Ultrahigh Sensitive and Flexible Magnetoelectronics with Magnetic

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Ultrahigh Sensitive and Flexible Magnetoelectronics with Magnetic Nanocomposites: Toward an Additional Perception of Artificial Intelligence Shu-Yi Cai, Cheng-Han Chang, Hung-I Lin, Yuan-Fu Huang, Wei-Ju Lin, Shih-Yao Lin, Yi-Rou Liou, Tien Lin Shen, Yen-Hsiang Huang, Po-Wei Tsao, Chen-Yang Tzou, Yu-Ming Liao, and Yang-Fang Chen ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b04950 • Publication Date (Web): 30 Apr 2018 Downloaded from http://pubs.acs.org on May 4, 2018

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ACS Applied Materials & Interfaces

Ultrahigh Sensitive and Flexible Magnetoelectronics with Magnetic Nanocomposites: Toward an Additional Perception of Artificial Intelligence Shu-Yi Cai,† Cheng-Han Chang,† Hung-I Lin, Yuan-Fu Huang, Wei-Ju Lin, Shih-Yao Lin, Yi-Rou Liou, Tien-Lin Shen, Yen-Hsiang Huang, Po-Wei Tsao,‡ Chen-Yang Tzou, Yu-Ming Liao, and Yang-Fang Chen* Department of Physics, National Taiwan University, Taipei 10617, Taiwan *E-mail: [email protected]

ABSTRACT: In recent years, flexible magnetoelectronics has attracted a great attention for their intriguing functionalities and potential applications, such as healthcare, memory, soft robots, navigation and touchless human-machine interaction systems. Here, we provide the first attempt to demonstrate a new type of magneto-piezoresistance device, which possesses an ultrahigh sensitivity with several orders of resistance change under an external magnetic field (100 mT). In our device, the Fe-Ni alloy powders are embedded in the AgNWs-coated micro-pyramid PDMS films. Our devices can not only serve as an on/off switch, but also enable to act as a sensor that can detect different magnetic fields due to its ultra-high sensitivity, which is very useful for the

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application in analog signal communication. Moreover, our devices contain several key features, including large area and easy fabrication processes, fast response time, low working voltage, low power consumption, excellent flexibility and admirable compatibility onto a freeform surface, which are the critical criteria for the future development of touchless human-machine interaction systems. Based upon all these unique characteristics, we have demonstrated a non-touch piano keyboard, instantaneous magnetic field visualization and autonomous power system, making our new devices be the indigestible magnetic field softly coming into life applications. Our approach therefore paves a useful route for the development of wearable electronics and intelligent systems.

KEYWORDS: magnetoelectronic, touchless, ultra-sensitive, e-skin, full autonomy

Introduction Recent studies on wearable electronic have demonstrated great potential in a wide range of applications such as robotics,1 health monitoring devices,2 displays,3 and information storage,4 etc. One of the most important components of wearable devices is electronic skin (e-skin). The development of electronic skin has recently attracted a great attention due to their wide applications and significant benefits in various fields.5-6 E-skin has been widely studied in numerous forms with many functional devices, including organic light emitting devices (OLEDs), transistors, photodetectors, strain sensors, solar cells, batteries, and biosensors.6-16 Ultimately, a superior electronic skin should possess several unique features, such as ultrahigh sensitivity, multifunctionalities, low working voltage, high signal-to-noise ratio, simple fabrication process, low cost, excellent stability and repeatability, low power consumption, compatibility with other devices, and fast response time, and going beyond imitating human physiological features. To meet


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all these requirements is a great challenge, which needs great efforts through the collaboration of scientists from different fields. Magnetic field has been applied in fields of industrial cranes, healthcare, power generators, memory, navigation, etc. On the other hand, magnetoreception, which is presented in bacteria and animals, such as ants, bees, pigeons, and whales, allows organisms to detect the Earth’s magnetic field for orientation and navigation. However, human is unable to feel magnetic field, and thus we are thirsty to break the barrier to implement magnetoreception becoming one of our capabilities, i.e., an additional sense of human being. Indeed, wearable magnetoelectronics has been studied and the progress is quite impressive. For example, Oliver G. Schmidt’s group has reported imperceptible giant magnetoresistance (GMR) sensors, printable and flexible GMR sensors, wearable and flexible Hall sensors, and magnetic microrobots.17-20 Yang et al. reported selfpowered magnetic sensors.21 Zang et al. reported flexible organic field effect transistor (OFET) based sensitive magnetic sensor with a high sensitivity of 115.2 % mT−1.22 Huang et al. reported magnetic-assisted noncontact triboelectric nanogenerator.23 Zhao et al. reported flexible organic tribotronic

