Shu
Gong‡
ab,
Yan
Wang‡
ab,
Lim Wei
Yap
ab,
Yunzhi
Ling
ab,
Yunmeng
Zhao
ab,
Dashen
Dong
ab,
Qianqian
Shi
ab,
Yiyi
Liu
ab,
Hemayet
Uddin
c and
Wenlong
Cheng
*abc
aDepartment of Chemical Engineering, Monash University, Clayton, Victoria 3800, Australia. E-mail: wenlong.cheng@monash.edu
bNew Horizon Research Centre, Monash University, Clayton, Victoria 3800, Australia
cThe Melbourne Centre for Nanofabrication, Clayton, Victoria 3800, Australia
First published on 1st August 2018
Human skin can sense an external object in a location-specific manner, simultaneously recognizing whether it is sharp or blunt. Such tactile capability can be achieved in both natural and stretched states. It is impractical to mimic this tactile function of human skin by designing pixelated sensor arrays across our whole curvilinear human body. Here, we report a new tactile electronic skin sensor based on staircase-like vertically aligned gold nanowires (V-AuNWs). With a back-to-back linear or spiral assembly of two staircase structures into a single sensor, we are able to recognize pressure in a highly location-specific manner for both non-stretched and stretched states (up to 50% strain); with a concentric design on the fingertip, we can identify the sharpness of an external object. We believe that our strategy opens up a new route to highly specific second-skin-like tactile sensors for electronic skin (E-skin) applications.
Conceptual insightsWe report a new tactile electronic skin sensor based on staircase-like vertically aligned gold nanowires (V-AuNWs). With the back-to-back linear or spiral assembly of two antiparallel staircase structures into a single sensor, we are able to recognize pressure in a highly location-specific manner for both non-stretched and stretched states (up to 50% strain). With a concentric design on the fingertip, we can identify the sharpness of an external object in a similar way to human skin for the first time. Note that only location-specific pressure sensing under a non-stretched state has been demonstrated with existing unpixellated pressure sensors. Other important functions of human tactile sensing, such as the ability to discriminate sharp/blunt objects and location-specific sensing under stretched states, have not yet been achieved in the literature. We believe that our methodologies open up a new route to low-cost stretchable smart tactile sensors with potential facile integration and high location resolution into future wearable electronics, such as stretchable touch-on displays, soft robotics and prosthetic skins. The staircase structures and location-specific sensitivity could be extended to other novel nanomaterials and designs to form heterogeneous multifunctional optoelectronic devices, indicating broad application potentiality in next-generation skin-like electronics. |
Here, we report a non-pixelated tactile sensor based on staircase-like vertically-aligned gold nanowires (V-AuNWs). Using an antiparallel linear assembly, the sensor can recognize where an external load is applied and its strength. Such a location-specific sensing capability can also be achieved in the stretched state (up to 50% strain). Furthermore, we show that a staircase-like design can be extended to other configurations, such as spiral and concentric patterns. When a concentric pattern with antiparallel staircase V-AuNWs is attached to a human finger, a sharp or blunt object can be discriminated in a similar way to human skin.
Our design principle is based on the accurate thickness control of V-AuNWs, which is key to staircase structural design. Previously, carbon nanotubes,6,7,9,16 graphene,6,11 nanowires,5,10 nanoparticles17 and conductive polymers18 have been used for designing skin-like sensors; however, it is challenging to achieve staircase-like structures with nanoscale accuracy other than as gradient patches19 or threads.20 Note that only location-specific pressure sensing in the non-stretched state has been demonstrated with these gradient structural designs.19,20 Other important functions of human tactile sensing, such as the ability to discriminate sharp/blunt objects and location-specific sensing in stretched states, have not yet been achieved in the literature.
