Roughness Suppression in Electrochemical Nanoimprinting of Si for Applications in Silicon Photonics.

Metal-assisted electrochemical nanoimprinting (Mac-Imprint) scales the fabrication of micro- and nanoscale 3D freeform geometries in silicon and holds the promise to enable novel chip-scale optics operating at the near-infrared spectrum. However, Mac-Imprint of silicon concomitantly generates mesoscale roughness (e.g., protrusion size ≈45 nm) creating prohibitive levels of light scattering. This arises from the requirement to coat stamps with nanoporous gold catalyst that, while sustaining etchant diffusion, imprints its pores (e.g., average diameter ≈42 nm) onto silicon. In this work, roughness is reduced to sub-10 nm levels, which is in par with plasma etching, by decreasing pore size of the catalyst via dealloying in far-from equilibrium conditions. At this level, single-digit nanometric details such as grain-boundary grooves of the catalyst are imprinted and attributed to the resolution limit of Mac-Imprint, which is argued to be twice the Debye length (i.e., 1.7 nm)-a finding that broadly applies to metal-assisted chemical etching. Last, Mac-Imprint is employed to produce single-mode rib-waveguides on pre-patterned silicon-on-insulator wafers with root-mean-square line-edge roughness less than 10 nm while providing depth uniformity (i.e., 42.9 ± 5.5 nm), and limited levels of silicon defect formation (e.g., Raman peak shift < 0.1 cm-1 ) and sidewall scattering.

Electroless Dealloying of Thin-Film Nanocrystalline Au-Ag Alloys: Mechanisms of Ligament Nucleation and Sources of Its Synthesis Variability.

Control of ligament size in nanoporous gold through process inputs in chemical dealloying holds the potential to exploit its size dependent properties in applications in energy and biomedicine. While its morphology evolution is regulated by the kinetics of coarsening, recent studies are focused on the early stage of dealloying (e.g., ∼ 5-42 at. % in residual alloy content) to understand mechanisms of ligament nucleation and its role in altering process-structure relationships. This paper examines this stage in chemical dealloying of nanocrystalline Au49Ag51 thin films and finds that ligaments are nucleated uniformly through its thickness due to the dealloying front rapidly propagating through the thickness of the film. Further, through the establishment of process-structure relationships with large data sets (i.e., 80 samples), this paper quantifies sources of variability that alter the kinetics of ligament growth such as aging of the precursor (e.g., grain growth) and solution evaporation. It is found that ligament diameter is better predicted by the residual silver content rather than by the dealloying time even amidst both effects and independent control of ligament diameter and solid area fraction is demonstrated within a limited window.

Metal-Assisted Electrochemical Nanoimprinting of Porous and Solid Silicon Wafers.

Metal-assisted electrochemical imprinting (Mac-Imprint) is a combination of metal-assisted chemical etching (MACE) and nanoimprint lithography that is capable of direct patterning 3D micro- and nanoscale features in monocrystalline group IV (e.g., Si) and III-V (e.g., GaAs) semiconductors without the need of sacrificial templates and lithographical steps. During this process, a reusable stamp coated with a noble metal catalyst is brought in contact with a Si wafer in the presence of a hydrofluoric acid (HF) and hydrogen peroxide (H2O2) mixture, which leads to the selective etching of Si at the metal-semiconductor contact interface. In this protocol, we discuss the stamp and substrate preparation methods applied in two Mac-Imprint configurations: (1) Porous Si Mac-Imprint with a solid catalyst; and (2) Solid Si Mac-Imprint with a porous catalyst. This process is high throughput and is capable of centimeter-scale parallel patterning with sub-20 nm resolution. It also provides low defect density and large area patterning in a single operation and bypasses the need for dry etching such as deep reactive ion etching (DRIE).

Electrochemical nanoimprinting of silicon.

Scalable nanomanufacturing enables the commercialization of nanotechnology, particularly in applications such as nanophotonics, silicon photonics, photovoltaics, and biosensing. Nanoimprinting lithography (NIL) was the first scalable process to introduce 3D nanopatterning of polymeric films. Despite efforts to extend NIL's library of patternable media, imprinting of inorganic semiconductors has been plagued by concomitant generation of crystallography defects during imprinting. Here, we use an electrochemical nanoimprinting process-called Mac-Imprint-for directly patterning electronic-grade silicon with 3D microscale features. It is shown that stamps made of mesoporous metal catalysts allow for imprinting electronic-grade silicon without the concomitant generation of porous silicon damage while introducing mesoscale roughness. Unlike most NIL processes, Mac-Imprint does not rely on plastic deformation, and thus, it allows for replicating hard and brittle materials, such as silicon, from a reusable polymeric mold, which can be manufactured by almost any existing microfabrication technique.