Fluorinated alkyne-derived monolayers on oxide-free silicon nanowires via one-step hydrosilylation

Minh, Quyen Nguyen; Pujari, Sidharam P.; Wang, Bin; Wang, Zhaoyi; Haick, Hossam; Zuilhof, Han; Rijn, C.J.M. van

doi:10.1016/j.apsusc.2016.06.129

Cited by 13 publications

(17 citation statements)

References 49 publications

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“…32 Most modification processes for oxidized SiNW are based on silanization, 33 esterification, 34 and phosphonate attachment reactions, 35 although hydrosilylation in particular has been used heavily for oxide-free H-terminated SiNWs. 36−38 Each of these functionalization approaches typically requires at least several hours (sometimes even overnight) and often also elevated temperatures to reach completion, which strongly limits scale-up and concomitant industrial applications. Therefore, the quest for novel rapid and high-quality surface modification strategies is of utmost interest.…”

Section: Introductionmentioning

confidence: 99%

Organic Monolayers by B(C₆F₅)₃-Catalyzed Siloxanation of Oxidized Silicon Surfaces

2017

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Inspired by the homogeneous catalyst tris(pentafluorophenyl) borane [B(C6F5)3], which acts as a promotor of Si–H bond activation, we developed and studied a method of modifying silicon oxide surfaces using hydrosilanes with B(C6F5)3 as the catalyst. This dedihydrosiloxanation reaction yields complete surface coverage within 10 min at room temperature. Organic monolayers derived from hydrosilanes with varying carbon chain lengths (C8–C18) were prepared on oxidized Si(111) surfaces, and the thermal and hydrolytic stabilities of the obtained monolayers were investigated in acidic (pH 3) medium, basic (pH 11) medium, phosphate-buffered saline (PBS), and deionized water (neutral conditions) for up to 30 days. DFT calculations were carried out to gain insight into the mechanism, and the computational results support a mechanism involving silane activation with B(C6F5)3. This catalyzed reaction path proceeds through a low-barrier-height transition state compared to the noncatalyzed reaction path.

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Section: Introductionmentioning

confidence: 99%

Organic Monolayers by B(C₆F₅)₃-Catalyzed Siloxanation of Oxidized Silicon Surfaces

2017

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“…Similarly, the signal from silicon layer is given by (33) The carbon signal from the alkyl group is given by (34) The signal of adventitious carbon is given by (35) Similar to the ≡Si−(CH2)11−F surface, the total intensity of carbon signal is Substitution Level from the Ratio of C to Si. Taking the ratio of IC total /ISi also yields the same equation as Eq 23 23Similar to the ≡Si−(CH2)11−F surface, after putting all the constants into the Eq 22, the coverage is given by (24) For the ≡Si−(CH2)7−CH3 surface, the carbon to silicon ratio obtained from XPS is 0.362 (Table 4), Nchain = 8, and if we again assume k = 0.8, then the coverage is given by (36)a For the ≡Si−(CH2)11−CH3 surface, the carbon to silicon ratio obtained from XPS is 0.523 (Table 4), Nchain = 12, and if we again assume k = 0.8, then the coverage is given by (36)b…”

Section: Connection Between Attenuation Length and Atomic Density On mentioning

confidence: 99%

Reconsidering X-ray Photoelectron Spectroscopy Quantification of Substitution Levels of Monolayers on Unoxidized Silicon Surfaces