transistor

for

pressure

and

magnetic

sensing.24 In

addition,

wearable

magnetoelectronics has been attempted in several fields that show a great potential for applications in healthcare, memories, soft robots, navigation, touchless human-machine interaction systems, etc.17-19,22-23,25-32 In this work, we demonstrated a new type of magneto-piezoresistance sensor based on a unique mechanical response of microstructured tactile sensors, which meets the above desired requirements for low cost, large area and high-throughput fabrication process.33-34 In addition, we demonstrated an ultrahigh sensitive magnetoelectronics device up to 1507.9 % mT-1, which outperforms all the flexible magnetoelectronic devices ever reported. Such a high sensitivity arises


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from the unique microstructure of the organic/inorganic hybrid thin film.33-34 Simultaneously, our device is workable under the condition of low power consumption and low operating voltage, which is a great advantage for mobile electronic devices. In the same time, we also showed the excellent elastic deformation properties, which is stable more than 1000 times of bending. Moreover, the characteristics of our devices exhibit a fast response time of 1 ms, which is essential for real-time health monitoring and communication. With all these outstanding properties, our devices can be integrated with other electronic devices to achieve multifunctional smart systems. We demonstrated three intriguing applications of our devices. First of all, the instantaneous magnetic field visualization can immediately convert unfamiliar environment information into human-readable signals. Secondly, for the strategic full autonomy of e-skin, our devices can be incorporated with renewable energies and portable power supplies and solar cells. Finally, humanmachine interfaces are important topics of wearable devices, and therefore we presented touchless piano keyboards. Results and Discussion Owing to the highly developed technology using nano-microscale structures, here we synthesized the patterned pyramid to achieve the ultrahigh sensitive and flexible magnetoelectronics performances. The fabrication of mounds consists of photolithography and alkaline etching which are well-known technology nowadays. In the alkaline etching process, we chose KOH as alkaline solutions because of its well-controlled performance, which depends on the concentration of isopropyl alcohol (IPA) and etching temperature.35-36 To manufacture the flexible patterned-pyramids magnetic sensor as shown in Figure 1, FeNi alloy powder and silver nanowires (AgNWs) were selected as magnetic and conductive ingredient, respectively, for the sake of their superb magnetic properties and high electrical conductivity. The main component of


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our design is the thin film of polydimethylsiloxane (PDMS). PDMS is notable for its great elastic properties, which is suitable for our need. An AgNWs-coated microstructure of FeNi/PDMS thin film with high conductivity, outstanding magnetic properties and flexibility can be achieved. For the fabrication process, initially, PDMS with FeNi powder is spin-coated on the mound and dried in the oven. Then, the film is peeled off from the mound, and sprayed coating AgNWs on the film, and then heated on a hot plate with a temperature of 100 0C. Notably, the thickness of the AgNWs has to be precisely considered. If it is too thick, the pattern of PDMS film will become blurred. On the other hand, if the thickness is too thin, the conductivity will not be enough to reach high performance. Figure 2a shows the cross-sectional scanning electron microscope (SEM) images of the AgNWs-coated FeNi/PDMS thin film with 15 µm micro-pyramid structure.37 Finally, the microstructured FeNi/PDMS/AgNWs film is attached onto an ITO/PET substrate with a 50 m height and 1 cm width air gap. ITO/PET is a suitable substrate with high conductivity and elasticity for a flexible magnetic sensor. The small air gap in-between FeNi/PDMS/AgNWs film and ITO/PET plays an important role to enhance the sensitivity of our devices. It is because before applying a magnetic field, the device is in an insulating state due to the separation of the top and bottom electrodes. After an external magnetic field is applied, the top and bottom electrodes are in a contact mode, and the device turns into a conducting state. In other words, the small air gap can introduce insulating-conducting transition under an external magnetic field. The working process is schematically illustrated in Figure 2b. The underlying mechanism of our proposed magnetoelectric device is mainly determined by the change of current. Through an applied external magnetic field, the Fe\Ni alloy powder in the thin film will be magnetically polarized. The magnetic force caused by the magnetic field gradient between Fe/Ni coated PDMS layers and magnet will lead to the PDMS pyramids being attached to the bottom electrode hence


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to change the resistance. Then, by detecting the change of the current, the magnitude of the external magnetic field is perceptible. Basically, the relationship between the magnetic force and the external magnetic field is given by the expression:38

