Direct Quantitative Characterization of Polymer Brushes Obtained by Surface-Initiated ATRP on Silicon

Abstract

With respect to the increasing need for fully characterizing surface-tethered polymer brushes, the capacity of quantitative IR-Fourier transform infrared (FTIR) spectroscopy using a multiple-internal-reflection Si prism as the attenuated total reflection (ATR) element is investigated to directly characterize the surface chemical modifications occurring during a surface-initiated controlled polymerization. A simple two-step strategy is used involving first the covalent grafting of atom transfer radical polymerization (ATRP) initiators on a hydrogenated silicon surface and the subsequent polymerization of styrene. Three prefunctionalized surfaces designated Si-Br1, Si-Br2, and Si-Br3 are obtained by different procedures. The initiator grafting densities obtained by quantitative IR are 1.7 ± 0.3 nm–2 for Si-Br1, 1.5 ± 0.3 nm–2 for Si-Br2, and 0.9 ± 0.2 nm–2 for Si-Br3. After the polymerization of styrene under the same experimental conditions (grafting from without sacrificial initiators) and a careful Soxhlet rinse to remove physisorbed polymers formed in solution, almost no polymerization is observed using Si-Br1 with a value of the density in polymerized styrene units of 12 ± 2 nm–2, which is probably due to the chelating effect of the amino linkers used for grafting the initiators in Si-Br1. In contrast, the densities in styrene units are 54 ± 11 nm–2 using Si-Br2 and 141 ± 28 nm–2 using Si-Br3. The degree of polymerization (DP) has been evaluated by measuring the polymer thickness (by ellipsometry and atomic force microscopy, AFM) and using a scaling law relating the latter to DP for dry polymer brushes. High DP values of 200 and 1000 are found in the case of Si-Br2 and Si-Br3, respectively. The fraction of active polymerization initiators is found to be 15–18%, independent of the initiator surface density. In contrast, polymerization kinetics appear affected by steric hindrance and conformational disorder among grafted initiators. This approach for determining surface densities of grafted initiators and grafted polymer chains and DPs is fully generalizable to any other polymer system.

Threshold of Surface Initiator Concentration for Polymer Brush Growth by Surface-Initiated Atom Transfer Radical Polymerization

“…Based on these XPS results and the molecular size of organosilanes used, the maximum concentration of SIs within the SILs was estimated to be about 3 units/nm 2 from the atomic ratios (Table S6). This value was smaller than that of surface silanol (Si–OH) groups on the oxidized Si substrates (∼5 units/nm 2 ) and was in good agreement with previously reported values for the SAM-based SILs (3–4 units/nm 2 ) . Furthermore, the experimental SI concentration at DF of 10 (4.1 × 10 –1 units/nm 2 ) was in good agreement with that of the theoretical one (3.9 × 10 –1 units/nm 2 ) (Table S6).…”

“…This value was smaller than that of surface silanol (Si−OH) groups on the oxidized Si substrates (∼5 units/nm 2 ) 62 and was in good agreement with previously reported values for the SAM-based SILs (3−4 units/nm 2 ). 63 Furthermore, the experimental SI concentration at DF of 10 (4.1 × 10 −1 units/nm 2 ) was in good agreement with that of the theoretical one (3.9 × 10 −1 units/nm 2 ) (Table S6). Thus, our present results are concluded to be reasonable.…”

An ultrasensitive electrochemical sensor for phospholipase C via signal amplification based on breathing ATRP and its application

“…ATRP is typically performed in anaerobic environments because propagating radicals react with oxygen to form stable peroxy radicals and hydroperoxides, thus quenching chain growth. [20][21][22] Moreover, some ATRP methods use low-valence transition metal (such as Cu(I), Fe(II) and Ni(II)) complexes as catalysts, which are sensitive to O 2 . 23 Freeze-pump-thaw cycles, purging with inert gas, and working in a glovebox or Schlenk tube are the commonly used techniques to overcome the effect of oxygen for ATRP systems.…”