We report the superior capacitance of functionalized graphene prepared by controlled reduction of graphene oxide (GO). In a solvothermal method, GO dispersed in dimethylformamide (DMF) was thermally treated at a moderate temperature (150 °C), which allows a fine control of the density of functionalities. Surface functionalities on graphene would enable a high pseudocapacitance, good wetting property, and acceptable electric conductivity. A specific capacitance up to 276 F/g was achieved based on functionalized graphene at a discharge current of 0.1 A/g in a 1 M H 2 SO 4 electrolyte, which is much higher than the benchmark material. The excellent performance of the functionalized graphene signifies the importance of controlling the surface chemistry of graphene-based materials.

Metal-assisted chemical etching (MaCE) of silicon in conjunction with shaped catalysts was used to fabricate 3D nanostructures such as sloping channels, cycloids, and spirals along with traditional vertical channels. The investigation used silver nanorods, nanodonuts along with electron beam lithography (EBL)-patterned gold nanodiscs, nanolines, squares, grids, and star-shaped catalysts to show how catalyst shape and line width directly influence etching direction. Feature sizes ranging from micrometers down to 25 nm were achieved with aspect ratios of at least 10:1 and wall roughness of 10 nm or less. This research demonstrates the potential of MaCE as a new, maskless nanofabrication technology.

Pinned structures in conjunction with shaped catalysts are used in metalassisted chemical etching (MACE) of silicon to induce out-of-plane rotational etching. Sub-micro-and nanostructures are fabricated in silicon, which include scooped-out channels and curved subsurface horns, along with vertically oriented thin metal structures. Five different etching modes induced by catalyst and pinning geometry are identifi ed: 1) fully pinned-no etching, 2) rotation via twist, 3) rotation via delamination, 4) in-plane bending, and 5) swinging. The rotation angle is roughly controlled through catalyst geometry. The force and pressure experienced by the catalyst are calculated from the deformation of the catalyst and range between 0.5-3.5 μ N and 0.5-3.9 MPa, respectively. This is a new, simple method to fabricate 3D, heterogeneous sub-micro-and nanostructures in silicon with high feature fi delity on the order of tens of nanometers while providing a method to measure the forces responsible for catalyst motion during MACE.

In recent years metal-assisted chemical etching (MaCE) of silicon, in which etching is confined to a small region surrounding metal catalyst templates, has emerged as a promising low cost alternative to commonly used three-dimensional (3D) fabrication techniques. We report a new methodology for controllable folding of 2D metal catalyst films into 3D structures using MaCE. This method takes advantage of selective patterning of the catalyst layer into regions with mismatched characteristic dimensions, resulting in uneven etching rates along the notched boundary lines that produce hinged 2D templates for 3D folding. We explore the dynamics of the folding process of the hinged templates, demonstrating that the folding action combines rotational and translational motion of the catalyst template, which yields topologically complex 3D nanostructures with intimately integrated metal and silicon features.

The ability to fabricate 3D spiraling structures using metal-assisted chemical etching (MaCE) is one of the unique advantages of MaCE over traditional etching methods. However, control over the chirality of the spiraling structures has not been established. In this work, a systematic parametric study was undertaken for MaCE of star-shaped catalysts, examining the influence of arm shape, arm length, number of arms, center core diameter, and catalyst thickness on the rotation direction. This data was used to identify a set of geometric parameters that reliably induce rotation in a predefined direction such that large arrays of 3D spiraling structures can be fabricated with the same chirality. Electroless deposition into the MaCE template was used to examine the full etch path of the catalyst and an experimental fit was established to control rotation angle by adjusting the catalyst's center core diameter. The ability to fabricate large arrays of 3D spiraling structures with predefined chirality could have important applications in photonics and optoelectronics.

Metal-assisted Chemical Etching of silicon has recently emerged as a powerful technique to fabricate 1D, 2D, and 3D nanostructures in silicon with high feature fidelity. This work demonstrates that out-of-plane rotational catalysts utilizing polymer pinning structures can be designed with excellent control over rotation angle. A plastic deformation model was developed establishing that the catalyst is driven into the silicon substrate with a minimum pressure differential across the catalyst thickness of 0.4-0.6 MPa. Force-displacement curves were gathered between an Au tip and Si or SiO(2) substrates under acidic conditions to show that Derjaguin and Landau, Verwey and Overbeek (DLVO) based forces are capable of providing restorative forces on the order of 0.2-0.3 nN with a calculated 11-18 MPa pressure differential across the catalyst. This work illustrates that out-of-plane rotational structures can be designed with controllable rotation and also suggests a new model for the driving force for catalyst motion based on DLVO theory. This process enables the facile fabrication of vertically aligned thin-film metallic structures and scalloped nanostructures in silicon for applications in 3D micro/nano-electromechanical systems, photonic devices, nanofluidics, etc.

This work introduces and explores vapor phase metal‐assisted chemical etching (VP‐MaCE) of silicon as a method to bypass some of the challenges found in traditional liquid phase metal‐assisted chemical etching (LP‐MaCE). Average etch rates for Ag, Au, and Pd/Au catalysts are established at 31, 70, and 96 nm/min respectively, and the relationship between etch rate and substrate temperature is examined experimentally. Just as with LP‐MaCE, 3D catalyst motion is maintained and three‐dimensional structures are fabricated with nanoparticle‐ and lithography‐patterned catalysts. VP‐MaCE produces less microporous silicon compared with LP‐MaCE and the diffusion/reduction distance of Ag+ ions is significantly reduced. This process sacrifices etch rate for increased etch uniformity and lower stiction for applications in micro‐electromechanical systems (MEMS) processing.

In this work, we introduce a maskless, resist-free rapid prototyping method to fabricate three-dimensional structures using electron beam induced deposition (EBID) of amorphous carbon (aC) from a residual hydrocarbon precursor in combination with metal-assisted chemical etching (MaCE) of silicon. We demonstrate that EBID-made patterned aC coating, with thickness of even a few nanometers, acts as a negative "mask" for the etching process and is sufficient for localized termination of the MaCE of silicon. Optimal aC deposition settings and gold film thickness for fabrication of high-aspect-ratio nanoscale 3D silicon structures are determined. The speed necessary for optimal aC feature deposition is found to be comparable to the writing speed of standard Electron Beam Lithography and the MaCE etching rate is found to be comparable to standard deep reactive ion etching (DRIE) rate.