Ultrathin Flexible Piezoelectric Sensors for Monitoring

3 downloads 0 Views 2MB Size Report
Dec 28, 2017 - Keywords: ultrathin flexible piezoelectric sensor; eye fatigue; eyelid motion; ..... sensitive pressure sensor with ultrathin gold nanowires," Nature.
Journal of Micromechanics and Microengineering

ACCEPTED MANUSCRIPT

Ultrathin Flexible Piezoelectric Sensors for Monitoring Eye Fatigue To cite this article before publication: Chaofeng Lu et al 2017 J. Micromech. Microeng. in press https://doi.org/10.1088/1361-6439/aaa219

Manuscript version: Accepted Manuscript Accepted Manuscript is “the version of the article accepted for publication including all changes made as a result of the peer review process, and which may also include the addition to the article by IOP Publishing of a header, an article ID, a cover sheet and/or an ‘Accepted Manuscript’ watermark, but excluding any other editing, typesetting or other changes made by IOP Publishing and/or its licensors” This Accepted Manuscript is © 2017 IOP Publishing Ltd.

During the embargo period (the 12 month period from the publication of the Version of Record of this article), the Accepted Manuscript is fully protected by copyright and cannot be reused or reposted elsewhere. As the Version of Record of this article is going to be / has been published on a subscription basis, this Accepted Manuscript is available for reuse under a CC BY-NC-ND 3.0 licence after the 12 month embargo period. After the embargo period, everyone is permitted to use copy and redistribute this article for non-commercial purposes only, provided that they adhere to all the terms of the licence https://creativecommons.org/licences/by-nc-nd/3.0 Although reasonable endeavours have been taken to obtain all necessary permissions from third parties to include their copyrighted content within this article, their full citation and copyright line may not be present in this Accepted Manuscript version. Before using any content from this article, please refer to the Version of Record on IOPscience once published for full citation and copyright details, as permissions will likely be required. All third party content is fully copyright protected, unless specifically stated otherwise in the figure caption in the Version of Record. View the article online for updates and enhancements.

This content was downloaded from IP address 128.6.218.72 on 28/12/2017 at 06:33

Page 1 of 15

MS. NO. JMM-103325.R

Revised manuscript

cri pt

Ultrathin Flexible Piezoelectric Sensors for Monitoring Eye Fatigue Chaofeng Lü1,2,3†*, Shuang Wu1†, Bingwei Lu4, Yangyang Zhang1, Yangkun Du5, Xue Feng4 1. College of Civil Engineering and Architecture, Zhejiang University, Hangzhou 310058, P. R. China

2. Key Laboratory of Soft Machines and Smart Devices of Zhejiang Province, Zhejiang University, Hangzhou 310027, P. R. China

3. Soft Matter Research Center, Zhejiang University, Hangzhou 310027, P. R. China

4. Department of Engineering Mechanics, Tsinghua University, Beijing 100084, P. R. China

5. Department of Engineering Mechanics, Zhejiang University, Hangzhou 310027, P. R. China

us

† These authors contribute equally to this work.

*Corresponding author, E-mail: [email protected]

an

Abstract: Eye fatigue is a symptom induced by long-term work of both eyes and brains. Without proper treatment, eye fatigue may incur serious problems. Current studies on detecting eye fatigue mainly focus on computer vision detect technology which can be very unreliable due to occasional

dM

bad visual conditions. As a solution, we proposed a wearable conformal in vivo eye fatigue monitoring sensor that contains an array of piezoelectric nanoribbons integrated on an ultrathin flexible substrate. By detecting strains on the skin of eyelid, the sensors may collect information about eye blinking, and, therefore, reveal human’s fatigue state. We first report the design and fabrication of the piezoelectric sensor and experimental characterization of voltage responses of the piezoelectric sensors. Under bending stress, the output voltage curves yield key information about

pte

the motion of human eyelid. We also develop a theoretical model to reveal the underlying mechanism of detecting eyelid motion. Both mechanical load test and in vivo test are conducted to convince the working performance of the sensors. With satisfied durability and high sensitivity, this sensor may efficiently detect abnormal eyelid motions, such as overlong closure, high blinking

ce

frequency, low closing speed and weak gazing strength, and may hopefully provide feedback for assessing eye fatigue in time so that unexpected situations can be prevented.

