Elastomeric transparent capacitive sensors based on an interpenetrating composite of silver nanowires and polyurethane

Weili Hu, Xiaofan Niu, Ran Zhao, and Qibing Pei Citation: Appl. Phys. Lett. 102, 083303 (2013); doi: 10.1063/1.4794143 View online: http://dx.doi.org/10.1063/1.4794143 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v102/i8 Published by the American Institute of Physics.

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edu. degassed. A second R 0003-6951/2013/102(8)/083303/5/$30. 083303-1 C 2013 American Institute of Physics V Downloaded 23 Jun 2013 to 144. [http://dx. conformable. Shanghai 201620. accepted 18 February 2013. The challenge still remains unresolved in developing an elastomeric electrode with low surface resistance and high visual transparency.org/about/rights_and_permissions . Smooth-On USA LLC) were mixed. The elastomeric sensors employ a pair of compliant electrodes comprising silver nanowire networks embedded in the surface layer of polyurethane matrix.203.10 The high sheet resistance of the SWNT coatings could limit the data speed and active area of these devices. high conductivity. though not as sensitive to low pressures as their previously reported microstructured sensors.1. The capacitance of the sensor sheets increases linearly with strains up to 60% during uniaxial stretching.3. AgNWs in the network are uniformly distributed and randomly oriented over the entire coating area as shown in Figure 1(a). The composite electrodes retain high surface conductance at tensile strains up to 60%. and can take various form factors in order to realize a plethora of user-friendly applications such as expandable displays.00 102. University of California. hand grip. conformable photovoltaic sheets. Its dispersion obtained from Seashell Technologies was diluted with methanol to a concentration of 2 mg/ml. stretchable transparent electrode is an indispensable element.2 Xiaofan Niu. For the fabrication of capacitive sensor arrays. USA 2 State Key Laboratory for Modification of Chemical Fibers and Polymer Materials. Henry Samueli School of Engineering and Applied Science. Urethane liquid rubber compounds (Clear FlexV 95. published online 28 February 2013) Highly flexible transparent capacitive sensors have been demonstrated for the detection of deformation and pressure. and can be stretched repeatedly with minimal loss of electrical conductivity under both slow and fast strain rates. The transparency could expand the application scope.doi. The preparation of the elastomeric transparent electrodes started with the formation of a conductive AgNW coating on glass. Replacing the touch screen with an electronic skin would significantly increase the amount of data input or the “livelihood” in each finger touch via pressure sensitivity. patterned AgNW coatings were deposited by spray-coating through a contact mask. In these device applications.1063/1. Reuse of AIP content is subject to the terms at: http://apl.ucla.13 This sensor. A variable capacitor using a pair of compliant electrodes sandwiching an elastomeric spacer can detect pressure or deformation in the change of capacitance. high transparency. California 90095. we report the fabrication of a highperformance transparent electrode by embedding an ultrathin silver nanowire (AgNW) network in the surface layer of an elastomeric polyurethane (PU) matrix. coatings.122. which could detect pressures generated by a fly weighing about 20 mg.19 AgNWs with an average diameter of 60 nm and an average length of 10 lm were employed.5 Future robots wearing such a flexible pressuresensitive skin can “feel” a touch or pressure. and linearly with externally applied transverse pressure from 1 MPa down to 1 kPa. Stretchable sensor arrays consisting of 10 Â 10 pixels have also been fabricated by patterning the composite electrodes into X-Y addressable C 2013 American Institute of Physics. 