In comparison to other conductive films such as carbon nanotubes (CNTs) and evaporated gold films, the V-AuNWs produced by directly growing them on soft substrates possess the following attributes, which make them ideal for a stretchable unpixellated design. Firstly, the conductivity of our V-AuNWs sheet decreases when a localized pressure is applied. This is possibly due to the generation of cracks in the conductive thin film as a result of pressure-induced deformation of the Ecoflex substrate24 (Fig. S2a in ESI†). The pressure-induced deformation is confirmed by the results of a finite element analysis (FEA) of the strain distribution of a 25 × 5 × 0.5 mm3 V-AuNWs/Ecoflex film. The localized strain will lead to an increase in resistance of the composite film (Fig. S2b in ESI†). The formation of a pressure-induced crack is evidenced by optical images of V-AuNWs when a localized pressure is applied to the back (Fig. S3 in ESI†), which is similar to other stretchable crack-based pressure/strain gauge sensors we have previously reported.22,23 The conductivity of the film is fully reversible with both static and dynamic pressures up to 40 kPa (Fig. S4a–c in ESI†), which was further proved by a durability test of over 5000 cycles with an applied pressure of 2 kPa (Fig. S4d in ESI†). In comparison, the resistance of an evaporated gold film on Ecoflex showed only irreversible changes when a pressure is applied (Fig. S5a in ESI†); whereas a spray-coated CNT film is not sensitive to a point load of 0.1 N (Fig. S5b and c in ESI†).
Secondly, the as-prepared V-AuNWs/Ecoflex thin film is intrinsically stretchable without the need for any external structural design. It exhibited reversible resistance changes under a repeated strain of 0%–60%–0% for over 2000 cycles, due to negligible morphological changes before and after the cycling experiment (Fig. S6a–c in ESI†). As a control, an evaporated gold film showed irreversible conductivity losses of >100% after only 10 cycles (Fig. S6d in ESI†), which is due to the strain-induced permanent cracks and delamination of the gold film (Fig. S6e and f in ESI†). The superior mechatronic properties of our V-AuNWs are mainly attributable to a combination of their vertically aligned morphology and strong adhesion to soft substrates, which mean they are firmly bonded to Ecoflex and remain undamaged when a stress in a horizontal direction is introduced. The strong adhesion of V-AuNWs originates from their growth mechanism,21 where strong chemical bonding between amine moieties and gold nanowires mean they can even survive the PI tape test (ESI,† Movie 1). In comparison, neither spray-coated CNTs nor evaporated gold film can pass the PI tape test because of their poor adhesion to soft substrates (ESI,† Movie 1).
Another attribute is that the length of the AuNWs can be accurately controlled, allowing facile fabrication of a staircase structure with high precision. To fabricate a staircase V-AuNWs film, we develop a simple yet efficient mask-assisted step-by-step growth strategy, as illustrated in Fig. 1a. In brief, an Ecoflex substrate is chemically modified by (3-aminopropyl)trimethoxysilane (APTMS), followed by immersion in a 3 nm gold nanoparticle seed suspension for 2 hours. This leads to immobilisation of the seeds onto Ecoflex surfaces via electrostatic attraction. Then a 1st-step V-AuNW layer can be achieved by seed-mediated growth in a nanowire growth solution containing mercaptobenzoic acid (MBA, 90%), gold(III) chloride trihydrate (HAuCl4·3H2O, 99.9%), and L-ascorbic acid for 2 minutes. The 1st-step V-AuNW layer is partially passivated by a polyimide (PI) mask and the rest of the exposed part is immersed in a nanowire growth solution again for another 2 minutes. This leads to further elongation of the primary nanowire layers to form the 2nd-step V-AuNW layer. The 2nd growth of the gold nanowire is possible because the dense film is permeable, enabling gold precursors to reach the nanowire-substrate interface, where the nucleation/growth site is situated (Fig. S7, ESI†). The mask-assisted step-growth process can be repeated multiple times to form 3rd-step, 4th-step,…nth-step V-AuNW layers. The n-step staircase V-AuNWs structure on an elastomer substrate can then be obtained simply by peeling off the PI masks.
The staircase morphology of V-AuNWs film is confirmed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Fig. 1b shows the AFM images and the corresponding line scan profiles of a three-step staircase V-AuNWs film. The step heights for the first, second and third staircase are ∼0.35 μm, ∼0.48 μm and ∼0.71 μm, respectively. The overall height of the 3rd-step V-AuNW layer to the Ecoflex substrate is estimated from the AFM line scan profile to be ∼1.5 μm. The staircase structures are further confirmed by SEM characterization (Fig. 1c and Fig. S8 in ESI†). The cross-sectional SEM image of the V-AuNWs clearly demonstrates enokitake-like standing nanowire structures at each step (Fig. 1d). It should be noted that such unique staircase-like structures have not been reported in previous gradient films.19,20,24,25 The time-controllable nanowire heights in conjunction with PI masking allow for the precise fabrication of staircase conducting films with well-defined hierarchical structures.