Keywords: ultrathin flexible piezoelectric sensor; eye fatigue; eyelid motion; real-time monitoring;

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

electromechanical analyses 1

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

1. Introduction Eye fatigue has been recognized as an important public health issue that is most commonly

cri pt

caused by reading, writing, or driving. Eye fatigue has serious adverse impacts on maintaining daily behavior and physical fitness. For example, eye fatigue may induce ophthalmic diseases, among

which computer vision syndrome is a common condition that results from focusing the eyes on computers or other digital devices for protracted, uninterrupted periods [1]. In contrast, fatigue

driving that is always accompanied with eye fatigue could be most dangerous and may even lead to mass casualties [2, 3]. A survey suggests that among all injuries or deaths, traffic accidents from

us

work to home is one of the major causes while fatigue is responsible for up to 20~30% of all road

fatalities [4]. For professionals who engage in special occupations, e.g. surgeons, eye fatigue can result in work faults and cause potential safety hazard [5]. Therefore, developing a fatigue

an

monitoring system and assessment method is essential for preventing accidents.

Among various techniques, most researchers have been focusing on those developed for collecting physiological signals such as electroencephalogram (EEG), electrocardiogram (ECG), or

dM

pulse rate [6, 7]. However, these methods are not convenient for practical use under work or driving circumstances because contacting hard electrodes and cables are indispensable. Head-mounted devices developed for monitoring eyelid motion and eye gaze [8], although remove the inconveniences of using electrodes and cables, are subject to limitations for their distractions to human’s daily activities. To avoid these distractions, computer vision detect technologies have been

pte

proposed to monitor eye fatigue through real-time eye movement capturing [9]. However, the success of applying these vision detect techniques relies significantly on image resolution, light condition, and other environmental conditions, and is not yet satisfying in veracity and instantaneity [10].

ce

Recent progresses in flexible/stretchable electronics [11-14], that may be integrated in conformal contact with human skin and deform into arbitrary shapes without detachment from the epidermal surface, have offered new strategies to retrieve vita signals. Representative devices based on flexible/stretchable electronics include sensors for measuring body temperature[15], pulsing [16],

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 15

breathing [17], electro cardio[18], and blood flow[19] etc. as well as for supercapacitors [20-22]. Since the eye fatigue may be recognized through the eyelid motion [23], we herein introduce an 2

Page 3 of 15

ultrathin piezoelectric sensor to monitor the real-time eyelid motion, thus making assessment on the fatigue state of eyes. Here, we chose lead zirconium titanate (PZT) as the functioning material to

cri pt

monitor the eyelid motion. This is due to fact that the processing technics for PZT are well-developed due to its high Curie temperature, and the piezoelectric coefficient of PZT is high which makes it able to output as high voltage signal as possible when subject to a relative small

mechanical deformation. The core functional part of the sensor is made of PZT nanoribbons and the sensor has an entire thickness of the order 10 μm so that it can maintain conformal contact with the eyelid skin during eye blink. Mechanical load test and in vivo test are carried out to validate the

us

functionality and efficiency of the sensor for monitoring the real-time eyelid motion. A simple

theoretical electromechanical model is also developed to correlate the output voltage of the sensor with the physical motion of the eyelid, thus further demonstrate the functionality of the sensor for

2. Sensor design and fabrication

an

monitoring and assessing eye fatigue.

dM

Fig. 1(a) illustrates the exploded-view of the ultrathin flexible ribbon-structured sensor. The main functional element is designed into a sandwich-like structure with a layer of PZT ribbon (1.5 μm) laminated between top (Au/Cr, 200 nm/10 nm) and bottom (Pt, 300 nm) electrodes (Fig. 1b). The PZT sensing module consists of 6 groups of 2 such ribbon structures that are electrically connected in parallel by a layer of Au/Cu (100 nm/600 nm) interconnects. Each of the 6 groups is

pte

connected in series to its neighboring group so as to increase the output voltage. The whole functional module is encapsulated by a thin spin-casted layer of polyimide (PI) at above and Kapton substrate beneath.

