Surface-initiated Cu(0) mediated controlled radical polymerization (SI-CuCRP) using a copper plate

Zhang, Tao; Du, Yunhao; Müller, Felix; Amin, Ihsan; Jordan, Rainer

doi:10.1039/c5py00093a

Cited by 97 publications

(187 citation statements)

References 39 publications

(57 reference statements)

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“…X-ray photoelectron spectroscopy (XPS) unambiguously confirmed the identity of the PMETAC layer (Fig. In agreement with previous results with smaller substrates, 19 no free polymer could be isolated by a The monomer solution showed two layers due to the poor dissolution of MMA in methanol/water mixture, both of the two layers used for SI-CuCRP but only from the lower aqueous layer brush formation was obtained. Optical inspection of the wafer revealed only partial inhomogeneities and a thin, approx.…”

Section: Preparation Of Polymer Brushes On the Wafer-scalesupporting

confidence: 89%

“…19 The resulting brush layer thickness, h, was found to be a direct function of the distance, D, between the copper plate and the initiator bearing substrate. 19 The resulting brush layer thickness, h, was found to be a direct function of the distance, D, between the copper plate and the initiator bearing substrate.…”

Section: Copper Plate Proximity Printing (Cp 3 )mentioning

confidence: 97%

“…0.7 × 1.5 cm) modified with a SAM of a stan-dard ATRP initiator (surface-bound 2-bromoisobutyryl bromide, APTES-BiBB) was covered by a copper plate leaving a gap of D = 0.5 mm with the aid of two spacers and then fixed by a clamp. 19 Neither the solvent nor the monomers were de-oxygenated and the entire assembling was performed in air.…”

Section: Oxygen Tolerance Of Si-cucrpmentioning

confidence: 99%

“…copper) consumption by constant regeneration of the activator (Cu(I) species) from the Cu(II) deactivator by in situ reduction by chemical, 12,14 electro-15 or photochemical means 16 or with a sacrificial anode. 19 The SI-CuCRP is performed without the addition of copper salts or reducing agents and only with a solvent, a ligand, a monomer and a copper plate as the metal source is needed. Recently, Dunderdale et al 14 developed the "paint-on"-ATRP to create very thick poly(2-(dimethylamino)ethyl methacrylate) (PDMEMA) polymer brushes over very large areas and under ambient conditions with ascorbic acid as the reducing agent.…”

Section: Introductionmentioning

confidence: 99%

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Wafer-scale synthesis of defined polymer brushes under ambient conditions

et al. 2015

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A method is presented that allows for the first time the preparation of highly defined polymer brush coatings on the wafer-scale under ambient conditions (room temperature, exposure to air) from a broad variety of monomers. The discovered high oxygen-tolerance of the surface-initiated Cu(0)-mediated controlled radical polymerization (SI-CuCRP) yields entire wafers homogeneously covered by a polymer brush of linear, high molar mass polymers with narrow dispersities (Đ = 1.1) at extremely high grafting densities (≈1 chain per nm 2 ). The low-tech and air tolerant method requires only ≲4 mL reaction solution containing a monomer and a ligand between two facing substrates. Thus, the SI-CuCRP is scalable to any surface area with minimal costs and minimal equipment. Despite the simplicity of the method, the high endgroup fidelity of SI-CuCRP is demonstrated by the preparation of a tetrablock copolymer brush which is the first example of a higher order block copolymer brush prepared by any surface-initiated polymerization. Finally, we present a new facile lithographic technique, the copper plate proximity printing (CP 3 ), which relies on the proximity of the bulk copper surface to the initiator-bearing substrate. The CP 3 is resist-and development-free and transfers the copper plate profile (of a copper coin) directly into an image composed of a 3D polymer brush. † Electronic supplementary information (ESI) available. See

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Section: Preparation Of Polymer Brushes On the Wafer-scalesupporting

confidence: 89%

Section: Copper Plate Proximity Printing (Cp 3 )mentioning

confidence: 97%

Section: Oxygen Tolerance Of Si-cucrpmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Wafer-scale synthesis of defined polymer brushes under ambient conditions

et al. 2015

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“…16 Furthermore, the conductivity of conjugated polymers in cast films is hindered due to the disturbed transport of charge carriers as macromolecules in bulk are disordered. 23,24 However, formation of conjugated polymer brushes cannot be directly realized by such powerful and versatile methods like SI-CRP. Surface grafting is one of the methods, which enable the formation of a stable platform for covalently attached conjugated macromolecules that are perpendicularly oriented to the surface.…”

Section: Introductionmentioning

confidence: 99%

Conductive polythiophene-based brushes grafted from an ITO surface via a self-templating approach

2015

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Conductive polythiophene-based brushes grafted from an indium tin oxide substrate were fabricated as promising materials with directional conductivity for potential optoelectronic applications. The obtained brushes, thanks to their ordered structure and large conjugation length, exhibited high conductivity after chemical doping. Surface-initiated photoiniferter mediated polymerization of a 3-methylthienyl methacrylate monomer was used in the first step of grafting enabling formation of dense brushes. In the second step a self-templating approach that utilized oxidative polymerization of the pendant thiophene groups in the grafted multimonomer chains was used for the formation of ladder-like conjugated brushes. The polymerization conditions were optimized towards the largest possible effective conjugation lengths of the macromolecules. The rate of the undesirable spontaneous iodine dedoping process was followed for the first time using conductive atomic force microscopy. UV-VIS and grazing angle IR spectroscopy were applied to find correlations between various synthetic procedures and the conjugation lengths of the brushes. † Electronic supplementary information (ESI) available: Additional results of AFM measurements, grazing angle IR spectra, UV-VIS spectra, XPS spectra, estimations of the brush conductivity and a movie showing C-AFM images changing in time. See

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Biorelated Polymer Brushes by Surface Initiated Reversible Deactivation Radical Polymerization

Pfukwa

Hlalele

Klumperman

2017

Polymers for Biomedicine

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Surface-initiated Cu(0) mediated controlled radical polymerization (SI-CuCRP) using a copper plate

Abstract: We report on a new, extremely fast, very simple and versatile method to produce polymer brushes by surface-initiated controlled/living radical polymerization.

Cited by 97 publications

References 39 publications

Wafer-scale synthesis of defined polymer brushes under ambient conditions

Wafer-scale synthesis of defined polymer brushes under ambient conditions

Conductive polythiophene-based brushes grafted from an ITO surface via a self-templating approach

Biorelated Polymer Brushes by Surface Initiated Reversible Deactivation Radical Polymerization

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