Bioinspired Triboelectric Nanogenerators As Self‐Powered .

www.advancedsciencenews.comwww.afm-journal.dethe microstructured PDMS surface, the other triboelectriclayer composed of PTFE tiny burrs on the microstructuredPDMS surface, and a back electrode layer. The shielding layeris adopted to effectively screen electrostatic interferences toensure measurement accuracy, as recommended by previousstudy.[33] The cone-like PDMS microstructures on both the triboelectric layers are fabricated through the replication of thesurface of the C. zebrine leaf, which demonstrates relatively uniform cone-like morphology, as shown in Figure 1b and inset.The first molding of the original C. zebrine leaf allows the fabrications of PDMS with reverse patterns, and another moldingprocess on the resultant PDMS patterns yields the replicationof the array of cone morphology on PDMS substrate. Detailsof the fabrication processes are elaborated in the ExperimentalSection. This two-step templating approach allows facile replication of the array of the cone-shape microstructures, as shownin Figure 1c. The replicated microcones have an average heightof 25.7 µm with an average base diameter of 25.4 µm, and anaverage inter-cone distance of 33.6 µm. Under applied pressure, the arrays of cone-like microstructures on top and bottomtriboelectric layers can form interlocked contact, leading toenhanced frictional areas between the two layers. Due to thepercolation network in silicone matrix to achieve enhancedstretchability, AgNWs have been widely adopted to fabricateelectrodes and interconnects in stretchable electronics.[42] Inthis study, AgNWs were spray coated onto PDMS substrate toform the top shielding layer and back electrode, as well as thetriboelectric layer on the microstructured PDMS surface. Asshown in Figure 1d, the AgNWs conductive network can beclearly observed on the microcone structure. Meanwhile, sincePTFE has been known as an effective tribo-negative material,[29]PTFE tiny burrs in the size of micron or submicron weregenerated on top of microstructured PDMS surface throughevaporation and reactive ion etching (RIE) to enhance triboelectric effect, as shown in Figure 1e. It is pointed out that theformation of PTFE tiny burrs on the PDMS substrate is advantageous as they do not compromise the stretchability of the substrate. Therefore, the adoptions of silicone substrate, AgNWsand PTFE tiny burrs enable the stretchability of the overallTENG electronic skin sensor. The photograph of the overalldevice is shown in Figure 1f. Figure S1 (Supporting Information) illustrates the fabrication steps of the sensor and processdetails can be found in the Experimental Section.The working mechanism of the TENG e-skin as self-powered pressure sensor is based on triboelectric effect and electrostatic induction, as illustrated in Figure 2a. Under appliedpressure, the top and bottom triboelectric layers will be forcedto contact and the interlocking structures formed by the conelike morphology leads to increased frictional contact. Due to thedifferent abilities of electron affinities, equal amount of positive and negative charges are generated on the AgNWs of thetop tribo-layer and PTFE burrs/PDMS microstructures of thebottom tribo-layer, respectively (Figure 2aI). When the externalpressure is reduced and the two tribo-layers are separated, theAgNWs tribo-layer will have higher electric potential, while theback electrode of the bottom tribo-layer will have lower electricpotential. The electrostatic induction due to the difference inelectric potentials drives the electrons to flow from the backelectrode to the top AgNWs tribo-layer, leading to electric current flowing from top to bottom (Figure 2aII). This processproceeds until the external pressure reduces to zero withoutfurther variation, an electric equilibrium is achieved and thecharge transfer stops (Figure 2aIII). When the external pressureis applied again, electricity will flow in the reverse direction(Figure 2aIV), completing a full cycle of electricity generation.To investigate the performances of the TENG e-skin sensorfor pressure measurements, a motorized Z-stage was used incombination with a force gauge to apply well-defined pressure.The external pressure and electrical outputs were controlledand recorded simultaneously. Under cyclic loading pressure ofFigure 2. Detection of normal force. a) Working principle for detecting normal force. b–d) Open circuit voltage, short circuit current and transferredcharges of the TENG e-skin sensor under a pressure of 25 kPa. e) Synchronized force input and voltage output during cyclic loading of 25 kPa.Adv. Funct. Mater. 2019, 19073121907312 (3 of 9) 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.comwww.afm-journal.de25 kPa, the open circuit voltage (Voc), short circuit current Iscand transferred charge density σtr of the sensor are shown inFigure 2b–d, respectively. While all the output signals demonstrated excellent repeatability, the maximum ΔVoc, peak Isc andmaximum σtr reached 3.14 V, 26.29 nA, and 23.98 μC m 2,respectively. The ΔVoc is defined as Voc Vocnp, where Vocnp isthe negtive peak of the voltage signal. As one of the outputcharacteristics of the contact-separation mode TENGs, themaximum ΔVoc increases as the separation distance increases,as shown in Figure S2 (Supporting Information). The synchronized force input and open circuit voltage between theback electrode and top tribo-layer are shown in Figure 2e. Itis noticed that the voltage reached the maximum value whenthe applied force was fully retracted which corresponds to thelargest separation distance of the two tribo-layers. The voltagedecreased when the force was applied again and reached maximum value with reverse sign when the two tribo-layers completely contacted again (Figure 2e).It is noted that the combination of the bioinspired interlocking microstructures of cone-like morphology