Fig. 2 provides the schematic diagrams of the fabrication process of the functional module of

ce

the sensor. Here, we adopt the well-developed MEMS techniques [24-26], e.g. metal deposition and mask lithography, to create the sandwich-like PZT structures. First, for a PZT film with a bottom electrode Pt on a silicon wafer, a layer of Au/Cu is sputtered onto the PZT film as an upper electrode, and, photolithography and wet etch process is used subsequently to define the previously designed

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

patterns. Every layer is designed smaller in size than the layer below to make place for further mask lithography. This functional element is then integrated with a receiving substrate of Kapton using 3

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

the well-established technique of transfer printing [27]. As preparation, we use a thick mask of hard-baked (250oC for 1 hour) PI as protection layer for the PZT elements and undercut the

cri pt

sacrificial SiO2 layer with hydrofluoric acid (H2O : 49%HF=1:3 by volume). A PDMS stamp serves as vehicle to retrieve the PZT element from the donor substrate at room temperature. Following the

law of fracture competition [28], a fast peeling speed guarantees the capture of element. We then print the PZT element onto a Kapton substrate with a layer of pre-cured PI (from poly (pyromellitic

dianhydride-co-4, 40-oxydianiline) amic acid solution; 4,000 rpm for 30 s, pre-cured on a hot plate

at 110oC for 2 mins) by compressing the PDMS stamp. Heating the system up to around 150oC for a

us

few minutes may fully cure the tacky interface and finish the process of transfer printing. After removing the stamp, another layer of PI is spin-casted on the top as the isolation layer. To enhance the electric responses, another round of sputtering and patterning of Cu/Au are conducted to

an

interconnect all functional elements electrically in series and parallel following the manner as mentioned before. Since the top and bottom electrodes are of different heights, a negative photoresist enpi202 is studied and introduced to perforate horizontal paths for interconnection.

dM

Then, we hot-press a row of ACF cable onto the two ends of the circuit as for external connection (Fig. 1c). Finally, a layer of encapsulation is spin-casted onto the functional module as the overall protection. Upon two hours of polarization with a 90V DC voltage source and simultaneous 130oC heating, the PZT sensor is eventually activated.

3. Results and discussion

pte

Mechanical load test is performed first to validate the functionality of the sensor (length 2.0 cm) by forcing it to out-of-plane deformation with the help of a vibration exciter. The sensor is perfectly bonded onto a silicone ribbon (thickness 1.0 mm, length 5.0 cm) at the center part, for which one end is fixed on a glass chunk and the other is rigidly anchored with the hand tip of the vibration

ce

exciter (Fig. 3a). The vibration exciter outputs a triangular wave of 4 Hz to deform the structure back and forth with a maximal end-to-end displacement of  L  2.5 mm (Fig. 3b and red line in Fig. 3d). The output voltage of the sensor exhibits a very stable feature with a peak-to-valley value

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 15

of about 200 mV (Fig. 3c) that is sufficient large to record using an oscilloscope. This demonstrates the reliability of the sensor for detecting the periodic mechanical deformation of the 4

Page 5 of 15

silicone ribbon substrate. The correlation between output voltage of the sensor and the input mechanical stimulation

cri pt

can be captured by an analytical electromechanical model. Under the action of an end-to-end compression  L(t ) , the sensor (length L0 ) undergoes buckling with an out-of-plane displacement in a sinusoidal configuration, and the amplitude may be approximated as 2



 L  L0 [24]. The PZT ribbons, together with the electrodes, bend with the buckled sensor,

 PZT  4

zp

L

L0

L0

, where  is the ratio of bending

us

with an axial strain given analytically as

rigidity per unit width of the two-layered substrate (PI plus silicone ribbon) to that of the substrate with PZT ribbons and electrodes, while zp is the distance of the PZT ribbon from the bottom of

an

the substrate. The axial strain in the PZT ribbon induces an electrical charge of

Q  e31 Ap PZT  33 Ap VPZT hp [29], where e31 , 33 are the effective piezoelectric constant

dM

and permittivity, Ap and hp are the effective area and thickness of a single PZT ribbon, while

VPZT is the voltage drop across the PZT ribbon. Since the current PZT sensing module consists of 12 PZT ribbons with every 2 connected in parallel and then in series, the total output voltage V may be determined according to the definition of current and Ohm’s law by the following equation

pte

3hp e zh d dV  V  24 31 p p dt 33 Ap R 33 L0 dt

L ,

(1)

L0

with R denoting the electrical resistance of the oscilloscope. The input end-to-end displacement

 L may be derived by integrating the above equation with respect to time t . The material, geometrical, and circuit properties of the current sensor are e31  40.5 10

12

C/N ,

ce

33  8.854  108 F/m [30, 31], Ap  1.216 10 7 m 2 , hp  1.5 μm , zp  51.986 μm ,

  0.808 , and R  10 MΩ . By inputting the measured voltage in Fig. 3(c), the calculated

end-to-end displacement (blue line) agrees very well with the actual input signal (red line in Fig.

