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We compare the pH sensing performance of non-functionalized carbon nanotubes (CNT) field-effect transistors (p-CNTFET) and CNTFET functionalized with a conjugated polyfluorene polymer (labeled FF-UR) bearing urea-based moieties (f-CNTFET). The devices are electrolyte-gated, PMMA-passivated, 5 µm-channel FETs with unsorted, inkjet-printed single-walled CNT. In phosphate (PBS) and borate (BBS) buffer solutions, the p-CNTFETs exhibit a p-type operation while f-CNTFETs exhibit p-type behavior in BBS and ambipolarity in PBS. The sensitivity to pH is evaluated by measuring the drain current at a gate and drain voltage of −0.8 V. In PBS, p-CNTFETs show a linear, reversible pH response between pH 3 and pH 9 with a sensitivity of 26 ± 2.2%/pH unit; while f-CNTFETs have a much stronger, reversible pH response (373%/pH unit), but only over the range of pH 7 to pH 9. In BBS, both p-CNTFET and f-CNTFET show a linear pH response between pH 5 and 9, with sensitivities of 56%/pH and 96%/pH, respectively. Analysis of the I–V curves as a function of pH suggests that the increased pH sensitivity of f-CNTFET is consistent with interactions of FF-UR with phosphate ions in PBS and boric acid in BBS, with the ratio and charge of the complexed species depending on pH. The complexation affects the efficiency of electrolyte gating and the surface charge around the CNT, both of which modify the I–V response of the CNTFET, leading to the observed current sensitivity as a function of pH. The performances of p-CNTFET in PBS are comparable to the best results in the literature, while the performances of the f-CNTFET far exceed the current state-of-the-art by a factor of four in BBS and more than 10 over a limited range of pH in BBS. This is the first time that a functionalization other than carboxylate moieties has significantly improved the state-of-the-art of pH sensing with CNTFET or CNT chemistors. On the other hand, this study also highlights the challenge of transferring this performance to a real water matrix, where many different species may compete for interactions with FF-UR. [ABSTRACT FROM AUTHOR]

Tip-enhanced Raman spectroscopy (TERS) combines the high specificity and sensitivity of plasmon-enhanced Raman spectroscopy with the high spatial resolution of scanning probe microscopy. TERS has gained a lot of attention from many nanoscience fields, since this technique can provide chemical and structural information of surfaces and interfaces with nanometric spatial resolution. Multiwalled carbon nanotubes (MWCNTs) are very versatile nanostructures that can be dispersed in organic solvents or polymeric matrices, giving rise to new nanocomposite materials, showing improved mechanical, electrical and thermal properties. Moreover, MWCNTs can be easily functionalized with polymers in order to be employed as specific chemical sensors. In this context, TERS is strategic, since it can provide useful information on the cooperation of the two components at the nanoscale for the optimization of the macroscopic properties of the hybrid material. Nevertheless, efficient TERS characterization relies on the geometrical features and material composition of the plasmonic tip used. In this work, after comparing the TERS performance of commercial Ag coated nanotips and home-made bulk Au tips on bare MWCNTs, we show how TERS can be exploited for characterizing MWCNTs mixed with conjugated fluorene copolymers, thus contributing to the understanding of the polymer/CNT interaction process at the local scale. [ABSTRACT FROM AUTHOR]