Then, we thoroughly investigated the electrical conductivities of V-AuNWs films of different thickness. 10 V-AuNWs film (1 × 1 cm2) samples were fabricated on spun-coated Ecoflex on glass substrates by programming the growth time from 1 to 10 minutes. The 1 min growth V-AuNWs film has a sheet resistance of 2959 ± 586 Ω. As the nanowire growth time gradually increases, the sheet resistance quickly decreases initially, but almost reaches a steady resistance after 7 minutes of growing time (Fig. S9a in ESI†). With 10 minutes’ growth, a typical sheet resistance of 10.5 ± 3.9 Ω is obtained. The sheet resistances for all 10 samples reduced further once the Ecoflex was peeled off the glass substrates. Typically, the electrical resistances of wrinkled V-AuNWs film with growing times from 1 to 10 minutes range from 1728 ± 225 Ω to 8.4 ± 3.7 Ω. This may be attributed to shrinkage of the Ecoflex after releasing it from the glass substrate, which tightens the nanowire packing and causes the V-AuNWs to wrinkle, as can be seen from optical characterizations (Fig. S9b–i in ESI†). Furthermore, the electrical responses of V-AuNWs samples with growing times of 1–10 minutes were recorded under a constant pressure (Fig. S10a in ESI†). Note that the pressure sensitivity of V-AuNWs films reduces as the nanowires get longer, but reaches a steady value after 7 minutes (Fig. S10b in ESI†). The reduced sensitivity is due to a lower base resistance as the nanowires get longer (Fig. S9a in ESI†).
Using the antiparallel back-to-back assembly of two staircase V-AuNWs, we demonstrate its location-specific sensing capability. As shown in Fig. 2a, we fabricated two V-AuNWs sensor strips (30 × 5 mm2) on Ecoflex substrates with anti-directional 6-step staircase structures (5 × 5 mm2 for each staircase) with growing times at one-minute intervals. Due to the variation in thickness, the conductivity changes along the longitudinal dimension exhibited opposite directions for the front (sensor 1) and back (sensor 2) sensors (Fig. 2b). Consequently, the overall increase in resistance of the two strips subjected to loads at different steps enables the accurate calculation of both the applied load and its location along the sensing strip.19
In detail, we record the changes in resistance for sensor 1 and sensor 2 from the responses at each location (I to VI) to a constant pressure (Fig. 2c and d). In the calibration process, linear fits are adjusted at each specific location, giving a set of 6 linear fits for sensors 1 and 2. The pressure sensitivity S for each location can be defined as the slope of the traces.
We assume that a six-step staircase film could be regarded as six resistors connected in series. When a constant pressure P is applied on the nth-step, its sensitivity is defined as:
(1) |
The location-specific dimensionless parameter Ln, namely the sensitivity ratio of sensors 1 and 2 (Sn1/Sn2) at step n could be defined as:
(2) |
The relationship between the pressed location and Ln is shown in Fig. 2e, where a calculated value of the sensitivity ratio is obtained for each location based on the linear fittings in Fig. 2c and d. The location specificity agrees well with the calculated value over a wide range of pressures (4–40 kPa). Next, we tested the pressure specificity of sensor 1 by comparing the real value of the load and the calculated value of the load. Fig. 2f shows that these values are nearly identical between 0 and 40 kPa. Therefore, a V-AuNWs sensor can be used to accurately measure both the pressure and the location of the applied force.