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

3d). This indicates that the mechanical deformation of the silicone ribbon substrate can be well predicted by the theoretical electromechanical model together with the voltage outputs of the PZT 5

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

sensor. The in vivo test of the sensor yields a good relevancy between the output voltage and the

cri pt

actual motion of the eyelid (Fig. 4). The volunteer wears the sensor on the upper eyelid by a thin layer of biocompatible adhesive for medical use, and the sensor keeps as flat as possible when the

eye is closed (Fig. 4a). The adhesive used here was proved to be strong enough to bond the sensor

on the eyelid for several hours, but will not pose any uncomfortable feeling to the volunteer since the overall bending rigidity of the device/adhesive to that of the eyelid is only 0.69×10-4. A slight

out-of-plane buckling deformation almost in a sinusoidal form is observed in the sensor together

us

with the eyelid when the eye opens (Fig. 4b). The output voltage in Fig. 4(d) exhibits a steady variation (constant frequency and peak-valley value) that reveals very well the four stages of a normal eyelid motion, i.e. closing, closure, opening and gazing, which correspond to the voltage

an

rising until the peak, dropping back to zero, inverse rising to the valley, and decreasing until and remaining zero (Fig. 4c). For the normal eyelid motion in Fig. 4(c) and 4(d), the first three stages occurs within an extremely short period (~0.2 s) that is identical to published statistics [32]. In

dM

contrast to the mechanical load test, the substrate here is replaced by the eyelid with a typical thickness and modulus of 1.0 mm and 3.7 MPa [33, 34] , while zp  9.642 μm and

  0.793 . Using the measured voltage for normal eyelid motion in Fig. 4(d), the calculated end-to-end displacement of the sensor also exhibits a periodic feature (Fig. 4e), where an average gazing platform of 0.6~1.0 mm stands for a lucid and energetic mental state. The sharp decreasing

pte

of the displacement right after the blink attributes to a slight relaxation of the eyelid after opened consciously to a maximal extent during the in vivo test. An overlong closure during a series of normal eyelid motions is detected by the sensor which corresponds to the part of zero voltage before its inverse rising (Fig. 5a). This overlong closure

ce

may indicate high possibility of eye fatigue and is of great concern in the assessment of driving safety because it represents a completely blind driving distance [1-4]. Fig. 5(b) captures the moment of sudden rapid eye blinking that is normally recognized as a stress behavior of self-sobering when people feel tired or sleepy [35]. This can also be a supporting evidence of eye

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 15

fatigue. Fig. 5(c) demonstrates a gradually decreasing in voltage amplitude together with the lag of 6

Page 7 of 15

inverse rising, which provides typical combined signals for bluntness of eyelid behavior and thus suggests a state of sever eye fatigue. This eye fatigue phenomenon is further predicted by the

cri pt

electromechanical model for the end-to-end displacement of the sensor (Fig. 5d). After the gazing stage (nonzero platform), the closure keeps for a longer period (zero displacement) than that of the normal eye blink (Fig. 4e). In addition, the weakening phenomenon of the gazing state is also observed from the theoretical predictions where the nonzero platform decreases (Fig. 5d).

4. Conclusions

us

In summary, an ultrathin flexible piezoelectric sensor for monitoring eye fatigue was designed,

fabricated and tested. The sensor was fabricated using the conventional MEMS procedures together with the technique of transfer printing. The key functional module of the sensor is designed in an

an

ultrathin configuration of microscale so that it may contact conformally with the eyelid surface any distraction to the eyelid due to its extremely small bending rigidity. In addition, the use of piezoelectric materials makes the sensor free from external batteries. Both mechanical and in vivo

dM

tests validated the functionality and efficiency of the sensor to retrieve input mechanical deformations or eyelid motions, thus demonstrating its feasibility of monitoring the real-time eyelid motion. A simple electromechanical model was also developed to correlate the output voltage of the sensor with the eyelid motion. The predicted results may provide key information of the eyelid motion, e.g. blinking frequency, closing speed, closure period, and gazing period, that can also be

pte

reflected by the output voltage in time as evidences for assessment of eye fatigue. The results here suggest an innovative and efficient way of detecting eye fatigue and may provide guidance for

ce

future design of sensing devices.

