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4 Y. Yu, X. Wang / Extreme Mechanics Letters ( ) – Fig. 2. (a) Schematic of fluorocarbon plasma modification process. (b) SEM and (c) high-magnification SEM images of PDMS hierarchical structures after plasma treatment. (d) The variation of voltage output versus plasma treating cycles. (e, f) Calculated vertical ionization energy of model complexes of (e) pristine PDMS layer and (f) plasma deposited fluorocarbon layer. Higher ionization energy was obtained from the fluorocarbon treated film, meaning the promoted electron attracting capability of the modified PDMS. Source: Reprinted with permission from Ref. [63]. © 2014, Elsevier source. Fig. 2(a)–(c) are the schematic and scanning elec- tron microscope (SEM) pictures of the hierarchical PDMS film used in the plasma treatment and TENG fabrications. After the fluorocarbon plasma, small holes emerged on the surfaces of PDMS islands. Fig. 2(d) shows the voltage outputs of TENGs that assembled from pristine PDMS and PDMS with different cycles of C4F8 plasma treatment (12 s per cycles). 1-cycle treatment sharply increased the volt- age from 124 to 193 V. Subsequently, the voltage output could be further improved with the increase of treating cycles, which was ascribed to the increasing amount of F atoms. A maximum voltage of 265 V was attained with 8-cycle treatment. Further extending the treating cycles resulted in a decrease of voltage output. This output re- duction was attributed to two reasons: the degradation of electrostatic induction caused by the thicker fluorocar- bon layer; and the influence of the roughness factor on PDMS surfaces. From the SEM observation (Fig. 2(c)), 1- cycle treatment can induce significant etching on the PDMS surfaces. This roughness was assumed to contribute to the output improvement. Within 8 cycles, the PDMS surface was found to be partially covered by fluorocarbon and the etching remained effective. After 8 cycles, fluorocarbon polymeric layer capped the entire PDMS surface and thus reduced the roughness factor, diminishing the etching con- tribution. Since the electric output of this TENG was largely im- proved, the electron binding energy of PDMS was expected to be appreciably enhanced by the C4F8 treatment. This as- sumption was verified by the first principle calculations. The relative ability of losing one electron of pristine PDMS and C4F8 modified PDMS were analyzed by calculating the vertical ionization energies of two model complexes (CH3 )3 Si(OSi(CH3 )2 )2 OSi(CH3 )3 and CF3 (CF2 –CF2 )2 CF3 , re- spectively. As shown in Fig. 2(e) and (f), the ionization en- ergies of PDMS and C4F8 modified PDMS were 8.98 and 12.31 eV, respectively, affirming the latter has larger elec- tron binding energy and higher tendency to gain electrons. If the PDMS film is thin and treated before curing, this fluorocarbon plasma approach could create wrinkled PDMS film with chemically modified surfaces [64]. Fig. 3(a) depicted the fabrication procedure of a wrinkled PDMS film and the corresponding TENG setup. PET/ITO film was used as the substrate for the spin-coated PDMS film as well as the counter electrode of the TENG. SEM and laser scanning microscope (LSM) characterizations in Fig. 3(b) demonstrated the curved topology of PDMS with an average width of ∼15 μm and height of ∼12 μm. The formation of this wrinkled surface was probably caused by the velocity from the fluorocarbon polymer. The disordered momentum of fluorocarbon ions would introduce the random deformation of PDMS. Another possible reason could be the different surface tension between the PDMS and the fluorocarbon polymer layer during the curing process. The chemical composition and bonding state of the modified PDMS film was explored by X-ray photoelectronPDF Image | Chemical modification of polymer surfaces for advanced triboelectric nanogenerator development
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