A Pyrenylpropyl Phosphonic Acid Surface Modifier for Mitigating the Thermal Resistance of Carbon Nanotube Contacts

Efforts to utilize the high intrinsic thermal conductivity of carbon nanotubes (CNTs) for thermal transport applications, namely for thermal interface materials (TIMs), have been encumbered by the presence of high thermal contact resistances between the CNTs and connecting materials. Here, a pyrenylpropyl‐phosphonic acid surface modifier is synthesized and applied in a straight forward and repeatable approach to reduce the thermal contact resistance between CNTs and metal oxide surfaces. When used to bond nominally vertically aligned multi‐walled CNT forests to Cu oxide surfaces, the modifier facilitates a roughly 9‐fold reduction in the thermal contact resistance over dry contact, enabling CNT‐based TIMs with thermal resistances of 4.6 ± 0.5 mm² K W^?1, comparable to conventional metallic solders. Additional experimental characterization of the modifier suggests that it may be used to reduce the electrical resistance of CNT‐metal oxide contacts by similar orders of magnitude.     

Covalently Bonded Graphene Sheets on Carbon Nanotubes: Direct Growth and Outstanding Properties

Integrating 1D carbon nanotubes (CNTs) and 2D graphene with covalent bonds can inherit the outstanding properties of both components and obtain additional advantages. Here, this work reports the preparation of covalently bonded graphene/CNT (G/CNT) structure by a normal chemical vapor deposition method. Specifically, the pre-synthesized defects on the sidewall of CNTs act as nucleation sites for the growth of graphene sheets to form a branch-leaf structure. Graphene leaves restrict the sliding and re-stacking of CNTs, endowing G/CNT hybrid demonstrates excellent anti-agglomeration properties that are not present in either graphene or CNTs. In addition, the covalently bonded structure and high graphitization degree of graphene sheets and CNTs significantly enhance the comprehensive properties of the G/CNT hybrid material, such as large specific surface area, excellent thermal stability, and high electrical conductivity. Consequently, the microwave absorption properties of G/CNT are significantly enhanced compared with CNTs. This work provides a feasible pathway to synthesize high-performance covalently bonded G/CNT hybrids.     

Thermal interface materials for automotive electronic control unit: Trends, technology and R&D challenges

The under-hood automotive ambient is harsh and its impact on electronics used in electronic control unit (ECU) assembly is a concern. The introduction of Euro 6 standard (Latest European Union Legislation) leading to increase in power density of power electronics in ECU has even amplified the device thermal challenge. Heat generated within the unit coupled with ambient temperature makes the system reliability susceptible to thermal degradation which ultimately may result in failure. Previous investigations show that the technology of thermal interface materials (TIMs) is a key to achieving good heat conductions within a package and from a package to heat sinking device. With studies suggesting that current TIMs contribute about 60% interfacial thermal resistance, a review of engineering materials has become imperative to identify TIM that could enhance heat transfer. This paper critically reviews the state-of-the-art in TIMs which may be applicable to automotive ECU. Our review shows that carbon-nanotube (CNT) when used as the structure of TIM or TIM filler could considerably advance thermal management issues by improving heat dissipation from the ECU. This search identifies chemical vapor deposition (CVD) as a low cost process for the commercial production of CNTs. In addition, this review further highlights the capability of CVD to grow nanotubes directly on a desired substrate. Other low temperature techniques of growing CNT on sensitive substrates are also presented in this paper.     

Electric‐Field‐Assisted Growth of Vertical Graphene Arrays and the Application in Thermal Interface Materials

Owing to the development of electronic devices moving toward high power density, miniaturization, and multifunction, research on thermal interface materials (TIMs) is become increasingly significant. Graphene is regarded as the most promising thermal management material owing to its ultrahigh in‐plane thermal conductivity. However, the fabrication of high‐quality vertical graphene (VG) arrays and their utilization in TIMs still remains a big challenge. In this study, a rational approach is developed for growing VG arrays using an alcohol‐based electric‐field‐assisted plasma enhanced chemical vapor deposition. Alcohol‐based carbon sources are used to produce hydroxyl radicals to increase the growth rate and reduce the formation of defects. A vertical electric field is used to align the graphene sheets. Using this method, high‐quality and vertically aligned graphene with a height of 18.7 µm is obtained under an electric field of 30 V cm^?1. TIMs constructed with the VG arrays exhibit a high vertical thermal conductivity of 53.5 W m^?1 K^?1 and a low contact thermal resistance of 11.8 K mm² W^?1, indicating their significant potential for applications in heat dissipation technologies.     