Luber

Buriak

2020

J. Phys. Chem. C

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The covalent functionalization of unoxidized silicon surfaces is of interest for a wide range of applications, and for fundamental studies linking surface functionalization and electronic properties. Determination of the level of substitution (yield) of a reaction on a silicon surface is necessary as the number of functional groups bound to the surface is directly linked to properties. X-ray photoelectron spectroscopy (XPS), is the most common analytical method for determining the substitution level of the chemical handle on the silicon surface, typically a Si-H or Si-Cl bond, through which a new stable bond is formed to link the molecule to the surface. Calculations using the atomic ratio of carbon to silicon as determined by XPS do not take into account the effect of adventitious carbon, retained solvent and the substitution level is typically measured by first assuming 100% substitution of a fictitious hydrocarbon layer with an effective thickness that is determined by XPS intensity ratio of C to Si, and then the real substitution level is taken as the ratio of the effective thickness to the theoretical height of the molecule. In this work, we take an alternative and more physically meaningful approach to deriving expressions for the substitution level, where the photoelectron attenuation length is proportional to the substitution level. For all-hydrocarbon molecules grafted to a silicon surface, this new approach yields the same equations for substitution levels as an earlier effective thickness model. More importantly, unlike the effective thickness models, this method can be extended to include molecules with a heteroatom "tag", such as fluorine and chalcogenides, for determining coverage by XPS; this latter approach is shown to provide a greater degree of certainty with respect to calculating coverage on silicon. We finish with a simple flowchart to guide the reader to the appropriate equation for both Si(111) and Si(100) surfaces.

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“…Different headgroups to methyl could be used as well. For example, fluorinated 1‐hexadecyne‐derived monolayers on silicon nanowires showed a proper chemical passivation effect, since the contact angle hardly changed during exposure to acidic (pH 3) or basic solutions (pH 11) for 1 week . Next to the beneficial passivation effect observed for unsaturated end groups, these moieties allow for secondary functionalization.…”

Section: Surface Passivationmentioning

confidence: 99%

Applications of Monolayer‐Functionalized H‐Terminated Silicon Surfaces: A Review

Veerbeek

Huskens

2017

Small Methods

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Silicon is an attractive semiconductor material for wide‐ranging applications, from electronics and sensing to solar cells. Functionalization of H‐terminated silicon surfaces with molecular monolayers can be used to tune the properties of the material toward a desired application. Several applications require the removal of the, often insulating, silicon oxide between the silicon surface and a monolayer, thus precluding the more conventional silane‐based chemistry. Here, the applications of monolayer‐functionalized silicon surfaces are surveyed starting from H‐terminated silicon. The oxide‐free routes available for Si–C, Si–N, Si–O–C, and Si–S bond formation are described, of which the most commonly used techniques include hydrosilylation and a chlorination/alkylation route onto H‐terminated silicon. Applications are subdivided into the areas of surface passivation, electronics, doping, optics, biomedical devices, and sensors. Overall, these methods provide great prospects for the development of stabilized silicon micro‐/nanosystems with engineered functionalities.

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Fluorinated alkyne-derived monolayers on oxide-free silicon nanowires via one-step hydrosilylation

Cited by 13 publications

References 49 publications

Organic Monolayers by B(C₆F₅)₃-Catalyzed Siloxanation of Oxidized Silicon Surfaces

Organic Monolayers by B(C₆F₅)₃-Catalyzed Siloxanation of Oxidized Silicon Surfaces

Reconsidering X-ray Photoelectron Spectroscopy Quantification of Substitution Levels of Monolayers on Unoxidized Silicon Surfaces

Applications of Monolayer‐Functionalized H‐Terminated Silicon Surfaces: A Review

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Fluorinated alkyne-derived monolayers on oxide-free silicon nanowires via one-step hydrosilylation

Cited by 13 publications

References 49 publications

Organic Monolayers by B(C6F5)3-Catalyzed Siloxanation of Oxidized Silicon Surfaces

Organic Monolayers by B(C6F5)3-Catalyzed Siloxanation of Oxidized Silicon Surfaces

Reconsidering X-ray Photoelectron Spectroscopy Quantification of Substitution Levels of Monolayers on Unoxidized Silicon Surfaces

Applications of Monolayer‐Functionalized H‐Terminated Silicon Surfaces: A Review

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Organic Monolayers by B(C₆F₅)₃-Catalyzed Siloxanation of Oxidized Silicon Surfaces

Organic Monolayers by B(C₆F₅)₃-Catalyzed Siloxanation of Oxidized Silicon Surfaces