Remarkably, the location-specific pressure-sensing capability can be maintained even when the sensor is deformed. As shown in Fig. 3a, the sensor strip is subjected to 50% uniaxial elongation. The sensitivity ratio of sensors 1 and 2 from location I to location VI is demonstrated in Fig. 3b, and is independent of the applied pressure. The overall resistance of the staircase film is increased with an increase in strain level from 0% to 50% (Fig. S11 in ESI†), due to the generation of strain-induced cracks in each step of the film (Fig. S12 in ESI†). In addition, larger gaps and cracks are observed with thicker V-AuNWs steps (Fig. S12 in ESI†), leading to greater losses in conductivity compared to thinner V-AuNWs steps. Accordingly, the conductivity disparity between adjacent steps becomes smaller. As a result, the thicker V-AuNWs steps (locations IV, V, VI of sensor 1) are more responsive to pressure than thinner nanowire locations (location I, II, III of sensor 1) with the increasing level of strain (Fig. 3c and d).
The location-specific sensor design can also be extended to other topological structures, such as a spiral pattern (Fig. S13a in ESI†). When pressure was applied to a sheet of the 2D sensor platform, the top and bottom staircase V-AuNWs sensors responded to the strain with variable resistances (Fig. S13b in ESI†). According to the collected database in Fig. 2, the actual position and pressure of a force could be well predicted with high accuracy.
We further extended our design to concentric circle patterns to check whether a sharp or blunt object can be discriminated. The schematic design of the pressure area sensor is illustrated in Fig. 4a. Firstly, two concentric circle films with three-step staircase V-AuNWs were fabricated with variations in antiparallel thickness. The radii of the circles from inside to outside are 0.8 mm, 1.5 mm and 2.2 mm, respectively. The thickness of each circle is controlled by the growing time of the V-AuNWs at 2 minute intervals from 2 minutes to 6 minutes. The device is integrated by a back-to-back assembly of two antiparallel staircase films with a protective Ecoflex layer in between. Theoretically, the concentric circle pattern could be regarded as five resistors connected in series (Fig. S14a in ESI†). In addition, due to the low Young's modulus of soft Ecoflex thin film, stress concentration will occur in the edge area when the film is subjected to a uniform pressure (Fig. S14b–d in ESI†). Owing to the discrepancy in thickness for each circle between the top and bottom films, the top sensor is more responsive to a larger pressure area, as stresses are mostly concentrated in the outside thinner circle; while the bottom sensor is more sensitive to a smaller pressure area where the inside thinner circle is activated.
To evaluate the ability of our concentric circle sensors to detect sharpness, three cylinders with radii of 0.6 mm, 1.3 mm and 2 mm are utilized as probes. The force-dependent changes in resistance of the top and bottom sensors with the three cylindrical probes are demonstrated in Fig. 4b and c. The resistance of both sensors showed distinguishable signals to probes with different sizes over a wide range of forces from 0.0375 N to 0.1875 N, which could be used to evaluate the sharpness of the object. Note that the pressure area specificity is also demonstrated by pressure-dependent changes in the resistance of both sensors (Fig. S15 in ESI†), indicating that the ability of our system to resolve the contact area of objects is independent of the applied force or pressure. We further demonstrated the detection of sharpness by attaching wearable sensors integrated with a Bluetooth circuitry to human fingertips (Fig. 4d). Circular cone-shaped objects with various contact areas (0.75 cm2, 0.3 cm2 and 0.03 cm2) could be resolved (ESI,† Movie 2) by taping our sensors to the objects. The sharpness-specific dimensionless parameter SR, namely the sensitivity ratio of sensors 1 and 2 (S1/S2) pressed by cylinder with radius R could be defined as:
(3) |
From a practical standpoint, if the pressure is applied at the boundary of the staircase, complications may occur, interfering with our sharpness- and location-specific sensing concept. Nevertheless, we found that this can be avoided by applying a stiff encapsulation layer (e.g. polyethylene terephthalate, PET) on top of the V-AuNWs film (Fig. S16a and b in ESI†). The PET serves as a passivation material, preventing nanowire deformation when pressure is applied. Consequently, stiff PET sheets could cover the boundary areas of the staircase film to avoid problems in pressure/location detection at staircase boundaries (Fig. S16c, ESI†).
Footnotes |
† Electronic supplementary information (ESI) available: Experimental section, supporting figures and videos. See DOI: 10.1039/c8nh00125a |
‡ These two authors contribute equally to this work. |
This journal is © The Royal Society of Chemistry 2018 |