Aerosol Jet Printing of Graphene and Carbon Nanotube Patterns on Realistically Rugged Substrates.

Direct-write additive manufacturing of graphene and carbon nanotube (CNT) patterns by aerosol jet printing (AJP) is promising for the creation of thermal and electrical interconnects in (opto)electronics. In realistic application scenarios, this however often requires deposition of graphene and CNT patterns on rugged substrates such as, for example, roughly machined and surface-oxidized metal block heat sinks. Most AJP of graphene/CNT patterns has thus far however concentrated on flat wafer- or foil-type substrates. Here, we demonstrate AJP of graphene and single walled CNT (SWCNT) patterns on realistically rugged plasma-electrolytic-oxidized (PEO) Al blocks, which are promising heat sink materials. We show that AJP on the rugged substrates offers line resolution of down to ∼40 µm width for single AJP passes, however, at the cost of noncomplete substrate coverage including noncovered µm-sized pores in the PEO Al blocks. With multiple AJP passes, full coverage including coverage of the pores is, however, readily achieved. Comparing archetypical aqueous and organic graphene and SWCNT inks, we show that the choice of the ink system drastically influences the nanocarbon AJP parameter window, deposit microstructure including crystalline quality, compactness of deposit, and inter/intrapass layer adhesion for multiple passes. Simple electrical characterization indicates aqueous graphene inks as the most promising choice for AJP-deposited electrical interconnect applications. Our parameter space screening thereby forms a framework for rational process development for graphene and SWCNT AJP on application-relevant, rugged substrates.

Graphene-Based Films: Fabrication, Interfacial Modification, and Applications.

Graphene-based film attracts tremendous interest in many potential applications due to its excellent thermal, electrical, and mechanical properties. This review focused on a critical analysis of fabrication, processing methodology, the interfacial modification approach, and the applications of this novel and new class material. Strong attention was paid to the preparation strategy and interfacial modification approach to improve its mechanical and thermal properties. The overview also discussed the challenges and opportunities regarding its industrial production and the current status of the commercialization. This review showed that blade coating technology is an effective method for industrial mass-produced graphene film with controllable thickness. The synergistic effect of different interface interactions can effectively improve the mechanical properties of graphene-based film. At present, the application of graphene-based film on mobile phones has become an interesting example of the use of graphene. Looking for more application cases is of great significance for the development of graphene-based technology.

Degradation of Carbon Nanotube Array Thermal Interface Materials through Thermal Aging: Effects of Bonding, Array Height, and Catalyst Oxidation.

Carbon nanotube (CNT) array thermal interface materials (TIMs) are promising candidates for high-performance applications in terms of thermal performance. However, in order to be useful in commercial applications, the reliability of the interfaces is an equally important parameter, which so far has not been thoroughly investigated. In this study, the reliability of CNT array TIMs is investigated through accelerated aging. The roles of CNT array height and substrate configuration are studied for their relative impact on thermal resistance degradation. After aging, the CNT catalyst is analyzed using X-ray photoelectron spectroscopy to evaluate chemical changes. The CNT-catalyst bond appears to degrade during aging but not to the extent that the TIM performance is compromised. On the other hand, coefficient of thermal expansion mismatch between surfaces creates strain that needs to be absorbed, which requires CNT arrays with sufficient height. Transfer and bonding of both CNT roots and tips also create more reliable interfaces. Crucially, we find that the CNT array height of most previously reported CNT array TIMs is not enough to prevent significant reliability problems.

A Novel Graphene Quantum Dot-Based mRNA Delivery Platform.

During the last decades, there has been growing interest in using therapeutic messager RNA (mRNA) together with drug delivery systems. Naked, unformulated mRNA is, however, unable to cross the cell membrane and is susceptible to degradation. Here we use graphene quantum dots (GQDs) functionalized with polyethyleneimine (PEI) as a novel mRNA delivery system. Our results show that these modified GQDs can be used to deliver intact and functional mRNA to Huh-7 hepatocarcinoma cells at low doses and, that the GQDs are not toxic, although cellular toxicity is a problem for these first-generation modified particles. Functionalized GQDs represent a potentially interesting delivery system that is easy to manufacture, stable and effective.

Synthesis of graphene quantum dots and their applications in drug delivery.