F  kB

dB dz ,

(1)

where F is the magnetic force, k is the magnetic coefficient, z is the distance between the PDMS pyramids and the external magnetic source, and B is the strength of magnetic field. To explore the magnetic field responses of our magnetoelectronics devices, the I-V characteristics between the top and the bottom electrodes under different magnetic fields are examined. As shown in Figure 3a, the resistance of the device decreases with increasing the external magnetic field. This result can be attributed to the low resistance of ohmic contacts, which allows the charge transfer with a high efficiency in both directions between the two conductive layers. Without the external magnetic field, the suspended structure of PDMS/Ag NWs and the ITO electrode is separated, resulting in the open-circuit in between, while both of them contact with each other becoming in the turn-on condition by applying an external magnetic field. Figure 3b presents the real-time current responses with different magnetic fields (50, 100, and 350 mT) to demonstrate that the current raises immediately to the steady state under an applied external magnetic field, while drops rapidly to the off state when removing the magnet. The measurement also demonstrates that there is no pronounced hysteresis loop for increasing and decreasing magnetic field as shown in Figure S1 and Figure 3b. The advantage of the patterned pyramid structure is that the hysteresis between PDMS layer and ITO/PET is small enough to be neglected.33 Importantly, these results reveal that the repeatability, highly on/off ratio of currents and distinguishable signals that can be attributed


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to the suspended structure and pyramid-like 3D electrodes. Note that this experimental data was measured by an oscilloscope at a constant low operational voltage of 0.1V. Figure 3d presents the ultrahigh sensitivity of our magnetic sensor under different magnetic field.22 The sensitivity is defined as S  (I / I 0 ) / B , where ∆I is the change of current, I0 is defined as the threshold current response of 3.4 x 10-4 mA, which can be obtained from the off circuit under 35.2 mT when two electrodes are in initial contact under the threshold magnetic field as shown in Figure 3c, and ∆B is the change of the applied external magnetic field. Under the operating voltage of 0.1 V, three different slopes of the current responses with increasing applied magnetic field can be clearly seen. In the low magnetic field region (below 65.4 mT), the sensitivity is 206.0 %. The increasing current response is relatively slow, which can be interpreted as the small amount of the PDMS pyramids being touched to the bottom electrode, leading to the slight increment of the current response. With increasing the applied magnetic field (from 74.9 mT to 248.5 mT), a significant increase of the sensitivity achieves as high as 1507.9 % mT -1. This behaviour can be realized by the fact that the deformation of PDMS pyramids increases with increasing the applied magnetic field, which demonstrates that our magnetoelectric device can be operated within this magnetic field region quite well with a steady liner current response. On the other hand, with further increasing the magnetic field (above 287 mT), a decrease of the current response with a sensitivity of 134.5 % mT-1 is observed, which is due to the gradual saturation of the deformation of PDMS pyramids. Moreover, the current response under different width and height of the air gap are shown in Figure S2 to optimise the performance of the device. Compared with all previously published result, the sensitivity of our device is higher than all flexible and wearable magnetic sensors ever reported as shown in Table S1, Supporting Information for comparison.


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The response time is affected by the Young’s Modulus of the material and the structure of the suspended film.39 The excellent characteristics of PDMS deformation of the response time are shown in Figures 4a and 4b. Both of the response time and recovery time are about 1 ms, and the rapid voltage change is measured by the oscilloscope with and without applying the external magnetic field at 150 mT. Because the response time of the device is important for the detection of fast magnetic field change, methods to further improve the response time have been proposed in Supporting Information, Section Ⅰ.

Figure 5a shows the bending test of our device, which is operated under the magnetic field of 150 mT at a constant voltage of 0.1 V. The device is attached to different curvature radius substrates and the on/off current of the device shows a negligible difference with different bending radius. Figure 5b shows that the response current of our device does not have any change over 5000 bending cycles. In terms of this superior result, our device can be comfortably mounted on soft robots, thus, an external magnetic field intensity is perceptible. Hence, we can design a light weight soft robot without complex reading systems. With these great mechanical properties, our devices are suitable to be attached to curved surfaces and can work perfectly in a motion state. Therefore, our device is well suited for flexible electronic device applications with the functionalities beyond human skin. Note that soft robots and microrobots possessing special tasks with flexibility and adaptability, can be applied to artificial muscles, grippers, bioengineering applications.32,40-45 AgNWs and ITO are excellent conductive materials and form a good Ohmic contact, enabling to achieve a low working voltage and a low energy consumption device, which is immensely desirable. Therefore, it can be easily driven by light weight portable power sources, such as flexible


