Three-Dimensional Organic Conductive Networks Embedded in Paper

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Three-dimensional organic conductive networks embedded in paper for flexible and foldable devices Murilo Santhiago, Jefferson Bettini, Sidnei Ramis de Araujo, and Carlos César Bof Bufon ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b02589 • Publication Date (Web): 11 Apr 2016 Downloaded from http://pubs.acs.org on April 12, 2016

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ACS Applied Materials & Interfaces

Three-dimensional organic conductive networks embedded in paper for flexible and foldable devices Murilo Santhiago†, Jefferson Bettini†, Sidnei R. Araújo†, Carlos C. B. Bufon†,‡,§* †

Brazilian Nanotechnology National Laboratory (LNNano), CNPEM, 13083-970, Campinas, Brazil. ‡

§

Institute of Physics "Gleb Wataghin" (IFGW), UNICAMP, 13083-859, Campinas, Brazil.

Department of Physical Chemistry, Institute of Chemistry, University of Campinas, P.O. Box 6154, 13084-862 Campinas, SP Brazil.

KEYWORDS: paper microfluidics, polypyrrole, flexible electronics, foldable devices, paperbased devices, conductive paper and three-dimensional conductive devices.

ABSTRACT: The fabrication of three-dimensional (3D) polypyrrole conductive tracks through the porous structure of paper is demonstrated by the first time. We combined paper microfluidics and gas-phase pyrrole monomers to chemically synthesize polypyrrole-conducting channels embedded in-between the cellulose fibers. By using this method, foldable conductive structures can be created across the whole paper structure, allowing the electrical connection between both sides of the substrate. As a proof of concept, Top-Channel-Top (TCT) and Top-Channel-Bottom

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(TCB) conductive interconnections, as well as all-organic paper-based touch buttons are demonstrated.

Flexible and foldable devices have gain substantial attention in the field of low-cost electronics.1,2 Among the flexible materials used as substrates, paper is a very interesting candidate with several attractive advantages.3 For instance, paper is a natural polymer broadly available worldwide, lightweight, environmental-friendly, portable and foldable. In addition, paper has unique porous structures formed by cellulose fibers, which can drive solutions by capillary action.4 All these features have been recently employed to fabricate microfluidic paperbased sensors,5–7 electronics8,9 and electrochemical devices.10–14 Towards the further development of paper-based electronics, the capability of creating high performance conductive tracks on the paper substrates is essential. Therefore, conductive polymers,15 metals16,17 and carbon-based nanomaterials18 have been proposed to generate conductive current pathways on paper. Similar to standard silicon technology, the continuous development towards three-dimensional (3D) electronics is also an attractive option for future complex paper-based systems. In 3Delectronics, in order to obtain integrated devices, each conductive layer must be precisely connected and aligned with the structures patterned on top of the substrate.19 Recently, a stamping method was employed to integrate conductive paths on a single side of epoxy treated paper substrates.20 Nevertheless, by making use of both sides of the substrate, the versatility of flexible paper-based electronics can be further enhanced. Consequently, alternative approaches for producing conductive tracks and vertical interconnects on paper is a demand. Such achievement, however, is a challenge since the paper porosity works as a filter suppressing the penetration of many nanomaterials present in many ink formulations. In addition, taking into


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account the appealing features supporting paper as substrate for electronics, namely flexibility and foldability, the creation of reliable conducting tracks and vertical interconnects that bears mechanical stress has to be considered. Therefore, one alternative way to fabricate 3D conductive tracks and vertical interconnects may arise from the in situ synthesis of conductive polymers. Here we employ an alternative chemical route, defined as gas-phase polymerization, to incorporate polypyrrole (PPy) in paper substrates.21 In this way, by allowing ionic oxidant species to flow through the hydrophilic channels and further exposing the patterned structure to pyrrole monomers in the gas-phase, an in situ polymerization process takes place. To the best our knowledge, this work is the first demonstration of PPy conductive networks, deterministically embedded in the fibers of paper, to create electrical interconnects for flexible and foldable 3Delectronics. The first fabrication step consists of printing hydrophobic wax patterns on Whatman #1 chromatography paper. This step defines channels to guide and confine the oxidant aqueous solutions. The capillary action is the responsible for driving the solution through the hydrophilic zones. Mild oxidant agents, such as CuCl2, are used to oxidize pyrrole monomers.21 Figure 1a shows a picture of a device where CuCl2 fills the hydrophilic zones (green parts). After folding, the hydrophilic zones become sandwiched by two hydrophobic layers. Once the edges of the folded structure are sealed with double-sided tape, the influence of such hydrophobic barriers on the polymerization process can be verified. The dark color observed in the region previously occupied by the oxidant agent is the signature that PPy has been formed after exposing the structure to pyrrole monomers (see the fabrication process detailed in Figure S1 of the supplementary information). Consequently, wax-printed paper does not represent a physical