This review focuses on the recent advances in the synthesis of graphene quantum dots (GQDs) and their applications in drug delivery. To give a brief understanding about the preparation of GQDs, recent advances in methods of GQDs synthesis are first presented. Afterwards, various drug delivery-release modes of GQDs-based drug delivery systems such as EPR-pH delivery-release mode, ligand-pH delivery-release mode, EPR-Photothermal delivery-Release mode, and Core/Shell-photothermal/magnetic thermal delivery-release mode are reviewed. Finally, the current challenges and the prospective application of GQDs in drug delivery are discussed.

High porosity and light weight graphene foam heat sink and phase change material container for thermal management.

During the last decade, graphene foam emerged as a promising high porosity 3-dimensional (3D) structure for various applications. More specifically, it has attracted significant interest as a solution for thermal management in electronics. In this study, we investigate the possibility to use such porous materials as a heat sink and a container for a phase change material (PCM). Graphene foam (GF) was produced using chemical vapor deposition (CVD) process and attached to a thermal test chip using sintered silver nanoparticles (Ag NPs). The thermal conductivity of the graphene foam reached 1.3 W m-1 K-1, while the addition of Ag as a graphene foam silver composite (GF/Ag) enhanced further its effective thermal conductivity by 54%. Comparatively to nickel foam, GF and GF/Ag showed lower junction temperatures thanks to higher effective thermal conductivity and a better contact. A finite element model was developed to simulate the fluid flow through the foam structure model and showed a positive and a non-negligible contributions of the secondary microchannel within the graphene foam. A ratio of 15 times was found between the convective heat flux within the primary and secondary microchannel. Our paper successfully demonstrates the possibility of using such 3D porous material as a PCM container and heat sink and highlight the advantage of using the carbon-based high porosity material to take advantage of its additional secondary porosity.

Multiple growth of graphene from a pre-dissolved carbon source.

Mono- to few-layer graphene materials are successfully synthesized multiple times using Cu-Ni alloy as a catalyst after a single-chemical vapor deposition (CVD) process. The multiple synthesis is realized by extracting carbon source pre-dissolved in the catalyst substrate. Firstly, graphene is grown by the CVD method on Cu-Ni catalyst substrates. Secondly, the same Cu-Nicatalyst foils are annealed, in absence of any external carbon precursor, to grow graphene using the carbon atoms pre-dissolved in the catalyst during the CVD process. This annealing process is repeated to synthesize graphene successfully until carbon is exhausted in the Cu-Ni foils. After the CVD growth and each annealing growth process, the as-grown graphene is removed using a bubbling transfer method. A wide range of characterizations are performed to examine the quality of the obtained graphene material and to monitor the carbon concentration in the catalyst substrates. Results show that graphene from each annealing growth process possesses a similar quality, which confirmed the good reproducibility of the method. This technique brings great freedom to graphene growth and applications, and it could be also used for other 2D material synthesis.

Highly Oriented Graphite Aerogel Fabricated by Confined Liquid-Phase Expansion for Anisotropically Thermally Conductive Epoxy Composites.

Graphene-based thermally conductive polymer composites are of great importance for the removal of the excess heat generated by electronic devices. However, due to the orientation of graphene sheets in the polymer matrix, the through-plane thermal conductivity of polymer/graphene composites remains far from satisfactory. We here demonstrate a confined liquid-phase expansion strategy to fabricate highly oriented confined expanded graphite (CEG) aerogels. After being incorporated into epoxy resin (EP), the resulting EP/CEG composites exhibit a high through-plane thermal conductivity (4.14 ± 0.21 W m-1 K-1) at a quite low filler loading of 1.75 wt % (0.91 vol %), nearly 10 times higher than that of neat EP resin and 7.5 times higher than the in-plane thermal conductivity of the composite, indicating that the CEG aerogel has a high through-plane thermal conductivity enhancement efficiency that outperforms those of many graphite/graphene-based fillers. The facile preparation method holds great industrial application potential in fabricating anisotropic thermally conductive polymer composites.

Effects of high temperature treatment of carbon nanotube arrays on graphite: increased crystallinity, anchoring and inter-tube bonding.