and theformation of PTFE tiny burrs significantly enhanced the triboelectrification during contact of the tribo-layers, leading tohigher sensitivity for pressure measurements. TENG sensorsof different microstructures and surface conditions were fabricated and their performances as pressure sensors were evaluated, as shown in Figure 3. Five types of sensors of the samesize were compared to systematically investigate the impact oftribo-layer surface conditions on sensitivity, including sensorsof flat AgNWs tribo-layer and flat PDMS tribo-layer (Flat), flatAgNWs tribo-layer and PDMS tribo-layer with cone-like microstructures (Flat Microstructures), interlocking AgNWs andPDMS tribo-layers with cone-like microstructures on both surfaces (Interlocking), interlocking AgNWs and PTFE tribo-layerswith PTFE film on the cone-like surface (Interlocking PTFEfilm), as well as interlocking AgNWs and PDMS/PTFEtribo-layers with PTFE tiny burrs on the cone-like surface(Interlocking PTFE burrs). The horizontal axis of Figure 3arepresents the maximum ΔVoc of the sensor output underapplied pressure, and the pressure measurement sensitivity ofthose five different sensors are calculated as 9.08, 20.59, 59.65,17.5, and 127.22 mV kPa 1, respectively, in the pressure rangeof 5–50 kPa. The interlocking structures of AgNWs and PDMStribo-layers lead to larger effective contact areas than those withflat surfaces, resulting in higher measurement sensitivity. However, the sensor with interlocking structures and PTFE filmdemonstrated relatively low sensitivity. This is potentially dueto the fact that the relatively thick film ( 150 µm) of PTFE withlarge modulus (860 MPa–1.6 GPa[43,44]), which is about fourorders of magnitude larger than PDMS ( 1–3 MPa),[45] resultsin significantly increased stiffness of the microstructures whichprohibits the interlocking contact under external load. Therefore, the formation of PTFE tiny burrs through RIE is criticalfor improved measurement sensitivity after the deposition ofthe PTFE film, as the tiny burrs distributed on the cone-likeFigure 3. Performances of the TENG e-skin sensor. a) Sensitivity comparisons of sensors with different microstructures and surface condition.b,c) Current and charge density output of different sensors during cyclic loading with maximum pressures of 25 kPa. d) Durability of the sensor testedfor 5000 cycles under a pressure of 25 kPa.Adv. Funct. Mater. 2019, 19073121907312 (4 of 9) 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.comwww.afm-journal.dePDMS structures can enhance triboelectric effect withoutincreasing the overall structure stiffness. Therefore, the e-skinsensors with interlocking microstructures and PTFE burrs havemuch higher sensitivity than the rest. The enhancement of triboelectric effect is also confirmed by the short circuit current Iscand transferred charge density σtr of the sensors under 25 kPaof cyclic loading pressure, as shown in Figure 3b,c, respectively.It is clear that both Isc and σtr are significantly boosted, i.e.,about an order of magnitude increase was achieved comparedwith sensors with other designs, when the interlocking structures and PTFE burrs are adopted. It is pointed out that thepresent bio-inspired TENG e-skin sensor also possesses theadvantage of high measurement sensitivity when comparedwith previously reported TENG pressure sensors of the similardevice structure. For instance, the micropyramid array patternedtriboelectric sensor presented by Jiang et al. demonstrated asensitivity of only 2.82 0.187 mV kPa 1,[46] while the hemispheres-array-structured TENG pressure sensor reported byLee et al. achieved a sensitivity of 28.8 mV kPa 1.[47] The bettersensitivity is attributed to two reasons: i) the soft bioinspiredinterlocking microstructures enable the increase of effectivefrictional areas, which could cause a larger change in potentialdifference per unit area under external load; ii) the presence ofthe PTFE tiny burrs on the PDMS microstructures enhancesthe triboelectric effect as PTFE is one the most effective tribonegative materials. The bioinspired TENG e-skin sensor alsodemonstrates excellent durability and stability. Although slightwear of AgNWs on the PDMS pillar occurred (Figure S3, Supporting Information), the sensor output remained consistentwithout degradation after 5000 cycles of loading tests withloading pressure of 25 kPa at a frequency of 0.5 Hz, as shownin Figure 3d. The high durability of the sensor can be attributedto the elasticity of the interlocking microstructures and percolation network formed by the AgNWs in the device structure.The bioinspired TENG e-skin sensor may also be applied tomeasure tangential sliding forces due to the presence of interlocking tribo-layers, as shown in Figure S4 (Supporting Information). The measurement mechanism is illustrated in Figure S4a(Supporting Information). When the two tribo-layers are in contact, equal amount of positive and negative charges are generated. Relative sliding motion of those two tribo-layers caused bythe external tangential force will lead to the variation of contactareas and the resultant potential difference between the AgNWstribo-layer and the back electrode, similar as the mechanismdemonstrated in Figure 2a. For tangential sliding force of 1 N,the maximum ΔVoc reached 0.012 V with a certain sliding displacement of 1 mm, and the simultaneously recorded tangentialsliding force and the maximum ΔVoc are presented in Figure S4b(Supporting Information). Larger tangential sliding forcemeans larger friction and more triboelectric charges, resultingin higher value of Voc unde

challenges, flexible or stretchable sensors based on capacitance,[15] piezoresistive,[16] optical or photonic effects[17] have been extensively investigated. However, capaci-tive and piezoresistive sensors require external power supply, which may be challenging to achieve for flexible systems.[18]