Metal‐assisted chemical etching (MacEtch) has shown tremendous success as an anisotropic wet etching method to produce ultrahigh aspect ratio semiconductor nanowire arrays, where a metal mesh pattern serves as the catalyst. However, producing vertical via arrays using MacEtch, which requires a pattern of discrete metal disks as the catalyst, has often been challenging because of the detouring of individual catalyst disks off the vertical path while descending, especially at submicron scales. Here, the realization of ordered, vertical, and high aspect ratio silicon via arrays by MacEtch is reported, with diameters scaled from 900 all the way down to sub‐100 nm. Systematic variation of the diameter and pitch of the metal catalyst pattern and the etching solution composition allows the extraction of a physical model that, for the first time, clearly reveals the roles of the two fundamental kinetic mechanisms in MacEtch, carrier generation and mass transport. Ordered submicron diameter silicon via arrays with record aspect ratio are produced, which can directly impact the through‐silicon‐via technology, high density storage, photonic crystal membrane, and other related applications.
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.
more » « less- Award ID(s):
- 1944750
- NSF-PAR ID:
- 10468279
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 34
- Issue:
- 43
- ISSN:
- 0935-9648
- Subject(s) / Keyword(s):
- ["silicon micromachining","electrochemical nanoimprinting","silicon","patterning"]
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1002/adma.202206608