083303 (2013) Elastomeric transparent capacitive sensors based on an interpenetrating composite of silver nanowires and polyurethane Weili Hu. such as touch screens and electronic skins with various options of skin color. Donghua University. capacitive touch sensors found on most current smartphones and tablet computers do not differentiate pressure differences. Cohen et al. China 1 (Received 12 January 2013. drop-cast on a precleaned glass substrate. and in-shoe pressures.1.6 Being stretchable and able to detect the pressure or deformation at the same time would allow for feedback control. Here.4794143] passive matrix. An electronic skin could also be used for advanced prosthetic limbs or applied as surgical gloves to perform feel-real remote operations. The addition of pressure sensing could make the touch screen more intuitive for users. dried and annealed on a hotplate for 30 min at 190  C to form a conductive AgNW coating.1–4 Pressure sensors strategically placed on a flexible synthetic skin working in the pressure range of 1 kPa to 1 MPa would be able to detect fingertip texture. The resulting variable capacitors can detect pressure and deformation in a wide range of stretching and pressure conditions. is stretchable and transparent. and artificial skins. Patients with prosthetic hand or limbs equipped with such artificial skins could completely regain dexterity and maneuverability.1 Ran Zhao. Department of Materials Science and Engineering. In consumer electronics. Several methods have been reported in the literature for the preparation of stretchable electrodes. The patterned AgNW coatings were annealed under the same condition as the un-patterned AgNW coatings. This article is copyrighted as indicated in the abstract.1 and Qibing Pei1.a) Department of Materials Science and Engineering. Los Angeles. reported elastic strain gauges based on percolation SWNT a) Electronic mail: qpei@seas.APPLIED PHYSICS LETTERS 102. and a low-cost large-area fabrication.org/10.14–19 However.1.aip. V Future electronics are expected to be flexible. and then dropcast over the AgNW coatings on glass substrate. and a highly compliant dielectric spacer sandwiched between the electrodes.7 High visual transparency is required for such applications.8–12 The Bao’s group recently reported a skin-like capacitive sensor based on single-walled carbon nanotubes (SWNTs) with detectable pressure of 50 kPa and strain up to 50%. High-performance stretchable transparent capacitors can be readily fabricated by sandwiching an acrylic elastomer layer between two AgNW-PU composite electrodes. none has simultaneously achieved high stretchability.

Changes of the surface resistance of the AgNW-PU composites under various tensile strains were measured at room temperature. Appl.7 X/sq. This article is copyrighted as indicated in the abstract. The values are 1–2 orders of magnitude lower than typical SWNT percolation networks.3. The elongation was accompanied by an increase in the surface resistance R.2. Lett.2% at 24. (a) SEM image of a AgNW coating on a glass substrate. The composite sheets could be stretched reversibly up to 170% strain. Phys. the resulting composite is a transparent sheet with a thickness of 340 lm. At relatively small strains.0. 083303 (2013) FIG.7% at 550 nm wavelength when the sheet resistance is 44. and prevents the formation of voids between the nanowires and the matrix. which implies a complete transfer of the nanowires from the original glass substrate. the AgNWs on the surface form a conductive pathway and interconnect with the embedded AgNWs. These sheet resistance values are almost the same as the original AgNW coatings on glass. sheet of glass was pressed onto the liquid coating. 32. (a) Normalized resistance of the composite electrodes as a function of tensile strain with specified initial sheet resistances. the Rnorm increases with strain due to geometrical changes during a uniaxial stretching following the equation:21 Rnorm ¼ ð1 þ strainÞ2 : (1) As Figure 2(a) inset shows. The AgNW network is clearly seen to be buried in the surface of the composites and no voids are left on the composite surface. thanks to the ability of silver to fuse at the nanowire intersections.6% at 8. The PU employed exhibits rubbery elasticity. 1. (b) Normalized resistance of the composite electrodes with the initial sheet resistances of 8 X/sq during one stretching/releasing cycle at different stretching speeds. and 20. and the composite retains this property.122. the surface resistance remained unchanged.0 X/sq. 2. indicative of no nanowires being removed from the composite. This observation indicates that during smallstrain stretching. The transmittance. the normalized resistance increases somewhat linearly with strain for samples with various initial sheet resistances. defined as the ratio of the instantaneous resistance at a specific tensile strain to the initial resistance at zero strain. As strain is further increased.1 times the initial resistance for the films with initial sheet resistance values of 8.1.9. the resistance has increased to roughly 5.7 X/sq. At 60% strain. 