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Evidences for redox reaction driven charge transfer and mass transport in metal-assisted chemical etching of silicon.

ABSTRACT: In this work, we investigate the transport processes governing the metal-assisted chemical etching (MacEtch) of silicon (Si). We show that in the oxidation of Si during the MacEtch process, the transport of the hole charges can be accomplished by the diffusion of metal ions. The oxidation of Si is subsequently governed by a redox reaction between the ions and Si. This represents a fundamentally different proposition in MacEtch whereby such transport is understood to occur through hole carrier conduction followed by hole injection into (or electron extraction from) Si. Consistent with the ion transport model introduced, we showed the possibility in the dynamic redistribution of the metal atoms that resulted in the formation of pores/cracks for catalyst thin films that are ?30?nm thick. As such, the transport of the reagents and by-products are accomplished via these pores/cracks for the thin catalyst films. For thicker films, we show a saturation in the etch rate demonstrating a transport process that is dominated by diffusion via metal/Si boundaries. The new understanding in transport processes described in this work reconcile competing models in reagents/by-products transport, and also solution ions and thin film etching, which can form the foundation of future studies in the MacEtch process.

SUBMITTER: Kong L

PROVIDER: S-EPMC5100464 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Evidences for redox reaction driven charge transfer and mass transport in metal-assisted chemical etching of silicon.

Kong Lingyu L Dasgupta Binayak B Ren Yi Y Mohseni Parsian K PK Hong Minghui M Li Xiuling X Chim Wai Kin WK Chiam Sing Yang SY

Scientific reports 20161108

In this work, we investigate the transport processes governing the metal-assisted chemical etching (MacEtch) of silicon (Si). We show that in the oxidation of Si during the MacEtch process, the transport of the hole charges can be accomplished by the diffusion of metal ions. The oxidation of Si is subsequently governed by a redox reaction between the ions and Si. This represents a fundamentally different proposition in MacEtch whereby such transport is understood to occur through hole carrier co ...[more]

PMID: 27824123

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Project description:The combination of metal-assisted chemical etching (MACE) with colloidal lithography has emerged as a simple and cost-effective approach to nanostructure silicon. It is especially efficient at synthesizing Si micro- and nanowire arrays using a catalytic metal mesh, which sinks into the silicon substrate during the etching process. The approach provides a precise control over the array geometry, without requiring expensive nanopatterning techniques. Although MACE is a high-throughput solution-based approach, achieving large-scale homogeneity can be challenging because of the instability of the metal catalyst when the experimental parameters are not set appropriately. Such instabilities can lead to metal film fracture, significantly damaging the substrate and thus compromising the nanowire array quality. Here, we report on the critical parameters that influence the stability of the metal catalyst layer for achieving large-scale homogeneous MACE: etchant composition, metal film thickness, adhesion layer thickness, nanowire diameter and pitch, metal film coverage, Si/Au/etchant interface length, and crystalline quality of the colloidal template (grain size and defects). Our results investigate the origin of the catalyst film fracture and reveal that MACE experiments should be optimized for each Si wire array geometry by keeping the etch rate below a certain threshold. We show that the Si/Au/etchant interface length also affects the etch rate and should thus be considered when optimizing the MACE experimental parameters. Finally, our results demonstrate that colloidal templates with small grain sizes (i.e., <100 μm2) can yield significant problems during the pattern transfer because of a high density of defects at the grain boundaries that negatively affects the metal film stability. As such, this work provides guidelines for the large-scale synthesis of Si micro- and nanowire arrays via MACE, relevant for both new and experienced researchers working with MACE.

Dataset Information

Evidences for redox reaction driven charge transfer and mass transport in metal-assisted chemical etching of silicon.

Publications

Evidences for redox reaction driven charge transfer and mass transport in metal-assisted chemical etching of silicon.

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