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solar cells or triboelectric nanogenerators.46-48 In addition, we demonstrate that our new type of magnetoelectronic devices has an ultrahigh sensitivity, which is ten times more than the best record in all previous works.22 Such a high sensitivity and giant variation of resistance promise to simply read and directly integrate with other functional electronics without external intricate readout circuits. In addition, this magnetoelectronic can not only serve as an on/off switch but also be an analogy signal system for the application of communication in information technology due to its ultrahigh sensitivity with several orders change of the measured current under an external magnetic field. Moreover, we also compare our device with other devices of a similar structure in the previous reports. Going through the published reports, PDMS films with pyramid structures have been implemented in pressure sensors to achieve ultra-high sensitivity and energy harvesting devices to reach high-efficiency energy conversion.33-34,47 Nevertheless, the incorporation of magnetic particles with pyramid PDMS structure and the introduction of the air gap in-between top and bottom electrodes have not been reported by any other research groups. With these unique features, next, we present non-touch piano keyboard, instantaneous magnetic field visualization and energy autonomous systems. The most challenging issue for the soft touch panel is the location of the receiver. For example, when we equipped with a soft touch panel on an arbitrary surface, the panel on the corner or edge parts will be rarely touched or sensed. Therefore, the touchless human-machine interaction is a solution to solve this problem. In addition, optical and infrared sensors are commonly touchless receivers, while these sensors can be easily blocked by the entity objects. Magnetic field is able to penetrate biological tissues and other materials safely. Here, we demonstrate the touchless piano keyboards and play a song by applying an external magnetic field (Video S1, Supporting Information). The arrayed devices are attached to the arm and connected to an external electrical circuit. Some optical touchless receivers are


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malfunction by entity objects, but our device with a magnetic-assisted touchless manner can rule out this problem. In real life applications, portable and wearable electronics aim at light weight, high compatibility, low power consumption, simple structure, and foldability. Furthermore, the multifunctional devices in a wide range of applications need to integrate with many different functional electronic devices, which requires a driving energy. Consequently, it is necessary to develop power-efficient devices, light weight and stretchable batteries as well as green energy sources.49-51 For example, self-powered electronics, thermoelectric generators and triboelectric nanogenerators have been attracted an intensive interested. With all things considered together, a wearable electronic system that can sustain for a long time without an external power station is a trend. As can be expected, this kind of advanced discovery will be a significant breakthrough for the development of prostheses, soft robots as well as e-skin. Here we demonstrate an autonomous operation that based on the integration of a commercial silicon based solar cell with our device under the light irradiation of outdoor and indoor environment with the power density of 1.083 mW cm-2 and 0.144 mW cm-2, respectively. Figures 6a and 6b show the I-V and the I-T characteristics after integrating our device with a silicon based solar cell at the applied magnetic field of 150 mT. The dramatic current change is attributed to the highly tunable resistance, which can be realized as the superior properties of low power consumption, low working voltage, easily readout and simple electric circuits. In nature, the skin colors, such as chameleon, cuttlefish, frog and octopus change with the surroundings, temperature, and stress. This remarkable ability has been highly concerned by scientists. Electronic skin (e-skin) is deemed to be the next generation protecting technology that assists the human and robots to change their colors from the environmental effects. 52-53 For


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example, a chameleon-inspired e-skin can change its colors by touching the skin.54 Human beings are highly sensitive to the visual perception to interpret the environmental information, which can be explored other unfamiliar fields based on artificial skin. Here, we demonstrate that the novel magnetic field visualization can be varied by different applied magnetic field via the integration of our magnetoelectronic device with the red-green-blue light-emitting diodes (RGB LEDs). The magnetic sensor is connected to the red part of RGB LEDs as shown in Figure 7e. We fixed the illumination power of the green and blue part and changed the power of red part in Figure 7a-7c. It indicates that the colors can be manipulated under different magnetic field as shown in Figure 7d. In addition, the controllable intensity of light emitting spectrum through different applied magnetic field is shown in Supporting Information Video S2. Conclusion In summary, we have developed an ultrahigh performance magnetoelectronic device with an unprecedented sensitivity of 1507.9% mT-1. Our proposed patterned organic/inorganic hybrid electrode that integrates with PDMS, magnetic nanoparticles and metallic nanowires, which is suitable for large-area and high-throughput fabrication. Moreover, through an appropriately designed structure, our device shows a low working voltage (< 0.1 V) and low power consumption (< 0.1 mW) that goes along with high compatibility, fast response times (1 ms), great mechanical stability over different bending curves and more than 1000 bending cycles. Combined all these outstanding features together, this new magnetic sensor enables to be integrated with other functional devices toward multifunctional smart systems. We have successfully demonstrated the first direct integration of a commercial silicon based solar cell under room light condition to serve as a strategy towards the green powered autonomous system. In addition, we show that our magnetoelectric device possesses a great potential in touchless human machine interaction systems.