Thermal treatment of carbon nanotubes (CNTs) can significantly improve their mechanical, electrical and thermal properties due to reduced defects and increased crystallinity. In this work we investigate the effect of annealing at 3000 °C of vertically aligned CNT arrays synthesized by chemical vapor deposition (CVD) on graphite. Raman measurements show a drastically reduced amount of defects and, together with transmission electron microscope (TEM) diffraction measurements, an increased average crystallite size of around 50%, which corresponds to a 124% increase in Young's modulus. We also find a tendency for CNTs to bond to each other with van der Waals (vdW) forces, which causes individual CNTs to closely align with each other. This bonding causes a densification effect on the entire CNT array, which appears at temperatures >1000 °C. The densification onset temperature corresponds to the thermal decomposition of oxygen containing functional groups, which otherwise prevents close enough contact for vdW bonding. Finally, the remaining CVD catalyst on the bottom of the CNT array is evaporated during annealing, enabling direct anchoring of the CNTs to the underlying graphite substrate.

Thermally Reduced Graphene Oxide/Carbon Nanotube Composite Films for Thermal Packaging Applications.

Thermally reduced graphene oxide/carbon nanotube (rGO/CNT) composite films were successfully prepared by a high-temperature annealing process. Their microstructure, thermal conductivity and mechanical properties were systematically studied at different annealing temperatures. As the annealing temperature increased, more oxygen-containing functional groups were removed from the composite film, and the percentage of graphene continuously increased. When the annealing temperature increased from 1100 to 1400 °C, the thermal conductivity of the composite film also continuously increased from 673.9 to 1052.1 W m-1 K-1. Additionally, the Young's modulus was reduced by 63.6%, and the tensile strength was increased by 81.7%. In addition, the introduction of carbon nanotubes provided through-plane thermal conduction pathways for the composite films, which was beneficial for the improvement of their through-plane thermal conductivity. Furthermore, CNTs apparently improved the mechanical properties of rGO/CNT composite films. Compared with the rGO film, 1 wt% CNTs reduced the Young's modulus by 93.3% and increased the tensile strength of the rGO/CNT composite film by 60.3%, which could greatly improve its flexibility. Therefore, the rGO/CNT composite films show great potential for application as thermal interface materials (TIMs) due to their high in-plane thermal conductivity and good mechanical properties.

Improved Interfacial Bonding Strength and Reliability of Functionalized Graphene Oxide for Cement Reinforcement Applications.

Poor bonding strength between nanomaterials and cement composites inevitably lead to the failure of reinforcement. Herein, a novel functionalization method for the fabrication of functionalized graphene oxide (FGO), which is capable of forming highly reliable covalent bonds with cement hydration products, and therefore, suitable for use as an efficient reinforcing agent for cement composites, is discussed. The bonding strength between cement and aggregates was improved more than 21 times with the reinforcement of FGO. The fabricated FGO also demonstrated many important features, including high reliability in cement pastes, good dispersibility, and efficient structural refinement of cement hydration products. With the incorporation of FGO, cement mortar samples demonstrated up to 40 % increased early and ultimate strength. Such results make the fast demolding and manufacture of light constructions become highly possible, and show strong advantages on improving productivity, saving cost, and reducing CO2 emissions in practical applications.

Properties of Undoped Few-Layer Graphene-Based Transparent Heaters.

In many applications like sensors, displays, and defoggers, there is a need for transparent and efficient heater elements produced at low cost. For this reason, we evaluated the performance of graphene-based heaters with from one to five layers of graphene on flexible and transparent polyethylene terephthalate (PET) substrates in terms of their electrothermal properties like heating/cooling rates and steady-state temperatures as a function of the input power density. We found that the heating/cooling rates followed an exponential time dependence with a time constant of just below 6 s for monolayer heaters. From the relationship between the steady-state temperatures and the input power density, a convective heat-transfer coefficient of 60 W·m-2·°C-1 was found, indicating a performance much better than that of many other types of heaters like metal thin-film-based heaters and carbon nanotube-based heaters.

Atomic Layer Deposition of Buffer Layers for the Growth of Vertically Aligned Carbon Nanotube Arrays.

