We demonstrate direct production of graphene on SiO2 by CVD growth of graphene at the interface between a Ni film and the SiO2 substrate, followed by dry mechanical delamination of the Ni using adhesive tape. This result is enabled by understanding of the competition between stress evolution and microstructure development upon annealing of the Ni prior to the graphene growth step. When the Ni film remains adherent after graphene growth, the balance between residual stress and adhesion governs the ability to mechanically remove the Ni after the CVD process. In this study the graphene on SiO2 comprises micron-scale domains, ranging from monolayer to multilayer. The graphene has >90% coverage across centimeter-scale dimensions, limited by the size of our CVD chamber. Further engineering of the Ni film microstructure and stress state could enable manufacturing of highly uniform interfacial graphene followed by clean mechanical delamination over practically indefinite dimensions. Moreover, our findings suggest that preferential adhesion can enable production of 2-D materials directly on application-relevant substrates. This is attractive compared to transfer methods, which can cause mechanical damage and leave residues behind.

The properties of carbon nanotube (CNT) networks and analogous materials comprising filamentary nanostructures are governed by the intrinsic filament properties and their hierarchical organization and interconnection. As a result, direct knowledge of the collective dynamics of CNT synthesis and self-organization is essential to engineering improved CNT materials for applications such as membranes and thermal interfaces. Here, we use real-time environmental transmission electron microscopy (E-TEM) to observe nucleation and self-organization of CNTs into vertically aligned forests. Upon introduction of the carbon source, we observe a large scatter in the onset of nucleation of individual CNTs and the ensuing growth rates. Experiments performed at different temperatures and catalyst particle densities show the critical role of CNT density on the dynamics of self-organization; low-density CNT nucleation results in the CNTs becoming pinned to the substrate and forming random networks, whereas higher density CNT nucleation results in self-organization of the CNTs into bundles that are oriented perpendicular to the substrate. We also find that mechanical coupling between growing CNTs alters their growth trajectory and shape, causing significant deformations, buckling, and defects in the CNT walls. Therefore, it appears that CNT-CNT coupling not only is critical for self-organization but also directly influences CNT quality and likely the resulting properties of the forest. Our findings show that control of the time-distributed kinetics of CNT nucleation and bundle formation are critical to manufacturing well-organized CNT assemblies and that E-TEM can be a powerful tool to investigate the mesoscale dynamics of CNT networks.

The controlled synthesis of hierarchically functionalized core/multishell particles is highly desirable for applications in medicine, catalysis, and separation. Here, we describe the synthesis of hierarchically structured metal-organic framework multishells around magnetic core particles (magMOFs) via layer-by-layer (LbL) synthesis. The LbL deposition enables the design of multishell systems, where each MOF shell can be modified to install different functions. Here, we used this approach to create controlled release capsules, in which the inner shell serves as a reservoir and the outer shell serves as a membrane after postsynthetic conversion of the MOF structure to a polymer network. These capsules enable the controlled release of loaded dye molecules, depending on the surrounding media.

Laser-induced plasma from an aluminum target in one-atmosphere argon background has been investigated with ablation using nanosecond ultraviolet (UV: 355 nm) or infrared (IR: 1064 nm) laser pulses. Time- and space-resolved emission spectroscopy was used as a diagnostics tool to have access to the plasma parameters during its propagation into the background, such as optical emission intensity, electron density, and temperature. The specific feature of nanosecond laser ablation is that the pulse duration is significantly longer than the initiation time of the plasma. Laser-supported absorption wave due to post-ablation absorption of the laser radiation by the vapor plume and the shocked background gas plays a dominant role in the propagation and subsequently the behavior of the plasma. We demonstrate that the difference in absorption rate between UV and IR radiations leads to different propagation behaviors of the plasma produced with these radiations. The consequence is that higher electron density and temperature are observed for UV ablation. While for IR ablation, the plasma is found with lower electron density and temperature in a larger and more homogenous axial profile. The difference is also that for UV ablation, the background gas is principally evacuated by the expansion of the vapor plume as predicted by the standard piston model. While for IR ablation, the background gas is effectively mixed to the ejected vapor at least hundreds of nanoseconds after the initiation of the plasma. Our observations suggest a description by laser-supported combustion wave for the propagation of the plasma produced by UV laser, while that by laser-supported detonation wave for the propagation of the plasma produced by IR laser. Finally, practical consequences of specific expansion behavior for UV or IR ablation are discussed in terms of analytical performance promised by corresponding plasmas for application with laser-induced breakdown spectroscopy.