Acknowledgements

C.L. acknowledges the financial supports by the National Natural Science of China under

grant no. 11322216 and 11621062. X.F. acknowledges the financial supports by the National

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

Natural Science Foundation of China under grant no. 11320101001.

7

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

References

[6] [7]

[8] [9] [10] [11] [12]

[13] [14]

[15]

[16] [17]

ce

[18]

cri pt

[5]

us

[4]

an

[3]

dM

[2]

C. Blehm, S. Vishnu, A. Khattak, S. Mitra, and R. W. Yee, "Computer vision syndrome: A review," Survey of Ophthalmology, vol. 50, no.3, pp. 253-262, May-Jun 2005. J. A. Horne and L. A. Reyner, "Sleep related vehicle accidents," Bmj, vol. 310, no.310, pp. 565-567, March 4 1995. P. Philip, P. Sagaspe, N. Moore, J. Taillard, A. Charles, C. Guilleminault, and B. Bioulac, "Fatigue, sleep restriction and driving performance," Accid Anal Prev, vol. 37, no.3, pp. 473-8, May 2005. M. Personick and M. Mushinski, "Highway fatalities: leading cause of work-related deaths," Statistical Bulletin, vol. 78, no.2, pp. 19-25, Apr-Jun 1997. J. Huang, Y. Wang, Z. Y. Fu, and Z. J. Guo, "Fatigue among Clinicians and the Safety of Patients," Chinese Medical Ethics, vol. 347, no.16, pp. 1249-1255, October 17 2008. S. Saito, "Does fatigue exist in a quantitative measurement of eye movements?," Ergonomics, vol. 35, no.5-6, pp. 607-615, May 1992. J. D. Wu and T. R. Chen, "Development of a drowsiness warning system based on the fuzzy logic images analysis," Expert Systems with Applications, vol. 34, no.2, pp. 1556-1561, February 2008. M. Sodhi, B. Reimer, J. L. Cohen, E. Vastenburg, S. Kirschenbaum, and S. Kirschenbaum, "On-road driver eye movement tracking using head-mounted devices," Symposium on Eye Tracking Research & Applications, pp. 61-68, March 2002. Q. Ji, Z. Zhu, and P. Lan, "Real-time nonintrusive monitoring and prediction of driver fatigue," IEEE Transactions on Vehicular Technology, vol. 53, no.4, pp. 1052-1068, July 2004. S. K. Lal and A. Craig, "A critical review of the psychophysiology of driver fatigue," Biological Psychology, vol. 55, no.3, pp. 173-194, February 2001. J. A. Rogers, T. Someya, and Y. Huang, "Materials and Mechanics for Stretchable Electronics," Science, vol. 327, no.5973, pp. 1603-7, March 2010. M. L. Hammock, A. Chortos, B. C. K. Tee, J. B. H. Tok, and Z. A. Bao, "25th Anniversary Article: The Evolution of Electronic Skin (E-Skin): A Brief History, Design Considerations, and Recent Progress," Advanced Materials, vol. 25, no.42, pp. 5997-6037, Nov 2013. J. A. Rogers, "Soft Electronics for the Human Body," in 2016 46th European Solid-State Device Research Conference, ed New York, 2016, pp. 21-22. M. E. Stewart, C. R. Anderton, L. B. Thompson, J. Maria, S. K. Gray, J. A. Rogers, and R. G. Nuzzo, "Nanostructured plasmonic sensors," Chemical Reviews, vol. 108, no.2, pp. 494-521, Feb 2008. R. C. Webb, A. P. Bonifas, A. Behnaz, Y. Zhang, K. J. Yu, H. Cheng, M. Shi, Z. Bian, Z. Liu, and Y. S. Kim, "Ultrathin conformal devices for precise and continuous thermal characterization of human skin," Nature Materials, vol. 12, no.10, p. 938, September 2013. C. Dagdeviren, et al., "Conformable amplified lead zirconate titanate sensors with enhanced piezoelectric response for cutaneous pressure monitoring," Nat Commun, vol. 5, p. 4496, Aug 05 2014. Y. Y. Chiu, W. Y. Lin, H. Y. Wang, S. B. Huang, and M. H. Wu, "Development of a piezoelectric polyvinylidene fluoride (PVDF) polymer-based sensor patch for simultaneous heartbeat and respiration monitoring," Sensors and Actuators a-Physical, vol. 189, pp. 328-334, Jan 2013. X. X. Zhang, T. Beebe, N. Jen, C. A. Lee, Y. C. Tai, and T. K. Hsiai, "Flexible and waterproof micro-sensors to uncover zebrafish circadian rhythms: The next generation of cardiac monitoring for drug screening," Biosensors & Bioelectronics, vol. 71, pp. 150-157, Sep 2015. R. C. Webb, et al., "Epidermal devices for noninvasive, precise, and continuous mapping of macrovascular and microvascular blood flow," Science Advances, vol. 1, no.9, Oct 2015. S. Zheng, X. Li, B. Yan, Q. Hu, Y. Xu, X. Xiao, H. Xue, and H. Pang, "Transition-Metal (Fe, Co, Ni) Based Metal-Organic Frameworks for Electrochemical Energy Storage," Advanced Energy Materials, vol. 7, no.18, p. 1602733, September 2017. S. Zheng, H. Xue, and H. Pang, "Supercapacitors based on metal coordination materials," Coordination Chemistry Reviews, July 2017.

