One-Piece Triboelectric Nanosensor for Self-Triggered Alarm System

Oct 21, 2016 - The self-triggered idea based on the triboelectric nanogenerator is compatible with intelligent interactive interface. Besides, this TE...
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One-Piece Triboelectric Nanosensor for SelfTriggered Alarm System and Latent Fingerprint Detection Yang Jie,†,‡,# Huarui Zhu,‡,# Xia Cao,*,†,‡ Yue Zhang,§ Ning Wang,*,∥ Liqun Zhang,⊥ and Zhong Lin Wang*,‡,∇ †

School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China Beijing Institute of Nanoenergy and Nanosystems, Chinese Academy of Sciences; National Center for Nanoscience and Technology (NCNST), Beijing 100083, P. R. China § Key Laboratory of New Energy Materials and Technologies, University of Science and Technology Beijing, Beijing 100083, P. R. China ∥ Center for Green Innovation, School of Mathematics and Physics, University of Science and Technology Beijing, Beijing 100083, P. R. China ⊥ College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China ∇ School of Material Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245, United States ‡

S Supporting Information *

ABSTRACT: Tactile sensing is of great importance in developing human− machine interface, remote control, and security systems. Here, a selftriggered alarm system based on the one-piece triboelectric nanosensor (TENS) is reported. By using nitrocellulose (NC) membrane as the triboelectric material, the as-designed TENS can not only sensitively respond to physical contacts in a self-triggered mode but also securely detect the third-level details of latent fingerprint. The self-triggered idea based on the triboelectric nanogenerator is compatible with intelligent interactive interface. Besides, this TENS can be conveniently fabricated and integrated into arrays at a large scale due to its freestanding, simple, and low-cost characteristics. This work presents alternative perspectives for the practical applications of the multifunctionalized TENS. KEYWORDS: triboelectric nanogenerator, self-triggered nanosensor, latent fingerprint, nitrocellulose membrane

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Fingerprints probably have been used as a kind of signature since ancient times, though the individuality was suggested by Henry Fauld until 1880.13,14 When fingers touch varieties of things, fingerprints are deposited on the surface: either visible or latent.15 Fingerprints analysis is a major part of crime scene investigation, especially in the case to determine whether a victim or a suspect should be linked to the crime scene or not.16−18 However, the latent fingerprints are the most common type of fingermark evidence found at crime scenes, it is important and necessary to visualize for critical identification. The detection of latent fingerprints relies heavily on the chemistry of the residues, which can be considered as a mixture of natural secretions and surface contaminants on the

ith the development of modern society, remote monitoring systems such as security surveillance are playing an increasing significant role.1−3 The sensing unit is a crucial component, which must have the capacity of robust responses.4,5 However, most of sensing units have complex structure and require an external battery, which limits the sustainability and adaptability. Recently, triboelectric nanogenerator has been a burgeoning technology that has advantages such as flexibility, high efficiency, low cost, and environmentally friendliness.6−8 Although the self-powered idea based on triboelectric nanogenerator has been developed to fabricate sustainable systems,9−12 the output stability is not compatible with most of conventional electronic devices. Besides, the trend in miniaturization and portability of intelligent electronic devices needs simpler and tinier structure of power supply and interactive interface. © 2016 American Chemical Society

Received: September 9, 2016 Accepted: October 20, 2016 Published: October 21, 2016 10366

DOI: 10.1021/acsnano.6b06100 ACS Nano 2016, 10, 10366−10372

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Figure 1. (a) Schematic illustration of the self-triggered single electrode TENS. (b) Photograph of an assembled single electrode TENS. Inset: The TENS bent by hand. (c) Schematic illustration of the self-triggered freestanding TENS. (d) Photograph of an assembled freestanding TENS. Inset: The TENS bent by hand. (e) AFM image of the nitrocellulose membrane. (f) SEM micrograph of NC membrane. Inset: View of the SEM micrograph at a higher magnification.

finger surface. Up to now, most of detection techniques have been developed on the base of components of human skin secretions, but it is difficult to determine the latent fingerprints’ position and composition.19−21 In this work, we report a self-triggered alarm system based on one-piece triboelectric nanosensor (TENS), which can be used for latent fingerprint detection at the same time. The one-piece structure is flexible, thin, and simply fabricated, which is compatible with intelligent interactive interface. In this detection strategy, the nitrocellulose (NC) membrane, whose nitrate group can interact with the strong dipole of the peptide bonds in the protein,22,23 plays a key role. Meanwhile, NC membrane acts as the triboelectric layer of TENS to produce an output voltage of more than 60 V, which endows this system a self-triggered operation mode and excludes the reliance on external power supplies. When the sensitive response to tiny physical contact and detection of the third-level details of latent fingerprint is considered, this self-triggered alarm system represents a simple but multifunctional practical application of triboelectric nanogenerator in the field of security surveillance.