Charge‐Transport Behavior in Aligned Carbon Nanotubes: A Quantum‐Chemical Investigation

Correlated quantum‐chemical calculations are applied to analyze the amplitude of the electronic‐transfer integrals that describe charge transport in interacting carbon nanotubes (CNTs) by investigating the influences of: i) the relative positions of the CNTs, ii) the size of the CNTs, and iii) their chemical impurities. Our results indicate that the mobility of the charge carrier is extremely sensitive to the molecular packing and the presence of chemical impurities. The largest splitting for the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels is in the case of perfectly cofacial conformations where hexagons face hexagons in the dimer structure. We found that the diameter of the CNT determines the type of transporting carrier: for CNTs with large diameters hole transport dominates, while for thin CNTs electron transport dominates. In general, the carrier mobility for the perfect CNTs (n ≥ 3) is less pronounced than that of C₆₀ due to their relatively small strain. B‐ and N‐doped CNTs exhibit considerably larger mobilities owing to the possibility of metallic behavior. These results provide a plausible explanation for the high mobility found experimentally in a field‐effect transistor (FET) made from a large‐area, well‐aligned CNT array. In addition, these hole‐rich and electron‐rich dopants imply potential applications in nanoelectronics.     

Electrophoretically‐Deposited Metal‐Decorated CNT Nanoforests with High Thermal/Electric Conductivity and Wettability Tunable from Hydrophilic to Superhydrophobic

A single‐step, room‐temperature, and scalable electrophoretic deposition process is reported to form nanocomposites on any electrically conductive surface with metal nanoparticle decorated carbon nanotubes (CNTs). The contact angles (CAs) can be easily tuned from ≈60° to 168° by varying the deposition voltage, while hydrophobicity and superhydrophobicity surprisingly arise from the hydrophilic CNTs being deposited. The relatively high voltage tends to vertically align CNTs during deposition, leading to architectural micro/nanoscale roughness on the surface. The combination of the multiscale roughness along with the low surface energy of hydrocarbon functional groups on the CNT surface has enabled facile wettability control, including the Petal and Lotus effects. Further, the relatively vertical orientation of the CNTs, without any coating, allows for current and heat transfer along their axis with superior conductivity. Similar behavior in terms of CA control is seen for all three divalent metal ions in the deposition solution (i.e., Cu²⁺, Ni²⁺, and Zn²⁺) that are used to charge the CNTs while eventually getting co‐deposited. This implies that this method could possibly be extended to other metals by selecting appropriate charging salt. A patterning technique is also demonstrated for facile fabrication of superhydrophobic CNT‐metal islands surrounded by hydrophilic CNT coating.     

Origin and Control of Polyacrylonitrile Alignments on Carbon Nanotubes and Graphene Nanoribbons

While one of the most promising applications of carbon nanotubes (CNTs) is to enhance polymer orientation and crystallization to achieve advanced carbon fibers, the successful realization of this goal has been hindered by the insufficient atomistic understanding of polymer–CNT interfaces. Herein, polyacrylonitrile (PAN)‐CNT hybrid structures are theoretically studied as a representative example of polymer–CNT composites. Based on density functional theory calculations, it is first found that the relative orientation of polar PAN nitrile groups with respect to the CNT surface is the key factor that determines the PAN–CNT interface energetics and the lying‐down PAN configurations are much more preferable than their standing‐up counterparts. The CNT curvature is identified as another important factor, giving the largest binding energy in the zero‐curvature graphene limit. Charge transfer analysis explains the unique tendency of linear PAN alignments on the CNT surface and the possibility of ordered PAN–PAN assembly. Next, performing large‐scale molecular dynamics simulations, it is shown that the desirable linear PAN–CNT alignment can be achieved even for relatively large initial misorientations and further demonstrate that graphene nanoribbons are a promising carbon nano‐reinforcement candidate. The microscopic understanding accumulated in this study will provide design guidelines for the development of next‐generation carbon nanofibers.     

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.     

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.     

