Study of organic grafting of the silicon surface from 4-nitrobenzene diazonium tetrafluoroborate

Hadj, F. Ait El; Amiar, A.; Cherkaoui, Mohammed; Chazalviel, J.‐N.; Ozanam, F.

doi:10.1016/j.electacta.2012.03.072

Cited by 23 publications

(20 citation statements)

References 48 publications

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“…17 For instance, the modication of a silicon surface by graing using the electrochemical reduction of aryldiazonium salt has been conducted recently with the objective to passivate the silicon surface. 13,18,19 The aryldiazonium salt chemistry for surface modication, rst described by Pinson and co-workers, 20 is now quite common since diazonium salts are easily and rapidly prepared in one step from a wide range of anilines. 21 Furthermore, this technique allows the covalent attachment of aryl groups bearing functionalities such as alkyl, nitro, cyanide, carboxylic, ester, alcohol, thiol and halogenated groups to various surfaces (metals, semiconductors, textiles.).…”

Section: Introductionmentioning

confidence: 99%

Surface band structure of aryl-diazonium modified p-Si electrodes determined by X-ray photoelectron spectroscopy and electrochemical measurements

2013

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The influence of grafted organic layers, obtained by aryldiazonium cations reduction, on the surface properties of p-type silicon was investigated. These layers were characterized by X-ray photoelectron spectroscopy (XPS), infrared spectroscopy and electrochemical methods. The results indicate a passivation of the silicon surface, a decrease of the oxidation of silicon. The results from electrochemical and XPS measurements can be used together to quantify the shift of the surface energy bands of the semiconductor caused by the presence of these layers at the surface. These measurements are important to understand the interfacial properties of the semiconductor and this grafting method can thus be used to adjust the surface energy levels positions toward those of different chemical reactions.

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Section: Introductionmentioning

confidence: 99%

Surface band structure of aryl-diazonium modified p-Si electrodes determined by X-ray photoelectron spectroscopy and electrochemical measurements

2013

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“…The first cycle of both samples presents a reduction peak, located around −0.3 V vs. NHE for Si-H sample and around −1.1 V vs. NHE for the Si-OH sample. As the electroreduction of 4VP monomers in aqueous media is not possible, 10,17,28 the peak is attributed to the NBD reduction. Since the density of states of electrons in a semiconductor exists only above the conduction band and below the valence band, the transfer of electrons for the NBD reduction is carried out through the conduction band.…”

Section: Resultsmentioning

confidence: 99%

“…[17][18][19] Other studies on chemically oxidized Si surfaces [20][21][22][23][24] described a situation where the native oxide is thin enough to allow electron transfer for the NBD reduction to occur and gives rise to localized electron levels. These levels are called extrinsic surface states and are located in the bandgap of Si, modifying the property of the interface electric double layer.…”

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confidence: 99%

Review—The Mediating Effect of Chemically Oxidized Silicon Surface on the P4VP Electrografting for Silicon Electrical Insulation

Dequivre

Charlebois

Brisard

2017

ECS J. Solid State Sci. Technol.

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The P4VP electrografting process realized on chemically oxidized p-type silicon surface, instead of traditional oxide free surface, leads to a thicker grafted polymer film. In this paper, we studied the influence of the surface states generated during the chemical oxidation of the silicon surface, on the thickness of the P4VP film. We used electrochemical measurements and Mott-Schottky plot analysis to demonstrate that such an oxidized surface does not only allow the electrografting process to occur, but also increases the accumulation of electrons at the silicon interface. In this condition, the chemical oxidation of silicon surface enhances the electro-initiation of the P4VP electrografting process and promotes the polymer growth. Silicon based technologies are widely used in microelectronics. Traditionally, the electrical insulation of silicon surfaces is achieved through the Chemical Vapor Deposition (CVD) or the thermal growth of a silicon dioxide layer. Nevertheless, silicon insulation in highly non-planar microstructures like MEMS and vertical interconnects remains a challenge. For example, in 3D Integrated Circuit (3D IC) planar dies are stacked and connected to each other using vertical interconnections most often named Through Silicon Via (TSV).1,2 The insulation of high aspect ratio copper TSV using SiO 2 is problematic. Indeed, the insulation of the TSV must be realized at temperature below 400• C (to preserve the integrity of the underlying CMOS). The use of thermally grown silicon oxide is not possible as it requires a higher process temperature (typically over 600• C). CVD based SiO 2 processes are therefore utilized. Nevertheless, the deposition of a good conformal SiO 2 film to insulate high aspect ratio TSV is hardly achievable and is costly due to the required growth condition of CVD methods. 1,3 During the last decade, Si insulation using polymer films was developed as an alternative to traditional SiO 2 . Among them, the chemical vapor deposition of parylene (poly(p-xylylene)) films 3-6 and the electrografting of poly-4-vinylpyridine (P4VP) in aqueous media have shown promising results.7-9 Indeed, they can be deposited at room temperature or up to 300• C. 3,10 Parylene HT films have been demonstrated to be stable up to a temperature of 350• C 11 , to avoid the appearance of cracks and adhesion loss in the dielectric film. 5,12 Electrografted P4VP were shown to withstand temperatures up to 450• C, 8 making this process a more versatile alternative to SiO 2 and parylene for silicon insulation in microelectronic systems.The electrografted P4VP films present similar dielectric properties as those of SiO 2 films.8 They are highly conformal with strong adhesion properties (covalent bonds) with the Si surface. 7,10 It is also compatible with NiB electroless processes that can be used as a copper diffusion barrier layer.8 So far, the compatibility of the P4VP electrografting process has been reported on high aspect ratio copper TSV, such as used for silicon interposers 7,8 and in Via-Last integratio...

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“…After rinsing with distilled water, the substrate was immersed in hydrofluoric acid (HF 50% v/v) in order to eliminate the oxide layer formed. The cleaning cycle can be repeated several times until a perfectly hydrophobic surface is obtained indicating the substitution of Si-O bonds by Si-H bonds (hydrophobic) and consequently the disappearance of the oxide layer 18 . The silicon surface is finally rinsed rapidly and dried with nitrogen.…”

Section: Methodsmentioning

confidence: 99%

Electroless deposition of Ni-P on a silicon surface

et al. 2017

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The present article concerns the metallization of silicon substrates by deposition of the nickelphosphorus alloy produced by an autocatalytic chemical process. The deposition electrolyte is composed of a metal salt, a reducing agent (sodium hypophosphite), a complexing agent (sodium citrate) and a buffer (ammonium acetate). The deposition could only be carried out after activation of the silicon by fixing catalytic species on its surface. The immersion of the silicon samples in palladium chloride made it possible to produce relatively thick and regular Ni-P coatings. The immersion time was optimized. The activation of Si was characterized by XPS and the Ni-P coating by XPS and SEM. The electrochemical study did not show any real mechanism changes compared to the Ni-P deposition on a conductive surface.

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Study of organic grafting of the silicon surface from 4-nitrobenzene diazonium tetrafluoroborate

Cited by 23 publications

References 48 publications

Surface band structure of aryl-diazonium modified p-Si electrodes determined by X-ray photoelectron spectroscopy and electrochemical measurements

Surface band structure of aryl-diazonium modified p-Si electrodes determined by X-ray photoelectron spectroscopy and electrochemical measurements

Review—The Mediating Effect of Chemically Oxidized Silicon Surface on the P4VP Electrografting for Silicon Electrical Insulation

Electroless deposition of Ni-P on a silicon surface

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