pte

[1]

[19]

[20]

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 15

[21]

8

Page 9 of 15

[26] [27]

[28]

[29] [30]

[31]

[32] [33]

[34]

ce

pte

[35]

cri pt

[25]

us

[24]

an

[23]

Y. Xu, S. Zheng, H. Tang, X. Guo, H. Xue, and H. Pang, "Prussian blue and its derivatives as electrode materials for electrochemical energy storage," Energy Storage Materials, vol. 9, pp. 11-30, October 2017. D. F. Dinges and R. Grace, "PERCLOS: A Valid Psychophysiological Measure of Alertness as Assessed by Psychomotor Vigilance," Tech Brief, vol. 35, no.5-6, pp. 607-615, October 1998. H. Chen, X. Feng, and Y. Chen, "Directionally controlled transfer printing using micropatterned stamps," Applied Physics Letters, vol. 103, no.15, Oct 7 2013. Y. Chen, B. W. Lu, Y. H. Chen, and X. Feng, "Breathable and Stretchable Temperature Sensors Inspired by Skin," Scientific Reports, vol. 5, Jun 2015. S. Gong, W. Schwalb, Y. Wang, Y. Chen, Y. Tang, J. Si, B. Shirinzadeh, and W. Cheng, "A wearable and highly sensitive pressure sensor with ultrathin gold nanowires," Nature Communications, vol. 5, Feb 2014. M. A. Meitl, Z.-T. Zhu, V. Kumar, K. J. Lee, X. Feng, Y. Y. Huang, I. Adesida, R. G. Nuzzo, and J. A. Rogers, "Transfer printing by kinetic control of adhesion to an elastomeric stamp," Nature Materials, vol. 5, no.1, pp. 33-38, December 2005. X. Feng, M. A. Meitl, A. M. Bowen, Y. G. Huang, R. G. Nuzzo, and J. A. Rogers, "Competing Fracture in Kinetically Controlled Transfer Printing," Langmuir the Acs Journal of Surfaces & Colloids, vol. 23, no.25, p. 12555, September 2007. H. J. Ding and C. W. Qiu, "3 Dimensional Problems of Piezoelasticity," Nova Biomedical, 2015. M. H. Lente and J. A. Eiras, "Interrelationship Between Self-Heating and Ferroelectric Properties in PZT Ceramics During Polarization Reorientation," Journal of Physics Condensed Matter, vol. 12, no.27, p. 5939, March 2000. J. A. Mitchell and J. N. Reddy, "A refined hybrid plate theory for composite laminates with piezoelectric laminae," International Journal of Solids & Structures, vol. 32, no.16, pp. 2345-2367, August 1995. C. D. Von and U. Schuri, "Blink frequency and speed motor activity," Neuropsychologia, vol. 18, no.4-5, p. 603, January 1980. Y. Takema, Y. Yorimoto, M. Kawai, and G. Imokawa, "Age-related changes in the elastic properties and thickness of human facial skin," British Journal of Dermatology, vol. 131, no.5, p. 641, November 1994. J. L. Gennisson, T. Baldeweck, M. Tanter, and S. Catheline, "Assessment of elastic parameters of human skin using dynamic elastography," IEEE Transactions on Ultrasonics Ferroelectrics & Frequency Control, vol. 51, no.8, p. 980, August 2004. K. Schmidtke and J. A. Büttnerennever, "NERVOUS CONTROL OF EYELID FUNCTION," Brain, vol. 115, no.1, pp. 227-247, February 1992.