Vertically aligned carbon nanotube arrays (VACNTs) show a great potential for various applications, such as thermal interface materials (TIMs). Besides the thermally oxidized SiO2, atomic layer deposition (ALD) was also used to synthesize oxide buffer layers before the deposition of the catalyst, such as Al2O3, TiO2, and ZnO. The growth of VACNTs was found to be largely dependent on different oxide buffer layers, which generally prevented the diffusion of the catalyst into the substrate. Among them, the thickest and densest VACNTs could be achieved on Al2O3, and carbon nanotubes were mostly triple-walled. Besides, the deposition temperature was critical to the growth of VACNTs on Al2O3, and their growth rate obviously reduced above 650 °C, which might be related to the Ostwald ripening of the catalyst nanoparticles or subsurface diffusion of the catalyst. Furthermore, the VACNTs/graphene composite film was prepared as the thermal interface material. The VACNTs and graphene were proved to be the effective vertical and transverse heat transfer pathways in it, respectively.

Chemical Vapor Deposition of Vertically Aligned Carbon Nanotube Arrays: Critical Effects of Oxide Buffer Layers.

Vertically aligned carbon nanotubes (VACNTs) were synthesized on different oxide buffer layers using chemical vapor deposition (CVD). The growth of the VACNTs was mainly determined by three factors: the Ostwald ripening of catalyst nanoparticles, subsurface diffusion of Fe, and their activation energy for nucleation and initial growth. The surface roughness of buffer layers largely influenced the diameter and density of catalyst nanoparticles after annealing, which apparently affected the lifetime of the nanoparticles and the thickness of the prepared VACNTs. In addition, the growth of the VACNTs was also affected by the deposition temperature, and the lifetime of the catalyst nanoparticles apparently decreased when the deposition temperature was greater than 600 °C due to their serious Ostwald ripening. Furthermore, in addition to the number of catalyst nanoparticles, the density of the VACNTs was also largely dependent on their activation energy for nucleation and initial growth.

Manufacturing Graphene-Encapsulated Copper Particles by Chemical Vapor Deposition in a Cold Wall Reactor.

Functional fillers, such as Ag, are commonly employed for effectively improving the thermal or electrical conductivity in polymer composites. However, a disadvantage of such a strategy is that the cost and performance cannot be balanced simultaneously. Therefore, the drive to find a material with both a cost efficient fabrication process and excellent performance attracts intense research interest. In this work, inspired by the core-shell structure, we developed a facile manufacturing method to prepare graphene-encapsulated Cu nanoparticles (GCPs) through utilizing an improved chemical vapor deposition (CVD) system with a cold wall reactor. The obtained GCPs could retain their spherical shape and exhibited an outstanding thermal stability up to 179 °C. Owing to the superior thermal conductivity of graphene and excellent oxidation resistance of GCPs, the produced GCPs are practically used in a thermally conductive adhesive (TCA), which commonly consists of Ag as the functional filler. Measurement shows a substantial 74.6 % improvement by partial replacement of Ag with GCPs.

Tailoring the Thermal and Mechanical Properties of Graphene Film by Structural Engineering.

Due to substantial phonon scattering induced by various structural defects, the in-plane thermal conductivity (K) of graphene films (GFs) is still inferior to the commercial pyrolytic graphite sheet (PGS). Here, the problem is solved by engineering the structures of GFs in the aspects of grain size, film alignment, and thickness, and interlayer binding energy. The maximum K of GFs reaches to 3200 W m-1 K-1 and outperforms PGS by 60%. The superior K of GFs is strongly related to its large and intact grains, which are over four times larger than the best PGS. The large smooth features about 11 µm and good layer alignment of GFs also benefit on reducing phonon scattering induced by wrinkles/defects. In addition, the presence of substantial turbostratic-stacking graphene is found up to 37% in thin GFs. The lacking of order in turbostratic-stacking graphene leads to very weak interlayer binding energy, which can significantly decrease the phonon interfacial scattering. The GFs also demonstrate excellent flexibility and high tensile strength, which is about three times higher than PGS. Therefore, GFs with optimized structures and properties show great potentials in thermal management of form-factor-driven electronics and other high-power-driven systems.

Conductive Adhesive Based on Mussel-Inspired Graphene Decoration with Silver Nanoparticles.