Ultrahigh Electrical Resistance of Poly(cyclohexyl methacrylate)/Carbon Nanotube Composites Prepared Using Surface‐Initiated Polymerization

Multiwalled carbon nanotubes on which poly(cyclohexyl methacrylate)s are densely grafted (PCHMA‐CNTs), are synthesized using a modified surface‐initiated atom transfer radical polymerization technique. The electrical resistance of PCHMA‐CNT is systematically characterized under direct current (DC) and alternating current and compared to that of conventional nanocomposites prepared by blending PCHMA with the CNT (PCHMA/CNT). At a comparable volume fraction of CNT, DC volume resistivity of PCHMA‐CNT is 14 orders of magnitude higher than that of PCHMA/CNT. This is because the grafted polymer with a combination of the high molecular weight and the high grafting density isolates individual CNTs at a long distance in the PCHMA‐CNT system. In addition, impedance analysis reveals that the highly insulated PCHMA‐CNT has the same electrical nature as neat PCHMA, i.e., it is a dielectric. Furthermore, dynamic mechanical analysis shows PCHMA‐CNT has a good mechanical properties as well as ultrahigh electrical resistance.     

Directed Growth and Electrical‐ Transport Properties of Carbon Nanotube Architectures on Indium Tin Oxide Films on Silicon‐Based Substrates

Growing aligned carbon nanotubes (CNTs) on electrically conducting and/or optically transparent materials is potentially useful for accessing CNT properties through electrical and optical stimuli. Here, we report a new approach to growing aligned bundles of multiwalled CNTs on a porous back contact of optically transparent and electrically conducting indium tin oxide (ITO) films on silicon and silica substrates without the use of a predeposited catalyst. CNTs grow from a xylene/ferrocene mixture, which traverses through the pores in the thin ITO film, and decomposes on an interfacial silica layer formed via the reaction between ITO and the Si substrate. The CNTs inherit the topography of the silica substrate, enabling back‐contact formation for CNTs grown in any predetermined orientation. These features can be harnessed to form CNT contacts with other substrate materials which, upon reduction by Si, results in a conducting interfacial layer. The ITO‐contacted CNTs exhibit thermally activated ohmic behavior across a 100 ± 10 meV barrier at electric fields below ～ 100 V cm^–1 due to carrier transport through the outermost shells of the CNTs. At higher electric fields, we observe superlinear behavior due to carrier tunneling and transport through the inner graphene shells. Our findings open up new possibilities for integrating CNTs with Si‐based device technologies.     

Graphene Reinforced Carbon Nanotube Networks for Wearable Strain Sensors

Transparent, stretchable films of carbon nanotubes (CNTs) have attracted significant attention for applications in flexible electronics, while the lack of structural strength in CNT networks leads to deformation and failure under high mechanical load. In this work, enhancement of the strength and load transfer capabilities of CNT networks by chemical vapor deposition of graphene in the nanotube voids is proposed. The graphene hybridization significantly strengthens the CNT networks, especially at nanotube joints, and enhances their resistance to buckling and bundling under large cyclic strain up to 20%. The hybridized films show linear and reproducible responses to tensile strains, which have been applied in strain sensors to detect human motions with fast response, high sensitivity, and durability.     

Carbon Nanotube‐Encapsulated Noble Metal Nanoparticle Hybrid as a Cathode Material for Li‐Oxygen Batteries

Although Li‐oxygen batteries offer extremely high theoretical specific energy, their practical application still faces critical challenges. One of the main obstacles is the high charge overpotential caused by sluggish kinetics of charge transfer that is closely related to the morphology of discharge products and their distribution on the cathode. Here, a series of noble metal nanoparticles (Pd, Pt, Ru and Au) are encapsulated inside end‐opened carbon nanotubes (CNTs) by wet impregnation followed by thermal annealing. The resultant cathode materials exhibit a dramatic reduction of charge overpotentials compared to their counterparts with nanoparticles supported on CNT surface. Notably, the charge overpotential can be as low as 0.3 V when CNT‐encapsulated Pd nanoparticles are used on the cathode. The cathode also shows good stability during discharge–charge cycling. Density functional theory (DFT) calculations reveal that encapsulation of “guest” noble metal nanoparticles in “host” CNTs is able to strengthen the electron density on CNT surfaces, and to avoid the regional enrichment of electron density caused by the direct exposure of nanoparticles on CNT surface. These unique properties ensure the uniform coverage of Li₂O₂ nanocrystals on CNT surfaces instead of localized distribution of Li₂O₂ aggregation, thus providing efficient charge transfer for the decomposition of Li₂O₂.     