RESULTS AND DISCUSSION Two kinds of one-piece TENS including single electrode TENS and freestanding TENS were designed for the self-triggered alarm system. The polyethylene terephthalate (PET) thin film (50 μm) was chosen as the substrate due to its excellent impact strength, lightweight, and easy processing, and patterns of 200 nm thick Cu layers were deposited as electrodes. As illustrated in Figure 1a, the single electrode TENS has a simple structure includes three layers: PET layer, Cu layer, and NC membrane. The NC membrane (pore size: 0.22 μm) is the important triboelectric surface as well as the substrate for latent fingerprint detection. Figure 1b exhibits photographs of an assembled TENS (2 cm × 2 cm) for the alarm system, which shows its simple and flexible characteristics. As for the freestanding TENS, the structure and photographs are displayed in Figure 1c and d, respectively. There are two Cu electrodes in different sizes and shapes: 2 cm × 2 and 2 cm × 0.5 cm, and the gap between two adjacent Cu electrodes is 0.5 cm. The NC membrane was tailored into a 3 cm × 2 cm rectangle and adhered on the copper electrodes. Both of structural designs are compatible to large-scale fabrication or array integration. Figure 1e shows an atomic force microscopy (AFM) image of NC membrane, which has the rough surface on the micro-/ 10367

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Figure 2. Working principle of the self-triggered alarm system. (a,d) Initial state when active object contacts with NC membrane, inducing negative triboelectric charges on the active object side and positive charges on the NC membrane. (b,e) Separation of the charged surfaces, with the potential difference produced and electrons in external circuit driven. (c,f) Fully separated position: signal transmitter works and alarm whistles.

alarm system because of their high voltage. Interestingly, though the structure of single electrode TENS is simpler, the freestanding TENS has better applicability and higher stability because the former needs an external ground-lead circuit. Thus, the freestanding TENS was selected for assembling the selftriggered alarm system. As shown in Figure 3d, the output voltage of freestanding TENS rises with increasing of the contact pressure. When the micro/nano structure of NC membrane is considered, this increasing voltage should be attributed to the increase of effective contact area, which can impart higher density of surface charges. And it is noticed that the output voltage is rather high even in the extremely low pressure region, which is very important for the operation of self-triggered alarm system. In addition to the stability and sensitivity, the output voltage of freestanding TENS is independent of the location of the active object. As shown in Figure 3e, this point is very important because the active object may be smaller than the surface of TENS. Here, the size of TENS was 12 cm × 8 cm, whereas the area of the active object of rubber was 2 cm × 2 cm. Besides, whether the alarm system can be triggered by active objects made of various materials is also important. Figure 3f presents that the output voltages of TENS are more than 60 V in response to different materials that are common in our daily life. It can be concluded that this type of freestanding TENS could be used for self-triggered alarm system in varieties of circumstances. After investigating the performance of TENS above, a complete self-triggered alarm system was assembled on the base of freestanding TENS. As demonstrated in Figure 4a, the selftriggered alarm system consists of a freestanding TENS (3 cm × 2 cm), a processing circuit (signal transmitter) and a wireless alarm. The large voltage signal generated by the TENS can be easily recognized by the processing circuit and can trigger the wireless alarm immediately. (Figure S1, Supporting Information) Compared to traditional security monitoring systems, this self-triggered alarm system provides a reliable and simple technology, which excludes the reliance on the external power supplies. Besides, this freestanding TENS can be easily fabricated at a large scale and integrated into arrays due to its freestanding, simple, and low-cost advantages. Figure 4b schematically illustrates a self-triggered alarm system based on an array integration of freestanding TENS and the inset shows