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barrier to gas phase monomers, even though the wax treated regions become hydrophobic. The time necessary for small gaseous molecules to flow through the entire thickness of paper ( 10 cm. In this case, the design of equally spaced hydrophilic windows, on the top of the devices, allows fast vertical and lateral distribution of the oxidant agent along the channel (Figure 2c). The homogeneous long PPy track is shown in Figure 2d after unfolding the polymerized structure. The resistance versus length plot (Figure 2e) indicates that each delivery window distributes the oxidant agent homogeneously. The sheet resistance (Rsh) of the PPy incorporated in Whatman #1 paper, after removing the contact resistance (Figure S8), was found 40 ± 1 Ω sq-1. The fabrication of PPy conductive tracks, working as vertical interconnects between both sides of multiple paper layers, is further demonstrated. The patterning of hydrophilic windows on both


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sides of the substrate (Figure 3a), produces Top-Channel-Bottom (TCB) conductive tracks, which can be used to fabricate a variety of functional structures. Here, such approach was employed to power up a light emitting diode (LED) after folding (Figure 3b). In addition, as shown in Figure 3c, more complex geometries, consisting of PPy tracks crossing each other without creating an electrical short circuit, are demonstrated. The combination of the folding capabilities of paper substrates, with the fabrication of centimeter-long and vertical conductive tracks, allow us to create all-organic PPy touch buttons. Figure 3d shows a picture of the assembled device, where the principle of operation is based on the flexibility of the PPy embedded in the paper substrate. Once the buttons are pushed, the flexible PPy paper touches the LED contact pads lighting it up (see video in supplementary information). Figures S9 and S10 show the details of the fabrication process of the all-organic PPy touch button. This example highlights the potentiality of integrating organic conductive networks in paper.


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Figure 3. (a) Layout of the top-channel-bottom 3D conductive PPy tracks on paper. (b) Picture of the paper-based structure with outer/inner PPy contact pads lighting an LED. (c) Complex five layer (i-v) top-channel-bottom 3D PPy conductive tracks on paper. (d) Individually addressed linear touch buttons made of foldable paper-structures and long conductive PPy tracks. In conclusion, we have reported the fabrication of polypyrrole conductive networks embedded in conventional and commercially available paper substrates, as lightweight and foldable 3D devices. We have successfully demonstrated that such conductive networks can be formed over long channels (> 10 cm) as well as multilayered paper substrates. The combination of methods reported here is a promising alternative for creating of 3D paper-based devices and systems, including electrochemical biosensors, batteries and energy harvesting tools. ASSOCIATED CONTENT


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Supporting Information. Detailed experimental section, electrical characterization, device pictures, SEM images, theoretical information, touch button operation video and layout of devices. This material is available free of charge via the Internet at http://pubs.acs.org.” AUTHOR INFORMATION Corresponding Author *[email protected], phone +55(19)35175098 Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. ACKNOWLEDGMENT We would like to thank National Center for Research in Energy and Materials (CNPEM) and Brazilian Nanotechnology National Laboratory (LNNano). We also thank Davi H. S. de Camargo and Rafael Furlan de Oliveira for their valuable help and suggestions. CCBB is a productivity research fellow from CNPq (308782/2012-7). The authors acknowledge CNPq (Project 483550/2013-2) and FAPESP (Project 2013/22127-2) for the financial support. ABBREVIATIONS PPy, polypyrrole; ALD, atomic layer deposition; SEM, scanning electron microscopy; EDS, energy dispersive spectroscopy; TCT, top-channel-top; TCB, top-channel-bottom; ELR, electrical linear resistance. REFERENCES


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Three-Dimensional Organic Conductive Networks Embedded in Paper

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