24.1. 14. The PU monomer deposited on the AgNW coating can infiltrate the pores in the network. Composite sheets with higher sheet resistance tend to exhibit lower stretchability. The thin AgNW network is embedded in the surface of the PU sheet and imparts the surface with high conductivity. In the composite. The relative motion or sliding during stretching could induce more significant loss of nanowire FIG. is shown in Figure 2(a).19 The PU liquid monomer and polymer both contain -N(H). and the stretched sheets relaxed back fairly rapidly to the original shape when the external load was removed.2X/sq.0. 8. and 74. respectively. 11. (b) SEM image of the conductive surface of AgNW-PU composite electrode with the sheet resistance of 16 X/sq.203. After curing. The resulting AgNW-PU composite sheet was peeled off and cut into various sample sizes.groups. whose bulk conductivities do not change with stretching. Reuse of AIP content is subject to the terms at: http://apl.org/about/rights_and_permissions . approaches 82. Figure 1(b) shows the SEM image of the conductive surface of the composite electrodes with a sheet resistance of 16 X/sq. Rnorm of the electrode with 8.083303-2 Hu et al. In repeated Scotch tape test.0 X/sq initial sheet resistance follows this equation fairly well until about 20% strain. the Rnorm rises superlinearly.aip. 102.4. For conductive materials.0. which further proves the complete transfer of AgNWs. 16. which bond to the nanowire surfaces. Figure 1(c) shows the transmittance spectra and photograph of AgNW-PU composite electrodes with various sheet resistances. The urethane compounds were then cured at room temperature for 24 h. the loss of nanowire interconnections is insignificant. inclusive of the PU substrate. An adhesive tape with 340 lm thickness was used as the spacer between the two sheets of glass to control the thickness of the sandwiched liquid layer. and 44. but should not disrupt the conductive network. The normalized resistance (Rnorm). 79. (c) Transmittance spectra of AgNW-PU composite electrodes with sheet resistance specified. Inset: photographs of the composites with specified sheet resistance.20 The strong bonding between the PU matrix and the AgNW network plays an important role in the transfer of the nanowires. Downloaded 23 Jun 2013 to 144.

3. and electronics should operate under all strain or stress conditions.4 times. 102. Appl. The stability of the composite electrodes at different strain rates was thus performed.84 pF. (c) Change in capacitance versus time over 10 stretching/releasing cycles with 60% stretching strain. Figure 2(b) shows resistance changes during a full cycle of strain from 0% ! 60% ! 0% at various strain rates.122. to sandwich a clear acrylic elastomeric dielectric spacer (3 MTM VHBTM Tape 4905 or 3 MTM Scotch 924 ATG Tape). In each stretching cycle. or 80%).aip. with the conducting surface facing inward.1. In practical applications. Varying the stretching speed has no discernible effect on the change of capacitance. (a) Change of capacitance DC=C0 versus strain. It is unclear what causes such a strain rate effect.23 As shown in Figures 3(a) and 3(b). Electrical contacts were made using a conductive copper tape onto each of the patterned AgNW lines. a capacitor was stretched to 60% strain or pressed at 1 MPa and then released. 60%. which thus causes larger increase of macroscopic resistance. resistance change is quite reversible. and d is the thickness of the spacer. The transient Rnorm during cyclic stretching at different strain rates are shown in Figure S1. its capacitance varies with the strain according to10 DC ¼ a à el à C0 .13. 