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6 Y. Yu, X. Wang / Extreme Mechanics Letters ( ) – Fig. 4. (a) Schematic illustration of ICP plasma modification process and the modified PET surface. (b) Open-circuit voltage, (c) short-circuit current, and (d) induced charge of TENGs assembled from pristine PET, plasma treated PET and PTFE films. (e, f) High-resolution XPS characterization and devolution of the C1s peak from the pristine (e) and modified (f) PET surfaces. (g) Schematics of two fluorination mechanisms during the plasma treatment. Source: Reprinted with permission from Ref. [65]. © 2015, Wiley-VCH the elemental compositions and their local chemical environments on the pristine and modified PET surfaces. Strong fluorine peak emerged in the full survey spectrum of the modified PET sample and no fluorine peak was found from the pristine PET film. C1s peaks were individually scanned with high resolution. As shown in Fig. 4(e), for the pristine PET, 66.3% of C–C, 18.4% of C–O and 15.3% of C=O bond can be recognized in the deconvoluted curves, agreeing well with the PET molecular formula. On the other hand, the deconvolution of C1s peak in the modified PET exhibited apparently reduced amount of C–C (23.3%), increased percentage of C–O (33.9%) and similar amount of C=O (13.3%) (Fig. 4(f)). Three new peaks were identified including CF (9.5%), CF2 (11.4%) and CF3 (8.6%). Based on these measurements, two possible reaction mechanisms were proposed for this fluorination process. During the plasma discharging, CF4 gas was decomposed into free radicals such as ·CF3 and :CF2. These active radicals were eager to recombine into CF4. However, the presence of O2 suppressed this process by forming ·COF and CO2, and releasing more ·F free radicals [67]. These free radicals reacted with PET macromolecules via two possible routes, named as ‘‘implantation’’ and ‘‘graphing’’ (Fig. 4(g)). For the ‘‘implantation’’ path, free radicals replaced hydrogen or added to pi bonds of the aromatic rings, forming reactive saturated intermediates [68]. For the ‘‘graphing’’ path, :CF2 radicals first replaced hydrogen, then further reacted with other free :CF2 , and eventually bonded to –CF2 –CF2 - chains [69]. In summary, developing fluorinated surfaces is a straightforward and effective approach to chemically mod- ifying triboelectric polymers. For the fluorocarbon plasma process, chemically and morphologically modified surfaces can be achieved simultaneously. Since the electron affin- ity of fluorine atom is extraordinarily high, fluorination could significantly enhance the materials’ ability of hold- ing electrons, giving rise to drastic performance gain of TENG devices. However, for the same reason, this method is only effective for improving polymers with negative tri- boelectric polarity. Although the majority of current TENGs are built on polymers with negative polarity, materials with positive polarity are frequently used for certain ap- plications (e.g. cottons for wearable electronics). Fluorina- tion would obviously jeopardize their performance by sup- pressing their tendency of losing electrons. 3. Ion injection Ion injection is another chemical modification approach with relatively broad source and target selections since aPDF Image | Chemical modification of polymer surfaces for advanced triboelectric nanogenerator development
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