dM

[22]

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

9

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

Figure captions

cri pt

Figure 1 The flexible piezoelectric sensor for monitoring eyelid motion and eye fatigue. (a) Schematic diagram of multilayered structure of the sensor from tilted view and top view; (b) Optical microscope images during fabricating processes; (c) Photograph of a PZT sensor with ACF cables for external connection; (d) Photograph of a PZT sensor on Eco-flex substrate revealing its flexibility. Figure 2 Fabrication flow chart of the flexible piezoelectric sensor.

us

Figure 3 Mechanical load test on the PZT sensor and theoretical predictions on the input mechanical load. (a) Experimental setup of the mechanical load test; (b) Bending of the

piezoelectric sensor together with the silicon ribbon substrate under an end-to-end

an

displacement load ΔL; (c) The output voltage of the sensor under a triangular wave load input; (d) The theoretical prediction of the input load compares well with actual triangular load.

dM

Figure 4 In vivo monitoring of normal eyelid motion and the theoretical predictions. (a) Photograph of the PZT sensor with eyelid closed; (b) Photograph of the PZT sensor with eyelid open; (c) Correspondence of the output voltage to the four stages of a period of eyelid motion in normal mental state; (d) Output voltage of a series of normal eyelid motion; (e) Theoretical predictions of the end-to-end displacement of the sensor based

pte

on the measured voltage in (d) and its correspondence to the real-time eyelid motion. Figure 5 In vivo monitoring of three main types of abnormal eyelid motion and theoretical predictions. (a) Output voltage of eyelid motions with a significant overlong closure before the next eye opening; (b) Output voltage of normal eyelid motions with a

ce

subsequent transition to hastily eye blinking; (c) Output voltage of eyelid motions with gradual bluntness that represents a sever eye fatigue; (d) Theoretical predictions of the end-to-end displacement of the sensor based on the measured voltage in (c).

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 15

10

Page 11 of 15

Au PZT Pt

(a)

cri pt

Figure 1

Perforated(PI)

Tilted view

1cm

ce

pte

dM

ACF cable

an

(c)

(b)

us

Interconnections Top view

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

Eco-flex

Kapton

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

Au/Cr PZT Pt SiO2 Si

cri pt

Figure 2 Photolithography and etching

Undercut of SiO2

After deposition of Au/Cr Printing

Peeling up

Kapton Isolation with PI

Interconnection with Au/Cu

ce

pte

dM

an

PI

us

PDMS stamp

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 15

Au/Cu

Page 13 of 15

cri pt

Figure 3 (b)

(a)

L0 - D L

0 -100 1

2

3 Time (s)

4

5

2 1 0 -1

ce

pte

dM

-200

Actual Theoretical

3

0

1

2 3 Time (s)

an

100

4

2cm

us

(d)

200

Displacement (mm)

Voltage (mV)

(c)

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

4

5

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

(c)

(b)

Voltage (mV)

(a)

20

10 Closing 0 -10

10 0

0

1

2 3 Time (s)

4

5

ce

pte

dM

-20

0.8

1.0

1.2 1.4 Time (s)

1.6

1.8

Normal eye blink

Normal gazing zone

1.2 0.6 0.0

an

-10

Opening

us

20

(e) 1.8

Eyelid opening

Displacement (mm)

Voltage (mV)

Eyelid closing

Closure

Gazing

-20 0.6

(d)

cri pt

Figure 4

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 15

0

1

2 3 Time (s)

4

5

Page 15 of 15

Figure 5

0

1

2 3 Time (s)

4

5

0 -10 2 3 Time (s)

ce

pte

1

0 -10 -20 0

4

1

5

2 3 Time (s)

4

5

Overlong closure

Normal gazing zone

1.2

an

10

0

10

(d) 1.8

20

-20

20

hastily eye blink

cri pt

-10

30 Normal eye blink

us

0

Displacement (mm)

Voltage (mV)

Voltage (mV)

10

-20

(c)

(b)

Overlong closure

dM

Voltage (mV)

(a) 20

Ac

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

AUTHOR SUBMITTED MANUSCRIPT - JMM-103325.R1

0.6 0.0

0

1

2 3 Time (s)

4

5