083303 (2013) interconnections for the thinner AgNW networks. With the assumption that the elastomers in capacitor are isotropic.25 mm thick. but is generally less than 1 in experimental measurements.0 times increase at the 60% peak strain when stretched at a speed of 1 mm/s. high stretching speed leads to high transient resistance. The resulting capacitor is elastomeric and useful for strain and pressure sensing.203. Figure 3(c) shows the transient capacitance change during the cyclic test. strain can be encountered at various rates. The strain was applied as a uniaxial elongation using a stretching setup with precise length control. This article is copyrighted as indicated in the abstract. When the capacitor is stretched. it shrinks in width and thickness due to Poisson’s effect. however.5 over the range of 0% to 60% strain for the stretchable devices.01 mm/s. Apparently. Transparent variable capacitive sensors were fabricated by laminating two AgNW-PU composite electrodes. er is the permittivity of the dielectric. Lett.083303-3 Hu et al. the capacitance increases to 1.org/about/rights_and_permissions . and the process was repeated for 10 cycles. Longitudinal stretching and transverse stress applied both cause an increase in capacitor area and reduction of the dielectric spacer.3 FIG. the composite strips were mounted onto a pair of tensile grips in a dynamic mechanical analyzer. the changes in capacitance exhibit a linear response to strains up to 60% and pressure to 1 MPa. the resistance change is fully reversible: it recovers the initial value after being relaxed to 0% strain. Capacitances were measured at 1 kHz frequency with a 1 V ac signal.5 In order to study the stability of the devices. The low resistance at the 0% strain state is retained even after 200 stretching cycles. Phys. The capacitance of a parallel plate capacitor is given by C¼ e0 er A . 40%. Downloaded 23 Jun 2013 to 144. It can be seen that the sheet resistance of the composite electrodes increases with stretching speed. (3) where el is the longitudinal strain and a is the capacitive gauge factor. A is the overlapping electrode area. The smallest change in capacitance that can be distinguished from instrument noise is 20 kPa. which in turn increase the capacitance. The capacitive gauge factor is 0. (b) Change of capacitance DC=C0 versus pressure. which corresponds to human fingertip texture and shape sensing. The resistance shows 20. The (transverse) pressure was applied by a vertical load on the surface of the device. the resistance increase at the same peak strain is 5. For cyclic stretching/ releasing tests. d (2) where eo is the permittivity of free space. (d) Change in capacitance versus time over 10 pressing/releasing cycles with 1 MPa pressure. However. The variable capacitor sensor samples had a 15  8 mm2 overlapping area between the opposite electrodes. Reuse of AIP content is subject to the terms at: http://apl. The calculated capacitance of the samples at 0% strain is 25. At 0. The gauge factor has a theoretical value of 1 for a pure Poisson deformation. and the dielectric spacer was 0.22 The peaks of the profiles are the resistance at the strain peak (20%.

(b) Photograph of a pressure sensor array (10 Â 10 pixels). Figure 4(e) shows a characteristic response of capacitance of a sensor pixel to transverse pressures up to 100 KPa.5 pF. This leads to the change of the fringing capacitance directly above the capacitor. which increased to 33. (a) The schematic illustration of the fabrication of a transparent capacitive array comprising an acrylic elastomer layer as the dielectric spacer between two transparent AgNW-PU composite electrodes.85 pF when released to 0% strain. Capacitive sensor arrays were also fabricated to emulate the spatial resolution of natural skin. a sample had a measured capacitance of 25.11 We investigated the change of capacitance of each pixel as a function of the applied uniaxial stretching with or without a delicate finger touch that did not cause any additional transverse deformation. (e) Change of capacitance DC=C0 of one pixel with transversely applied pressure.60 pF. The measured capacitances of pixels varied in the narrow range of 9. finger press. For instance. This article is copyrighted as indicated in the abstract. 