Thermal expansion behavior of thin films expanding freely on water surface.

Coefficient of thermal expansion (CTE) for thin film has been measured only from change in thickness because thin film has to be constrained on a solid substrate. However, thin film CTE shows different values depending on the supporting solid substrate. Here, a novel measurement method is suggested to quantitatively measure the in-plane thermal expansion of thin films floating on a water surface. In-plane thermal expansion of thin films on water surface is achieved by heating the water. The CTE is measured through a digital image correlation (DIC) technique. The DIC tracks displacement marks deposited on the film surface, and the in-plane thermal strain is defined as the change in distance between the patterns. The method can be applied to measure the CTE of polymer, metal, and graphene with a thickness ranging from a micrometer to one-atom-thickness. The in-plane thermal expansion of the polystyrene (PS) thin film decreased as the film thickness decreased. The negative CTE of graphene is also successfully explored without any substrate effects or complicated calculations. The CTE measurement method can provide understanding of the intrinsic thermal expansion behavior of thin films including emerging two-dimensional materials.

Controlling Interfacial Reactions and Intermetallic Compound Growth at the Interface of a Lead-free Solder Joint with Layer-by-Layer Transferred Graphene.

The immoderate growth of intermetallic compounds (IMCs) formed at the interface of a solder metal and the substrate during soldering can degrade the mechanical properties and reliability of a solder joint in electronic packaging. Therefore, it is critical to control IMC growth at the solder joints between the solder and the substrate. In this study, we investigated the control of interfacial reactions and IMC growth by the layer-by-layer transfer of graphene during the reflow process at the interface between Sn-3.0Ag-0.5Cu (in wt %) lead-free solder and Cu. As the number of graphene layers transferred onto the surface of the Cu substrate increased, the thickness of the total IMC (Cu6Sn5 and Cu3Sn) layer decreased. After 10 repetitions of the reflow process for 50 s above 217 °C, the melting temperature of Sn-3.0Ag-0.5Cu, with a peak temperature of 250 °C, the increase in thickness of the total IMC layer at the interface with multiple layers of graphene was decreased by more than 20% compared to that at the interface of bare Cu without graphene. Furthermore, the average diameter of the Cu6Sn5 scallops at the interface with multiple layers of graphene was smaller than that at the interface without graphene. Despite 10 repetitions of the reflow process, the growth of Cu3Sn at the interface with multiple layers of graphene was suppressed by more than 20% compared with that at the interface without graphene. The multiple layers of graphene at the interface between the solder metal and the Cu substrate hindered the diffusion of Cu atoms from the Cu substrate and suppressed the reactions between Cu and Sn in the solder. Thus, the multiple layers of graphene transferred at the interface between dissimilar metals can control the interfacial reaction and IMC growth occurring at the joining interface.

Healing Graphene Defects Using Selective Electrochemical Deposition: Toward Flexible and Stretchable Devices.

Graphene produced by chemical-vapor-deposition inevitably has defects such as grain boundaries, pinholes, wrinkles, and cracks, which are the most significant obstacles for the realization of superior properties of pristine graphene. Despite efforts to reduce these defects during synthesis, significant damages are further induced during integration and operation of flexible and stretchable applications. Therefore, defect healing is required in order to recover the ideal properties of graphene. Here, the electrical and mechanical properties of graphene are healed on the basis of selective electrochemical deposition on graphene defects. By exploiting the high current density on the defects during the electrodeposition, metal ions such as silver and gold can be selectively reduced. The process is universally applicable to conductive and insulating substrates because graphene can serve as a conducting channel of electrons. The physically filled metal on the defects improves the electrical conductivity and mechanical stretchability by means of reducing contact resistance and crack density. The healing of graphene defects is enabled by the solution-based room temperature electrodeposition process, which broadens the use of graphene as an engineering material.

Penetration and lateral diffusion characteristics of polycrystalline graphene barriers.

We report penetration and lateral diffusion behavior of environmental molecules on synthesized polycrystalline graphene. Penetration occurs through graphene grain boundaries resulting in local oxidation. However, when the penetrated molecules diffuse laterally, the oxidation region will expand. Therefore, we measured the lateral diffusion rate along the graphene-copper interface for the first time by the environment-assisted crack growth test. It is clearly shown that the lateral diffusion is suppressed due to the high van der Waals interaction. Finally, we employed bilayer graphene for a perfect diffusion barrier facilitated by decreased defect density and increased lateral diffusion path.

Superstrong encapsulated monolayer graphene by the modified anodic bonding.

We report a superstrong adhesive of monolayer graphene by modified anodic bonding. In this bonding, graphene plays the role of a superstrong and ultra-thin adhesive between SiO2 and glass substrates. As a result, monolayer graphene presented a strong adhesion energy of 1.4 J m(-2) about 310% that of van der Waals bonding (0.45 J m(-2)) to SiO2 and glass substrates. This flexible solid state graphene adhesive can tremendously decrease the adhesive thickness from about several tens of µm to 0.34 nm for epoxy or glue at the desired bonding area. As plausible causes of this superstrong adhesion, we suggest conformal contact with the rough surface of substrates and generation of C-O chemical bonding between graphene and the substrate due to the bonding process, and characterized these properties using optical microscopy, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy.

Enhanced mechanical properties of graphene/copper nanocomposites using a molecular-level mixing process.

RGO flakes are homogeneously dispersed in a Cu matrix through a molecular-level mixing process. This novel fabrication process prevents the agglomeration of the RGO and enhances adhesion between the RGO and the Cu. The yield strength of the 2.5 vol% RGO/Cu nanocomposite is 1.8 times higher than that of pure Cu. The strengthening mechanism of the RGO is investigated by a double cantilever beam test using the graphene/Cu model structure.

Direct measurement of adhesion energy of monolayer graphene as-grown on copper and its application to renewable transfer process.

Direct measurement of the adhesion energy of monolayer graphene as-grown on metal substrates is important to better understand its bonding mechanism and control the mechanical release of the graphene from the substrates, but it has not been reported yet. We report the adhesion energy of large-area monolayer graphene synthesized on copper measured by double cantilever beam fracture mechanics testing. The adhesion energy of 0.72 ± 0.07 J m(-2) was found. Knowing the directly measured value, we further demonstrate the etching-free renewable transfer process of monolayer graphene that utilizes the repetition of the mechanical delamination followed by the regrowth of monolayer graphene on a copper substrate.