Nanostructuring of Si substrates by a metal-assisted chemical etching and dewetting process

Stafiniak, Andrzej; Prazmowska, Joanna; Macherzyński, W.; Paszkiewicz, R.

doi:10.1039/c8ra03711f

Cited by 14 publications

(18 citation statements)

References 34 publications

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“…The wet chemical structuring of silicon is of great importance for various applications in photonics, microsystems technology, microelectronics and sensor technology [ 1 ]. The process of metal-assisted etching to create special spatial structures is the topic of interest [ 2 , 3 , 4 ]. Despite very intensive investigations, not all details of the reactions occurring during metal-assisted etching have yet been clarified [ 5 ].…”

Section: Introductionmentioning

confidence: 99%

The Kinetics and Stoichiometry of Metal Cation Reduction on Multi-Crystalline Silicon in a Dilute Hydrofluoric Acid Matrix

Schönekerl

Acker

2020

Nanomaterials

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In this study, the process of metal cation reduction on multi-crystalline silicon in a dilute hydrofluoric acid (HF) matrix is described using Ag(I), Cu(II), Au(III) and Pt(IV). The experimental basis utilized batch tests with various solutions of different metal cation and HF concentrations and multi-crystalline silicon wafers. The metal deposition kinetics and the stoichiometry of metal deposition and silicon dissolution were calculated by means of consecutive sampling and analysis of the solutions. Several reaction mechanisms and reaction steps of the process were discussed by overlaying the results with theoretical considerations. It was deduced that the metal deposition was fastest if the holes formed during metal ion reduction could be transferred to the valence bands of the bulk and surface silicon with hydrogen termination. By contrast, the kinetics were lowest when the redox levels of the metal ion/metal half-cells were weak and the equilibrium potential of the H3O+/H2 half-cells was high. Further minima were identified at the thresholds where H3O+ reduction was inhibited, the valence transfer via valence band mechanism was limited by a Schottky barrier and the dissolution of oxidized silicon was restricted by the activity of the HF species F−, HF2− and H2F3−. The findings of the stoichiometric conditions provided further indications of the involvement of H3O+ and H2O as oxidizing agents in addition to metal ions, and the hydrogen of the surface silicon termination as a reducing agent in addition to the silicon. The H3O+ reduction is the predominant process in dilute metal ion solutions unless it is disabled due to the metal-dependent equilibrium potential of the H3O+/H2 half-cell and the energetic level of the valence bands of the silicon. As silicon is not oxidized up to the oxidation state +IV by the reduction of the metal ions and H3O+, water is suspected of acting as a secondary oxidant. The stoichiometric ratios increased up to a maximum with higher molalities of the metal ions, in the manner of a sigmoidal function. If, owing to the redox level of the metal half-cells and the energetic level of the valence band at the metal–silicon contact, the surface silicon can be oxidized, the hydrogen of the termination is the further reducing agent.

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Section: Introductionmentioning

confidence: 99%

The Kinetics and Stoichiometry of Metal Cation Reduction on Multi-Crystalline Silicon in a Dilute Hydrofluoric Acid Matrix

Schönekerl

Acker

2020

Nanomaterials

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“…The dissolution by H2O2 of deposited Ag followed by its re-deposition may also play a role in remote etching. This process has been demonstrated, for example, by Chiappini et al 20 Most commonly, Ag is used as the catalyst in MACE, although other noble metals, such as Au, Pd and Pt 37 as well as Ru, 38 Rh 39 and Ni 40 have been reported. MACE may either be performed in a onestep (metal precursor and oxidant combined) or two-step (metal precursor and oxidant in separate solutions) process 1,4,32,41 .…”

Section: Table Of Contents Graphicmentioning

confidence: 98%

Controlling the Nature of Etched Si Nanostructures: High- versus Low-Load Metal-Assisted Catalytic Etching (MACE) of Si Powders

Tamarov

Swanson

Unger

et al. 2019

ACS Appl. Mater. Interfaces

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“…Their approach is considered to be an economical improvement of large-scale production of BSi solar cells because of the self-assembly properties of Ni-etched MACE. The lift-off problem during the MACE method was previously addressed by Stafiniak et al where they proposed the use of Ni nanoparticles because they can be easily removed from the Si substrate, compared to other metal nanoparticles, and they are not oxidized at room temperature and do not leave any unwanted stains on the BSi surface [71]. Their experimental study aimed to fabricate patterned BSi textured surfaces with wider ranges of lateral dimension and density.…”

Section: Nickel (Ni)mentioning

confidence: 99%

Fabrication of Black Silicon via Metal-Assisted Chemical Etching—A Review

et al. 2021

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The metal-assisted chemical etching (MACE) technique is commonly employed for texturing the wafer surfaces when fabricating black silicon (BSi) solar cells and is considered to be a potential technique to improve the efficiency of traditional Si-based solar cells. This article aims to review the MACE technique along with its mechanism for Ag-, Cu- and Ni-assisted etching. Primarily, several essential aspects of the fabrication of BSi are discussed, including chemical reaction, etching direction, mass transfer, and the overall etching process of the MACE method. Thereafter, three metal catalysts (Ag, Cu, and Ni) are critically analyzed to identify their roles in producing cost-effective and sustainable BSi solar cells with higher quality and efficiency. The conducted study revealed that Ag-etched BSi wafers are more suitable for the growth of higher quality and efficiency Si solar cells compared to Cu- and Ni-etched BSi wafers. However, both Cu and Ni seem to be more cost-effective and more appropriate for the mass production of BSi solar cells than Ag-etched wafers. Meanwhile, the Ni-assisted chemical etching process takes a longer time than Cu but the Ni-etched BSi solar cells possess enhanced light absorption capacity and lower activity in terms of the dissolution and oxidation process than Cu-etched BSi solar cells.

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Nanostructuring of Si substrates by a metal-assisted chemical etching and dewetting process

Abstract: In this work, we reported on the development of lithography-free technology for the fabrication of nanopatterned Si substrates.

Cited by 14 publications

References 34 publications

The Kinetics and Stoichiometry of Metal Cation Reduction on Multi-Crystalline Silicon in a Dilute Hydrofluoric Acid Matrix

The Kinetics and Stoichiometry of Metal Cation Reduction on Multi-Crystalline Silicon in a Dilute Hydrofluoric Acid Matrix

Controlling the Nature of Etched Si Nanostructures: High- versus Low-Load Metal-Assisted Catalytic Etching (MACE) of Si Powders

Fabrication of Black Silicon via Metal-Assisted Chemical Etching—A Review

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