083303 (2013) times its original value and reverses back to the initial number after released to 0% strain. and firm hand grip. Figure 3(d) shows a similar plot during cyclic testing under 1 MPa transverse pressure. with a mean average of 10.8 to 11. the change of capacitance of the addressed pixel is at least eight times higher than the neighboring pixels. The capacitance change described above is caused by geometrical changes of the variable capacitors. As shown in Figure 4(f). (f) Mapping of the measured capacitance changes of pixels in the area where a pressure of 30 KPa was applied on the central pixel. Phys. (c) Photograph of the sensor array bent at 180 . A highly porous dielectric film (3 M Scotch 924 ATG Tape) was used as the dielectric spacer in the variable capacitor arrays to increase sensitivity toward small pressures. For a typical measurement.203. The curve is linear with a standard deviation R2 of 0.aip. Reuse of AIP content is subject to the terms at: http://apl.995. In cases where a finger or object touches on the top surface of the sensor which does not cause any geometrical deformation. the capacitance could still change if the fringing electric field above the sensor is disturbed. The reversibility during both stretching and compressing tests is high in these cycles. the capacitance would decrease because the charges are (partially) grounded. Figure 4(d) shows SEM image of a surface area with the upper half comprising patterned AgNWs. 4.76 pF exhibits a linear response FIG.122.5 mm2 and separated by 1 mm from each other. The crosstalk between adjacent pixels for this 10 Â 10 pixel pressure sensor was investigated by applying a pressure of 30 KPa to one pixel. 102. this sensor can meet the application requirement in tactile robotics.5 The inset of Figure 4(e) shows that the lowest detectable pressure is about 1 kPa. which is important for the capacitor pixels to have the same base capacitance before any external load is applied. Two of such patterned electrodes in perpendicular orientation were used to laminate the porous dielectric film.1. As shown in Figure 5(a). and can detect in the pressure range of 1 kPa to 100 KPa to sense gentle touch.083303-4 Hu et al.5 Â 1. Overall. which exhibits high optical transparency and mechanical flexibility. The capacitance increase is 51% of its original value. Therefore. The fabrication process is illustrated in Figure 4(a).94 pF when stretched to 60%. and returned to 25. Downloaded 23 Jun 2013 to 144. The AgNW-PU composite electrodes were patterned into parallel conductive stripes with 1.5 mm width and spaced by 1 mm. which corresponds to fingerprint sensing. Appl.84 pF when unstretched. Lett. the flexible transparent capacitive sensors have sufficient spatial resolution for robotic sensory skins and touchpanels. The AgNW patterns have a well-defined edge. each pixel being a square area of 1. (d) SEM image of a surface area half of which comprises patterned AgNW-PU electrode. The transmittance of the sheet at 550 nm is 78% in areas without AgNWs and 72% in areas where the perpendicular AgNW lines overlap each other. the sensor with an initial capacitance of 10. Figures 4(b) and 4(c) show photographs of an as-prepared capacitor array. and measuring the capacitance change of this as well as its neighboring pixels.org/about/rights_and_permissions . when the contact material is an earthed conducting medium such as finger or pencil.

Lee. Adv. Pei. Tao. Bao. J. 12 S. 45. Yu. 226 (2012). D. In alternative experiments. Mitra. S. A. Adv. Huang. pressure-sensitive bandages. Lee. R. 1603 (2010). ACS Appl. Yun. P. 3223 (2012). Cheng. 90. 18 S. Reuse of AIP content is subject to the terms at: http://apl. S. J. Yun. H. L. 103001 (2012). Lett. Li. M. or touch screens for wearable electronics. Muir. T. Y. H. G. 24. capacitive sensor sheets have been fabricated by employing highly compliant polymer composite electrodes and dielectric spacer. 29 (2009). Hu. Mater. Italy. Cotton.1063/1. Rogers. Su. or stretched. 102. while it was stretched to various strains. 16 P. Nanotechnol. and S. Adv. 5. Y. 6. The capacitive sensors can be operated reliably when they are pressed. Hong.05 pF/%. IEEE Sens. Rogers. Peterson. Omenetto. H. W. S. 21. Vosgueritchian. 9 C. Lett. A. W. Y. K. Tee. and J. C. M. P. and S. Lee. H. H. 1484–1487. I.” SEM was taken at the Scanning Probe Microscopy facility at the Nano and Pico Characterization Laboratory. Mater. 9. which covers gentle finger touch. robotics. 788 (2011). 473 (2007). I. L. L. California NanoSystems Institute. G. A. and Q. Nanotechnology 23. Someya. 