An Anisotropically High Thermal Conductive Boron Nitride/Epoxy Composite Based on Nacre‐Mimetic 3D Network

Polymer‐based thermal interface materials (TIMs) with excellent thermal conductivity and electrical resistivity are in high demand in the electronics industry. In the past decade, thermally conductive fillers, such as boron nitride nanosheets (BNNS), were usually incorporated into the polymer‐based TIMs to improve their thermal conductivity for efficient heat management. However, the thermal performance of those composites means that they are still far from practical applications, mainly because of poor control over the 3D conductive network. In the present work, a high thermally conductive BNNS/epoxy composite is fabricated by building a nacre‐mimetic 3D conductive network within an epoxy resin matrix, realized by a unique bidirectional freezing technique. The as‐prepared composite exhibits a high thermal conductivity (6.07 W m^?1 K^?1) at 15 vol% BNNS loading, outstanding electrical resistivity, and thermal stability, making it attractive to electronic packaging applications. In addition, this research provides a promising strategy to achieve high thermal conductive polymer‐based TIMs by building efficient 3D conductive networks.     

Thermal contact resistance of cured gel polymeric thermal interface material

This paper reports the experimental results on the contact resistance of curable polymer gel thermal interface materials (TIMs) that have different mechanical properties due to difference in the rheology of the polymers. A semi-analytical model for the prediction of the thermal contact resistance of cured gel TIMs is also introduced in this paper. A novel method of finding the transition from grease type behavior to gel type behavior, which is very important for post reliability stress performance, based on G' (storage shear modulus) and G' (loss shear modulus) measurements is reported. Further, post thermal cycling thermal resistance degradation rate of gel TIMs are related to the ratio of G and G'. Finally, design guidelines for gel TIMs for use in flip-chip packages comprising heat spreaders are proposed.     

Wide Range Control of Microstructure and Mechanical Properties of Carbon Nanotube Forests: A Comparison Between Fixed and Floating Catalyst CVD Techniques

Vertically aligned carbon nanotube (CNT) forests may be used as miniature springs, compliant thermal interfaces, and shock absorbers, and for these and other applications it is vital to understand how to engineer their mechanical properties. Herein is investigated how the diameter and packing density within CNT forests govern their deformation behavior, structural stiffness, and elastic energy absorption properties. The mechanical behavior of low‐density CNT forests grown by fixed catalyst CVD methods and high‐density CNT forests grown by a floating catalyst CVD method are studied by in situ SEM compression testing and tribometer measurements of force‐displacement relationships. Low‐density and small‐diameter CNT columns (fixed catalyst) exhibit large plastic deformation and can be pre‐deformed to act as springs within a specified elastic range, whereas high‐density and large‐diameter CNT columns (floating catalyst) exhibit significant elastic recovery after deformation. In this work the energy absorption capacity of CNT forests is tuned over three orders of magnitude and it is shown that CNT forest density can be tuned over a range of conventional foam materials, but corresponding stiffness is ～10× higher. It is proposed that the elastic behavior of CNT forests is analogous to open‐cell foams and a simple model is presented. It is also shown that this model can be useful as a first‐order design tool to establish design guidelines for the mechanical properties of CNT forests and selection of the appropriate synthesis method.     

Face‐to‐Face Contact and Open‐Void Coinvolved Si/C Nanohybrids Lithium‐Ion Battery Anodes with Extremely Long Cycle Life

