Ideal Passivation of Luminescent Porous Silicon by Thermal, Noncatalytic Reaction with Alkenes and Aldehydes

Boukherroub, Rabah; Morin, Sylvie; Wayner, Danial D. M.; Bensebaa, Farid; Sproule, G. I.; Baribeau, J.‐M.; Lockwood, D. J.

doi:10.1021/cm000790b

Cited by 151 publications

(150 citation statements)

References 54 publications

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“…Monolayers -A 0.2 M solution of succinimidyl 10-undecenoate in mesitylene containing 20 mM triethylsilyl chloride as an in situ drying agent [3,4] was placed into a flame-dried Schlenk flask kept under argon, degassed by five freeze-pump-thaw cycles (liquid N 2 , high vacuum, T room ) and held at room temperature under an argon atmosphere. The degassed solution was refluxed at 170˚ C for 15 minutes in an oil-bath to react residual water remaining in the flask with Et 3 SiCl, brought to 150˚ C and the freshly etched silicon rugate filter added.…”

Section: Modification Of Psi Rugate Filters Withmentioning

confidence: 99%

Introducing Distinctly Different Chemical Functionalities onto the Internal and External Surfaces of Mesoporous Materials

et al. 2008

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Section: Modification Of Psi Rugate Filters Withmentioning

confidence: 99%

Introducing Distinctly Different Chemical Functionalities onto the Internal and External Surfaces of Mesoporous Materials

et al. 2008

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“…23 As a result, modification of the porous silicon surface appears highly attractive since it might provide a more stable surface which could be used as a tool, either for device applications or for the test of fundamental models aiming at explaining the mechanisms involved in the luminescence of porous silicon. 24 One strategy for achieving stability of PSi is to tether passivative ligands to the surface by reacting it with the silicon hydride covering freshly formed porous silicon, [25][26][27] but the stabilizing effect of the bulk silicon that leads to slow reaction kinetics hinders their use as surface modification agents. 28 As to silicon-based substrates, the most commonly used method for surface derivative is silanization, which generally occurs at the surface of SiO 2 .…”

Section: Introductionmentioning

confidence: 99%

Vapor-phase silanization of oxidized porous silicon for stabilizing composition and photoluminescence

Zhu

et al. 2009

Journal of Applied Physics

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A vapor-phase deposition approach to the silanization modification of the oxidized porous silicon ͑PSi͒ surface using ͑CH 3 O͒ 3 Si͑CH 2 ͒ 3 NH 2 has been exploited. Standard clean ͑SC͒-1 ͑NH 3 H 2 O / H 2 O 2 / H 2 O, 1:1:5,v/ v͒ and SC-2 ͓HCl/ H 2 O 2 / H 2 O ͑1:1:6,v/ v͔͒ solutions are utilized for the first time to obtain oxidized PSi and have been proved to be a very efficient combination for creating Si-OH species on the PSi surface. After the modification, an amine group terminated surface was successfully created as demonstrated by the contact angle with water, the x-ray photoelectron spectroscopy, and the Fourier transform infrared ͑FTIR͒ spectra. The influences of the surface derivatives on the composition stability of the PSi layer and on its photoluminescence properties were investigated by means of FTIR spectra, photoluminescence spectra, and time-resolved photoluminescence measurements.

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“…Thermal-and UVassisted hydrosilylation reactions are perhaps the most commonly cited silicon surface alkylation reactions. [81][82][83][84][85][86][87][88] These reactions have long been accepted by most (not all 83 ) groups to proceed via the addition of surface silicon radicals to unsaturated carboncarbon bonds. Furthermore, these reactions are commonly accepted to be initiated by the homolytic cleavage of the Si-H bond, which is accomplished either thermally or photolytically and results in reactive silicon radicals.…”

Section: Si H + Simentioning

confidence: 99%

Investigation into Effects of Instability and Reactivity of Hydride-Passivated Silicon Nanoparticles on Interband Photoluminescence

Radlinger¹

2000

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While silicon has long been utilized for its electronic properties, its use as an optical material has largely been limited due to the poor efficiency of interband transitions. However, discovery of visible photoluminescence (PL) from nanocrystalline silicon in 1990 triggered many ensuing research efforts to optimize PL from nanocrystalline silicon for optical applications. Currently, use of photoluminescent silicon nanoparticles (Si NPs) is commercially limited by: 1) the instability of the energy and intensity of the PL, and 2) the low quantum yield of interband PL from Si NPs.Herein, red-emitting, hydrogen-passivated silicon nanoparticles (H-Si NPs) were synthesized by thermally-induced disproportionation of a HSiCl 3 -derived (HSiO 1.5 )n polymer. The H-Si NPs produced by this method were then subjected to various chemical and physical environments to assess the long-term stability of the optical properties as a function of changing surface composition. This dissertation is intended to elucidate correlations between the reported PL instability and the observed changes in the Si NP surface chemistry over time and as a function of environment.First, the stability of the H-Si NP surface at slightly elevated temperatures towards reactivity with a simple alkane was probed. The H-Si NPs were observed by FT-IR spectroscopy to undergo partial hydrosilylation upon heating in refluxing hexane, in addition to varying degrees of surface oxidation. The unexpected reactivity of the Si surface in n-hexane supports the unstable nature of the H-Si NP surface, and furthermore implicates the presence of highly-reactive Si radicals on the surfaces of the Si NPs. We propose that reaction of alkene impurities with the Si surface radicals is largely responsible for the observed surface alkylation. However, we also present an alternate ii mechanism by which Si surface radicals could react with alkanes to result in alkylation of the surface.Next, the energy and intensity stability of the interband PL from H-Si NPs in the presence of a radical trap was probed. Upon addition of (2,2,6,6,-tetramethyl-piperidin-1-yl)oxyl (TEMPO), the energy and intensity of the interband transition was observed to change over time, dependent on the reaction conditions. First, when the reaction occurred at 4ºC with minimal light exposure, the interband transition exhibited a gradual hypsochromic shift to between 595 nm and 655 nm, versus the λ max of the original low energy emission peak at 700 nm, depending on the amount of TEMPO in the sample.Second, when the reaction proceeded at room temperature with frequent exposure to 360 nm irradiation, the original interband transition at 660 nm was quenched while a new peak at 575 nm developed. Based on all the data collected and analyzed, we assign the 595 -655 nm transition as due to interband exciton recombination from Si NPs with reduced diameters relative to the original Si NPs. We furthermore assign the 575 nm transition as due to an oxide-related defect state resulting from rapid oxidation of pho...

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Ideal Passivation of Luminescent Porous Silicon by Thermal, Noncatalytic Reaction with Alkenes and Aldehydes

Cited by 151 publications

References 54 publications

Introducing Distinctly Different Chemical Functionalities onto the Internal and External Surfaces of Mesoporous Materials

Introducing Distinctly Different Chemical Functionalities onto the Internal and External Surfaces of Mesoporous Materials

Vapor-phase silanization of oxidized porous silicon for stabilizing composition and photoluminescence

Investigation into Effects of Instability and Reactivity of Hydride-Passivated Silicon Nanoparticles on Interband Photoluminescence

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