6 M. Akter and W. IzadiNajafabadi. H. X. H. K. A. Inset illustrates how the transverse pressure and uniaxial stretching are applied independently. Mater. B.aip. Bao. Adv. Ying. S.8 pF/100 kPa at 0% strain (no horizontal stretching applied) to 1. 91. R. Chung. V. Graz. and Z. H. Z. Hu. R. B. S.doi. Lu. independently applied strains. A. Yeo. Je. 3 D. Tee. J. J. D. Mannsfeld. J. Tok. Kim. 15 T. Lee. Lipomi. Liu. C. Phys. A. Cao and J. 7 M. Mater. solid-state sandwich structure. Biotechnol. and Y. Rogers. Stoltenberg. In conclusion. O. D Appl. the sensor retains the response linearity with strain and the same gauge factor when it is simultaneously stretched and touched. G. Li. The sheets can also be used for touch sensing which does not cause any physical deformation. which is in consistency with the results described above. V. The change of capacitance as a function of the transverse pressure remains linear at various horizontal. Koncar. (b) Change in capacitance versus independently applied transverse pressure and uniaxial elongation. and J. 9.4794143 for the supplementary result of the stability of the composite electrodes at different strain rates. Sokolov. Bioeng. McCormick.2 pF/100 kPa at 60% strain. F. Hayamizu. Nat. T. Futaba. Rogers. Ying. Yu. to strains up to 60% with a sensitivity (capacitance change divided by applied strain in %) of 0. C. Lacour. J. 4887 (2008). Appl. 3326 (2012). X. They can also detect transversely applied pressure in the range of 1–100 KPa. Kim and J. B. 19 W. while the sensitivity increases with the horizontal strain as shown in Figure 5(b). A. N. and M. The pressure sensitivity increased from 0. Nature Mater. Y.02 pF. Niu. Mater. Brochu. P. B. 23 Q. 37. H. H. 3989 (2011). Mater. and J. Kim. pressure. 838 (2011). Yu. UCLA. Y. 20. 17 Z. MRS Bull. Wang. L. Phys. Zhang. P. J. Y. but disturbs the fringing electric field above the sensor. 8 T. Chen. B. Phys. M. Evans. 221909 (2007). Inset illustrates how the two external operations are applied independently. Niu. Lecce. 344004 (2012). and Z. Pritchard. pp. 59 (2005). in The 7th IEEE Conference on Sensors. Liu. S. Haider. Mahfouz. M. K. Bonifas. 4 J. 083303 (2013) FIG. Nam. K. 13 D. Lewandowski. H. Kim. Suo. 6. R. Yomogida. C. as well as the high mechanical compliancy of the sheets should find potential applications in prosthetic limbs. B. J. Keum. S. A. 5 E. Niu. Ahn and J. T. Barman. Ko. 23. Interfaces 4. C. G. Pradeep. N. and Z. G. Li. 10 D. Cohen. B. V. F. S. Y. Huang. Z. Jain and T. J.203. M. J. Hata. Xu. These multifunctionalities of stretch. 296 (2011). 21 N. Huang. transverse pressures were applied on the surface of sensor. Kim. Y. Sensors 7. Ramuz. and Q. Lu. Phys. 22 See supplementary material at http://dx. Y. Coleman. A. Won. H.org/about/rights_and_permissions . Huang. 859 (2010). Lee. Nanotechnol. A. 11 D. H. Z. This article is copyrighted as indicated in the abstract. H. Chowdhury. Kim. Rogers. D. B. and M. H. Vlassak. M. Yamada. 26-29 October 2008. and K. N. Fox. F. 1821 (2012). B. Ameen. Mater. Eliza. Dufour. R. 20 P. M. Z. 12. A. K. N. Pei. and firm hand gripping. Ma. N. Wang. M. N. Maharbiz. S. Weili Hu thanks the “China Scholarship Council Postgraduate Scholarship Program. Bao. J. Nanotechnology 23. However. 24. D. 2008 (2009). Tee.5. Kim. S. Adv. W. X. Rogers. M. S. T. 1321 (2012). S. finger press. 344002 (2012). the capacitance dropped to 10. 24. M. The sheets have a relatively simple. Appl.122. D. P.1. A. Science 327. J. bent. The gauge factor is 0. Hellstrom. and J. 1855 (2012). H. J. and touch sensitivities. Nano Lett. Reese. C. 2 1 Downloaded 23 Jun 2013 to 144. Pei. Cochrane. Science 333. Lu. Wu. Y. B. Lee. X. (a) Change in capacitance combined with figure touch versus uniaxial stretching strain. Lu. S. H. 14 D. Nat. Yamamoto. The work reported here was supported by the Air Force Office of Scientific Research (FA9550-12-1-0074) and National Science Foundation (ECCS-1028412).org/10. and C. The sheets can be stretched up to 60% strain and the corresponding capacitance change can be employed to detect the in-plane deformation. When the user delicately touches the surface of the capacitive arrays. G. exhibit good stretchability and transparency. Z. S. Yu. Islam.083303-5 Hu et al. S. and Q. N. C. B. K. Adv.

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