S at 20% relative humidity (RH) up to 2.7 × 10^?5 S at 90% RH. The films are used to realize a humidity‐sensitive electrical switching system in which the reversible actuation is due to water desorption induced by the Joule effect. Due to their ease of preparation and tunable properties, this new class of graphene‐based materials is suitable for the realization of humidity‐driven and electrically responsive actuators and sensors.     

On Proton Conductivity in Porous and Dense Yttria Stabilized Zirconia at Low Temperature

The electrical conductivity of dense and nanoporous zirconia‐based thin films is compared to results obtained on bulk yttria stabilized zirconia (YSZ) ceramics. Different thin film preparation methods are used in order to vary grain size, grain shape, and porosity of the thin films. In porous films, a rather high conductivity is found at room temperature which decreases with increasing temperature to 120 °C. This conductivity is attributed to proton conduction along physisorbed water (Grotthuss mechanism) at the inner surfaces. It is highly dependent on the humidity of the surrounding atmosphere. At temperatures above 120 °C, the conductivity is thermally activated with activation energies between 0.4 and 1.1 eV. In this temperature regime the conduction is due to oxygen ions as well as protons. Proton conduction is caused by hydroxyl groups at the inner surface of the porous films. The effect vanishes above 400 °C, and pure oxygen ion conductivity with an activation energy of 0.9 to 1.3 eV prevails. The same behavior can also be observed in nanoporous bulk ceramic YSZ. In contrast to the nanoporous YSZ, fully dense nanocrystalline thin films only show oxygen ion conductivity, even down to 70 °C with an expected activation energy of 1.0 ± 0.1 eV. No proton conductivity through grain boundaries could be detected in these nanocrystalline, but dense thin films.