nanoscale. The micro-/nanostructure of NC membrane is able to improve the performance of TENS by inducing a larger triboelectric charge density.2 As revealed by a scanning electron microscopy image in Figure 1f, the NC membrane has uniformly distributed pores. In general, NC membranes are made up of randomly oriented fibers that are bonded together to form a tortuous maze of highly porous channels. Because of the flexible and one-piece structural characteristics, the asfabricated system is of good agility, lightweight, and easy preparation. The working principle of self-triggered TENS is illustrated in Figure 2. The touching or tapping of an active object (such as a finger, rubber glove, and poly(vinyl chloride) film) on the top surface of NC membrane induces changes in the electrical potential of the patterned Cu electrodes underneath, and charge transfer occurs between electrodes to balance the electrostatic potential. Because of the difference in their ability to attract and retain electrons in the triboelectric series, electrons are transferred from the surface that easily gives away electrons to the surface that attracts electrons (Table 1 in Supporting Information).8,24 When the charged active object separates from the NC membrane, a potential drop is created, which drives electrons in the electrodes to flow. The amount of the transferred charges and the electric potential both reach maximum values when the active object moves far away, as shown in Figure 2c,f. At this time, the alarm can be triggered by the TENS through the signal transmitter. When the active object contacts the NC membrane again, the alarm system can be triggered in another cycle. In order to investigate the touching response of the TENS, repetitive contact and separation were carried out by a linear motor that can provide precisely controlled reciprocating motions, as shown in Figure 3a. Figure 3b shows the output voltage of a single electrode TENS triggered by rubber at a contact force of 100 mN with a frequency of 1 Hz, which can produce pulsed output voltages with a maximum amplitude of 36 V. The tapping surface was covered by a rubber membrane with a size of 2 cm × 2 cm. Figure 3c shows the pulsed output voltages of the freestanding TENS with average amplitude of 65 V under the same condition. The performance of freestanding TENS is better than that of single electrode TENS due to the suppressed built-in voltages in single electrode TENS.25 Of course, both TENS can be used to fabricate the self-triggered 10368

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Figure 3. (a) Testing setup with linear motor. (b) Output voltage of single electrode TENS triggered with rubber. (c) Output voltage of freestanding TENS triggered with rubber. (d) Dependence of output voltage on the pressure from the contact. (e) Distribution of output voltage when finger contacts slightly at different positions on a large freestanding TENS (12 cm × 8 cm). Inset: schematic illustration of the five contact locations on the TENS. (f) Output voltage of freestanding TENS in response to different contact materials (2 cm × 2 cm).

latex glove. Because of the inherent advantage of high output voltage of TENS (Figure 3f), this alarm system gives an sensitive touch detection. Fingerprints are immutable and the uniqueness depends on the type and number of features, which are composed of epidermic ridges and furrows. Simple and fast latent fingerprint detection has also been explored based on the TENS. Because the deposited latent fingerprint is usually invisible to naked eyes, it is important to enhance the visual contrast between the prints and background by taking full advantage of the protein adsorption ability and hydrophilicity of NC membrane. Figure 5a shows the difference of visibility of latent fingerprint on the NC membrane by wetting the NC membrane in water for about 3 s. Because of the different hydrophilicities, the ridge of the fingerprint can not be wet. Then a clear fingerprint profile is thus rapidly visualized on the wet NC membrane, as shown in Figure 5b. Besides, after being stored for 1 week, the latent fingerprint can be visualized again by this way.

photograph of a tiny TENS array. When the application for the latent fingerprint detection of NC membrane is considered, the pattern of Cu electrode can be designed on the PET substrate, whereas the NC membrane could be tailored into separate pieces. In order to quickly find the position of latent fingerprint, small separate TENS array are connected with different signal transmitter. For the alarm system triggered by a single freestanding TENS, the wireless alarm starts to work if the TENS-generated output voltage is high enough to be recognized by the processing circuit. Figure 4c shows the working state of alarm system and the output voltage of the TENS produced by a human finger. Once the surface of TENS is touched, the processing circuit lights LEDs and turns on the wireless alarm, resulting in a sharp alarm and flashing red light (Video S1, Supporting Information). At the same time, a latent fingerprint will be deposited on the NC membrane. Figure 4d presents the working state of alarm system triggered by a human finger with 10369

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Figure 4. (a) Complete self-triggered alarm system based on the freestanding TENS. (b) Schematic diagram of array of the freestanding TENS. Inset: Photograph of an array of freestanding TENS. (c) Alarm system being triggered gently by a finger tapping on the freestanding TENS and the generated output voltage. (d) Alarm system being triggered gently by a finger with a latex glove tapping on the freestanding TENS and the generated output voltage.