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Finally, our device exhibits a fast response speed that allows to the instantaneously transduce variation of magnetic field into electrical signals, optical signals or easy read-out signals. All these unique features show immensely potential applications, in which the high performance of our magnetoelectric devices can serve as a platform for further advanced developments in many different fields ranging from wearable electronics, robots, healthcare monitors, to communications. Methods In this experiment, the microstructured surface was fabricated by the mounds, which are made from silicon wafers (300 nm-SiO2). Initially, the solution of the PDMS (Dow Corning Sylgard 184; the weight ratio of base to cross linker was 10:1) with 33 wt % FeNi (Gredmann Group FeNi50) was stirred for one hour. In order to get the uniform distribution, the solution was spin coated (step 1: 500 rpm 30 s, step 2: 1000 rpm 40 s) on the mound and was dried in an oven for 90 minutes at 70 0C. Then, the FeNi/PDMS layer was peeled off from the mound and sprayed coating 50 wt % 2 ml AgNWs IPA solution (Kechuang, ave. diameter = 55~75 nm, length=10~20 μm) on the thin films, and then with the thermal treatment at 100 0C for 10 minutes. It resulted in a 4.27  sq-1 sheet resistance from the four-point probe measurement. Power supply (GW INSTEK GPC60300) is used for driving electromagnet, which is eminent for magnetic research due to its precisely controllable properties. On the other hand, the output performance of the magnetic sensor was measured by using power supply (Keithley 2410). When the current flows into the solenoid, the magnetic force will bend the micro-pyramid sensor, bringing in the observed current. In bending test, different curvature radius substrates (5.2 mm, 6.4 mm, 7.35 mm, 12.3 mm, and 18.2 mm) were used to measure the stability of the magnetic sensor under different degree of


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bending (Figure S3, Supporting Information), and magnet with translation stage is selected as the applied magnetic field in favour of simulating the real use in daily life, and the magnetic field of the magnet is measured by the Gauss meter (Bell model 5080).


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Figure 1. Schematic illustration of the device fabrication process.


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Figure 2. (a) SEM images of the AgNWs/PDMS film with pyramid microstructures. (b) Structure of device and working process.


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a

b 8

10-2

50 mT 100 mT 350 mT

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Current (A)

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-2 -4 -6 -8 -0.6

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1507.9% mT-1

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 I/I0(%)

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0.0

0

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Magnetic field (mT)

206.0% mT-1

50 100 150 200 250 300 350 400 450

Magnetic field (mT)

Figure 3. (a) I-V characteristics of the device under different magnetic field. (b) Real time current responses under different magnetic field at 0.1 V. (c) (d) The current responses under different magnetic fields at 0.1 V.


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Figure 4. Real-time response to the load/unload magnetic field at 150 mT (a) and 0.1 V (b).


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Figure 5. (a) The bending test of the magnetic sensor under different degree of bending at 150 mT and 0.1 V. (b) The bending cycles measurement of magnetic sensor over 5000 times with bending radius 5 mm.


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Figure 6. (a) I-V characteristics of the integrated magnetic sensor and solar cell under 1.083 and 0.144 mW cm-2 illumination at the magnetic field of 150 mT. (b) I-t characteristics of the integrated magnetic sensor and solar cell at the magnetic field of 150 mT. The inserted photo shows the combination of our device and a silicon based solar cell.


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Figure 7. (a)-(c) and (d) The magnetic sensor was directly integrated with RGB LEDs. The spectra and CIE coordinate were individually measured under different magnetic field of 100, 150, and 300 mT. (e) The circuit diagram of the magnetic sensor integrated with RGB LEDs.


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ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. (PDF) Comparison of sensitivities of flexible magnetic sensors; Supporting experimental results and discussion; Touchless piano keyboards (MP4); Magnetic field visualization (MP4) AUTHOR INFORMATION Corresponding Author *

E-mail: [email protected]

Present Addresses ‡ Institute of Optoelectronic Sciences, National Taiwan Ocean University, Keelung 202, Taiwan Author Contributions †

These authors contributed equally. Y. F. C supervised the project and conceived the study. The

manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Funding Sources This work was supported by the Ministry of Science and Technology and Ministry of Education of the Republic of China.


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Ultrahigh Sensitive and Flexible Magnetoelectronics with Magnetic

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