A mechanism for electroless Cu plating onto Si

Filho, Sebastião Gomes dos Santos; Pasa, AndréA.; Hasenack, C. M.

doi:10.1016/s0167-9317(96)00040-8

Cited by 34 publications

(17 citation statements)

References 7 publications

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“…In a previous work, it was established that the concentration of copper is approximately proportional to the immersion time and it is substantially higher if the agitation condition is used for the apparatus in figure 1 (16). oxidation process occurs next to the Cu/Si interface during Cu plating in D-HF/CuSO 4 baths and corroborates the a weak evidence already presented (16).…”

Section: Electroless Copper Plating Onto (100)si In Cuso 4 /D-hf Bathssupporting

confidence: 76%

“…On the other hand, in a previous work (16), we proposed an indirect displacement mechanism for copper plating onto silicon surfaces during immersion in diluted hydrofluoric solutions (D-HF) containing Cu 2+ species. In this case, Si oxidation occurs at the Cu/Si interface followed by HF oxide etching and two electrons are transferred from silicon to copper, so that, for each Cu atom that plates, one Si atom from substrate is consumed and goes to the solution according to reactions 4 to 7 as follows: where surface Si atoms were labeled "Si S " and "=Si S H 2 " represents a dihydride termination for <100> silicon surfaces.…”

Section: Introductionmentioning

confidence: 98%

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Mechanisms of Cu Electroless Plating onto Si(100) in Diluted HF Acid Solutions Containing CuSO4 or CuCl2

2008

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Presented in this work are the mechanisms of Cu plating onto (100) Si surfaces in diluted hydrofluoric acid (D-HF) solutions containing CuSO4 or CuCl2. For D-HF/CuSO4 baths, it was observed that: (a) Si dissolution occurs; (b) For each atom of Cu which plates, one atom of Si is consumed; (c) Si oxidation occurs at the Cu/Si interface; (d) Bubbles of an inflammable gas were uniformly distributed over the Cu films. Also, for D-HF/CuCl2 baths, it was observed that: (e) Si dissolution occurs; (f) for each two atoms of Cu which plate, one atom of Si is consumed; (g) Oxygen was detected across the Cu films; (h) No bubble of gas appeared. Based on these observations, Si oxidation followed by silicon oxide etching was inferred to occur during Cu plating in D-HF/CuSO4 baths and Si dissolution induced by fluorine ions was inferred to occur during Cu plating in D-HF/CuCl2 baths.

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Section: Electroless Copper Plating Onto (100)si In Cuso 4 /D-hf Bathssupporting

confidence: 76%

Section: Introductionmentioning

confidence: 98%

Mechanisms of Cu Electroless Plating onto Si(100) in Diluted HF Acid Solutions Containing CuSO4 or CuCl2

2008

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“…The nuclei expand to nanoclusters [ 16 ], islands or dendrites [ 17 , 18 , 19 , 20 ] on the silicon surface according to the Stranski–Krastanov and Volmer–Weber principles [ 21 , 22 ], and then form thin (nm to µm) [ 6 , 12 , 19 , 23 , 24 ], usually microporous layers [ 16 , 17 ] on the silicon surface. Adhesion forces between metal and silicon are usually low [ 6 , 25 , 26 , 27 ]. Depending on the metal, different shapes are formed on the silicon surface, such as pits (Cu) [ 18 , 28 , 29 ], pores (Ag, Au, Pt) [ 6 , 16 , 19 , 30 ], threads or nanowires (Ag, Au) [ 16 , 18 , 19 , 23 , 24 , 29 , 30 , 31 , 32 , 33 , 34 ].…”

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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“…Deposition proceeds until a dielectric barrier is formed, halting electron transfer . An oxide etching is therefore often added to the solution to yield thicker films . Precise control of nanoparticles diameter and density with this approach is difficult due to the relatively high kinetic of the nanoparticles’ growth on the surface …”

Section: Introductionmentioning

confidence: 99%

Cu Nanoparticles on TiN by Electroless Deposition: Surface‐Mediated Diameter Control and Application to Si Nanowires Growth

Roussey

Martínez

Copéret

et al. 2017

Helvetica Chimica Acta

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Cu Nanoparticles on TiN coated silicon substrates were prepared from well‐defined molecular precursors [CuOtBu]4 in non‐aqueous solutions. The formation of nanoparticles takes place via galvanic displacement and allows for the formation of narrowly distributed Cu nanoparticles with controlled size ranging from 8 to 35 nm through the control of the oxidation state of the TiN surface. The activity of these nanoparticles arrays in low temperature Si nanowires growth by the vapor‐solid‐solid mechanism was also investigated and larger Cu nanoparticles were found to yield higher Si nanowires density.

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A mechanism for electroless Cu plating onto Si

Cited by 34 publications

References 7 publications

Mechanisms of Cu Electroless Plating onto Si(100) in Diluted HF Acid Solutions Containing CuSO4 or CuCl2

Mechanisms of Cu Electroless Plating onto Si(100) in Diluted HF Acid Solutions Containing CuSO4 or CuCl2

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

Cu Nanoparticles on TiN by Electroless Deposition: Surface‐Mediated Diameter Control and Application to Si Nanowires Growth

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