Figure 5. (a) Photograph of sectional latent fingerprint when NC membrane is partially wetted by water. (b) Photograph of visualized latent fingerprint on the NC membrane. (c) First level detail of representative fingerprints enhanced by water: whorl direction of ridge. (d,e) Second level detail of representative fingerprints enhanced by water: bifurcation and ridge ending. (f,g,h) Third level detail of representative fingerprints enhanced by water: pattern, pore, and scar.

In order to get clearer visible details of latent fingerprint, an ordinary optical microscope was used to record the images.

Figure 5c shows the first level details of representative fingerprints of whorl direction of ridge. The spatial pattern of 10370

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ACS Nano the fingerprint is apparently enhanced by water, and the ridges contrast remarkably with the NC membrane. Figure 5d and e show the second level detail of representative fingerprints of bifurcation and ridge ending, respectively, which makes the fingerprint unique and forms the basis of personal identification. Moreover, because the latent fingerprint left on the scene is sometimes broken or imperfect, it is necessary to collect the third level details of fingerprint. As shown in Figure 5f,g,h, the third level details including distinctive pattern, pores and scar can be also easily collected. When the good protein adsorption ability of NC membrane is considered, this selftriggered alarm system is feasible to detect the latent fingerprint and examine the proteins from the latent fingerprint residues.

Video showing that when the surface of TENS is touched, the processing circuit lights LEDs and turns on the wireless alarm, resulting in a sharp alarm and flashing red light(AVI)

AUTHOR INFORMATION Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. *E-mail: [email protected]. Author Contributions #

These authors contributed equally to this work.

Author Contributions

CONCLUSIONS In summary, one-piece TENS for self-triggered alarm system and latent fingerprint detection has been demonstrated. The alarm system is triggered by the high efficient and freestanding flexible TENS in the absence of any external power supply. The self-triggered idea is introduced that the output of triboelectric nanogenerator is used as signal instead of power supply. Benefited from the high stability, uniformity, applicability, and especially the high sensitivity to very tiny pressure, the asdesigned alarm system secures sensitive touch detection. Besides, the good protein adsorption ability and special hydrophilicity of NC membrane provides a very easy and rapid detection to the third level details of latent fingerprint. When the advantages of scalability, low cost, and easy fabrication are considered, the one-piece TENS-based platform presents a promising prospect to achieve large-scale production and array-integration for other self-triggered monitoring systems.

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENTS We thanks to the support of the National Key R&D Project from Minister of Science and Technology, China (2016YFA0202702), the National Natural Science Foundation of China (NSFC Nos. 21275102, 21173017, 51272011, 21575009, and 21605004), the Science and Technology Research Projects from Education Ministry (213002A), the “Thousands Talents” Program for Pioneer Researcher and His Innovation Team, China, and the National Natural Science Foundation of China (Grant Nos. 51432005 and Y4YR011001). REFERENCES

METHODS Fabrication of a TENS. A 50 μm thick PET film was prepared with the desired dimensions to be substrate. A thin film of Cu (about 200 nm) was deposited on the substrate by ebeam evaporator. Before the deposition, the PET film was treated with ethanol and deionized water to remove the surface’s impurities. Then Cu lead wire was connected to electrode. Finally, a NC membrane was adhered on the device as an electrification layer. Latent Fingerprints Visualization. After the deposition of latent fingerprint, the NC membrane was split from the TENS and immersed into water for about 3 s. Then a clear fingerprint profile was rapidly visualized on the surface.26,27 In order to get clearer visible details of latent fingerprint, an ordinary optical microscope was used to record the images. Characterization. The surface morphology of the NC membrane was characterized by a Quanta FEG 450 field emission scanning electron microscope and a MFP-3D atomic force microscopy. For the measurement of the electric outputs of the TENS, an external force was applied by a commercial linear mechanical motor. The open-circuit voltage was measured by using a Keithley Model 6514 system electrometer.

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ASSOCIATED CONTENT S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.6b06100. Table of triboelectric series and circuit diagram of alarm system.(PDF) 10371

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NOTE ADDED AFTER ASAP PUBLICATION After this paper was published ASAP on October 24, 2016, corrections were made to the TOC graphic and Figure 5, and references 26 and 27 were added. The revised version was reposted November 1, 2016.

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