To develop high‐performance anode materials of lithium‐ion batteries (LIBs) instead of commercial graphite for practical applications, herein, a layer of silicon has been well‐anchored onto a 3D graphene/carbon nanotube (CNT) aerogels (CAs) framework with face‐to‐face contact and balanced open void by a simple chemical vapor deposition strategy. The engineered contact interface between CAs and Si creates high‐efficiency channels for the rapid electrons and lithium ions transport, and meanwhile, the balanced open‐void allows the free expansion of Si during cycling while maintaining high structural integrity due to the robust mechanical strength of 3D CAs framework. As a consequence, the as‐synthesized Si/CAs nanohybrids are highly stable anode materials for LIBs with a high reversible discharge capacity (1498 mAh g^?1 at 200 mA g^?1) and excellent rate capability (462 mAh g^?1 at 10 000 mA g^?1), which is much better than Si/graphene‐CNTs‐mixture (51 mAh g^?1 at 10 000 mA g^?1). More significantly, it is found that the Si/CAs nanohybrids display no obvious capacity decline even after 2000 cycles at a high current density of 10 000 mA g^?1. The present Si/CAs nanohybrids are one of the most stable Si‐based anode materials ever reported for LIBs to date.     

Luminescence of Functionalized Carbon Nanotubes as a Tool to Monitor Bundle Formation and Dissociation in Water: The Effect of Plasmid‐DNA Complexation

Functionalized carbon nanotubes (f‐CNTs) are explored as novel nanomaterials for biomedical applications. UV‐vis luminescence of aqueous dispersions of CNT–NH₃⁺ and CNT–NH–Ac (NH–Ac: acetamido) is observed using standard laboratory spectrophotometric instrumentation, and the measured fluorescence intensity is correlated with the aggregation state of the f‐CNTs: a high intensity indicates improved f‐CNT individualization and dispersion, while a decrease in fluorescence intensity indicates a higher degree of nanotube aggregation and bundling as a result of varying the sodium dodecyl sulfate (SDS) concentrations and pH in the aqueous phase. Moreover, utilization of this relationship between fluorescence intensity and the state of f‐CNT aggregation is carried out to elucidate the interactions between f‐CNTs and gene‐encoding plasmid DNA (pDNA). pDNA is shown to interact with CNT–NH₃⁺ primarily through electrostatic interactions that lead concomitantly to a higher degree of f‐CNT bundling. The CNT–NH₃⁺/pDNA interactions are successfully competed by SDS/f‐CNT surface interactions, resulting in the displacement of pDNA. These studies provide exemplification of the use of fluorescence spectrophotometry to accurately describe the aggregation state of water‐soluble f‐CNTs. Characterization of the complexes between pDNA and f‐CNTs elucidates the opportunities and limitations of such supramolecular systems as potential vectors for gene transfer.     

Open‐Ended,N‐Doped Carbon Nanotube–Graphene Hybrid Nanostructures as High‐Performance Catalyst Support

A hierarchical N‐doped carbon nanotube‐graphene hybrid nanostructure (NCNT‐GHN), in which the graphene layers are distributed inside the CNT inner cavities, was designed to efficiently support noble metal (e.g., PtRu) nanoparticles. Well‐dispersed PtRu nanoparticles with diameters of 2–4 nm were immobilized onto these NCNT‐GHN supports by a low‐temperature chemical reduction method without any pretreatment. Compared to conventional CNTs and commercial catalysts. a much better catalytic performance was achieved by a synergistic effect of the hierarchical structure (graphene‐CNT hybrid) and electronic modulation (N‐doping) during the methanol electrooxidation reaction. Improved single‐cell performances with long‐term stability are also demonstrated using NCNT‐GHN as catalyst support.     

Vacancy‐Controlled Contact Friction in Graphene

Defects‐controlled friction in graphene is of technological importance in many applications, but the underlying mechanism remains a subject of debate. Here it is shown that, during the controlled oxidation in oxygen plasma and subsequent reduction induced by high‐energy photons, the contact friction in chemical vapor deposition grown graphene is dominantly determined by the vacancies formed instead of the bonding with add‐atoms. This effect is attributed to the vacancy‐enhanced out‐of‐plane deformation flexibility in graphene, which tends to produce large puckering of graphene sheet near the contact edge and thus increases the effective contact area. Modified graphene with large contact friction has a large density of defects, but remains a good electrical conductor, in which the carrier transport is strongly affected by quantum localization effects even at room temperature. It is also found that the oxidation process in graphene is substrate‐sensitive. Comparing to monolayer graphene on SiO₂ substrate, the oxidation process progresses much faster when the substrate is SrTiO₃, while bilayer graphene exhibits great oxidation resistance on both substrates. The collection of observations provides important information for tailoring the mechanical, electrical, and chemical properties of graphene through selected defects and substrates.