Decoration with silver nanoparticles was obtained by coating graphene with a polydopamine layer, able to induce spontaneous metallic nanoparticles formation without any specific chemical interfacial modifier, neither using complex instrumentation. The choice of dopamine was inspired by the composition of adhesive proteins in mussels, related to their robust attach to solid surfaces. The synthesis procedure started from graphite and involved eco-friendly compounds, such as Vitamin C and glucose as reducing agent and water as reaction medium. Silver decorated graphene was inserted as secondary nanofiller in the formulation of a reference conductive adhesive based on epoxy resin and silver flakes. A wide characterization of the intermediate materials obtained along the step procedure for the adhesive preparation was carried out by several techniques. We have found that the presence of nanofiller yields, in addition to an improvement of the thermal conductivity (up to 7.6 W/m · K), a dramatic enhancement of the electrical conductivity of the adhesive. In particular, starting from 3 · 102 S/cm of the reference adhesive, we obtained a value of 4 · 104 S/cm at a nanofiller concentration of 11.5 wt%. The combined double filler conductivity was evaluated by Zallen's model. The effect of the temperature on the resistivity of the adhesive has been also studied.

Thermal Conductivity Enhancement of Coaxial Carbon@Boron Nitride Nanotube Arrays.

We demonstrate the thermal conductivity enhancement of the vertically aligned carbon nanotube (CNT) arrays (from ∼15.5 to 29.5 W/mK, ∼90% increase) by encapsulating outer boron nitride nanotube (BNNT, 0.97 nm-thick with ∼3-4 walls). The heat transfer enhancement mechanism of the coaxial C@BNNT was further revealed by molecular dynamics simulations. Because of their highly coherent lattice structures, the outer BNNT serves as additional heat conducting path without impairing the thermal conductance of inner CNT. This work provides deep insights into tailoring the heat transfer of arbitrary CNT arrays and will enable their broader applications as thermal interface material.

Stretchable Thermoelectric Generators Metallized with Liquid Alloy.

Conventional thermoelectric generators (TEGs) are normally hard, rigid, and flat. However, most objects have curvy surfaces, which require soft and even stretchable TEGs for maximizing efficiency of thermal energy harvesting. Here, soft and stretchable TEGs using conventional rigid Bi2Te3 pellets metallized with a liquid alloy is reported. The fabrication is implemented by means of a tailored layer-by-layer fabrication process. The STEGs exhibit an output power density of 40.6 µW/cm2 at room temperature. The STEGs are operational after being mechanically stretched-and-released more than 1000 times, thanks to the compliant contact between the liquid alloy interconnects and the rigid pellets. The demonstrated interconnect scheme will provide a new route to the development of soft and stretchable energy-harvesting avenues for a variety of emerging electronic applications.

Control of Nanoplane Orientation in voBN for High Thermal Anisotropy in a Dielectric Thin Film: A New Solution for Thermal Hotspot Mitigation in Electronics.

High anisotropic thermal materials, which allow heat to dissipate in a preferential direction, are of interest as a prospective material for electronics as an effective thermal management solution for hot spots. However, due to their preferential heat propagation in the in-plane direction, the heat spreads laterally instead of vertically. This limitation makes these materials ineffective as the density of hot spots increases. Here, we produce a new dielectric thin film material at room temperature, named vertically ordered nanocrystalline h-BN (voBN). It is produced such that its preferential thermally conductive direction is aligned in the vertical axis, which facilitates direct thermal extraction, thereby addressing the increasing challenge of thermal crosstalk. The uniqueness of voBN comes from its h-BN nanocrystals where all their basal planes are aligned in the direction normal to the substrate plane. Using the 3ω method, we show that voBN exhibits high anisotropic thermal conductivity (TC) with a 16-fold difference between through-film TC and in-plane TC (respectively 4.26 and 0.26 W·m-1·K-1). Molecular dynamics simulations also concurred with the experimental data, showing that the origin of this anisotropic behavior is due to the nature of voBN's plane ordering. While the consistent vertical ordering provides an uninterrupted and preferred propagation path for phonons in the through-film direction, discontinuity in the lateral direction leads to a reduced in-plane TC. In addition, we also use COMSOL to simulate how the dielectric and thermal properties of voBN enable an increase in hot spot density up to 295% compared with SiO2, without any temperature increase.