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Polymer Brushes via Surface-Initiated Electrochemically Mediated ATRP: Role of a Sacrificial Initiator in Polymerization of Acrylates on Silicon Substrates.

ABSTRACT: Silicon wafers as semiconductors are essential components of integrated circuits in electronic devices. For this reason, modification of the silicon surface is an important factor in the manufacturing of new hybrid materials applied in micro- and nanoelectronics. Herein, copolymer brushes of hydrophilic poly(2-hydroxyethyl acrylate) (PHEA) and hydrophobic poly(tert-butyl acrylate) (PtBA) were grafted from silicon wafers via simplified electrochemically mediated atom transfer radical polymerization (seATRP) according to a surface-initiated approach. The syntheses of PHEA-b-PtBA copolymers were carried out with diminished catalytic complex concentration (successively 25 and 6 ppm of Cu). In order to optimize the reaction condition, the effect of the addition of a supporting electrolyte was investigated. A controlled increase in PHEA brush thickness was confirmed by atomic force microscopy (AFM). Various other parameters including contact angles and free surface energy (FSE) for the modified silicon wafer were presented. Furthermore, the effect of the presence of a sacrificial initiator in solution on the thickness of the grafted brushes was reported. Successfully fabricated inorganic-organic hybrid nanomaterials show potential application in biomedicine and microelectronics devices, e.g., biosensors.

SUBMITTER: Flejszar M

PROVIDER: S-EPMC7475859 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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Polymer Brushes via Surface-Initiated Electrochemically Mediated ATRP: Role of a Sacrificial Initiator in Polymerization of Acrylates on Silicon Substrates.

Flejszar Monika M Chmielarz Paweł P Wolski Karol K Grześ Gabriela G Zapotoczny Szczepan S

Materials (Basel, Switzerland) 20200812 16

Silicon wafers as semiconductors are essential components of integrated circuits in electronic devices. For this reason, modification of the silicon surface is an important factor in the manufacturing of new hybrid materials applied in micro- and nanoelectronics. Herein, copolymer brushes of hydrophilic poly(2-hydroxyethyl acrylate) (PHEA) and hydrophobic poly(<i>tert</i>-butyl acrylate) (P<i>t</i>BA) were grafted from silicon wafers via simplified electrochemically mediated atom transfer radica ...[more]

PMID: 32806681

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Project description:Copper-catalyzed atom transfer radical polymerization (Cu-ATRP) is one of the most widely used controlled radical polymerization techniques. Notwithstanding the extensive mechanistic studies in the literature, the transition states of the activation/deactivation of the growing polymer chain, a key equilibrium in Cu-ATRP, have not been investigated computationally. Therefore, the understanding of the origin of ligand and initiator effects on the rates of activation/deactivation is still limited. Here, we present the first computational analysis of Cu-ATRP activation transition states to reveal factors that affect the rates of activation and deactivation. The Br atom transfer between the polymer chain and the Cu catalyst occurs through an unusual bent geometry that involves pronounced interactions between the polymer chain end and the ancillary ligand on the Cu catalyst. Therefore, the rates of activation/deactivation are determined by both the electronic properties of the Cu catalyst and the ligand-initiator steric repulsions. In addition, our calculations revealed the important role of ligand backbone flexibility on the activation. These theoretical analyses led to the identification of three chemically meaningful descriptors, namely HOMO energy of the catalyst ( EHOMO), percent buried volume ( Vbur%), and distortion energy of the catalyst (? Edist), to describe the electronic, steric, and flexibility effects on reactivity, respectively. A robust and simple predictive model for ligand effect on reactivity is thereby established by correlating these three descriptors with experimental activation rate constants using multivariate linear regression. Validation using a structurally diverse set of ligands revealed the average error is less than ±2 kcal/mol compared to the experimentally derived activation energies. The same approach was also applied to develop a predictive model for reactivity of different alkyl halide initiators using R-X bond dissociation energy (BDE) and Cu-X halogenophilicity as descriptors.

Dataset Information

Polymer Brushes via Surface-Initiated Electrochemically Mediated ATRP: Role of a Sacrificial Initiator in Polymerization of Acrylates on Silicon Substrates.

Publications

Polymer Brushes via Surface-Initiated Electrochemically Mediated ATRP: Role of a Sacrificial Initiator in Polymerization of Acrylates on Silicon Substrates.

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