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An Ultra-Flexible Transparent Oxide/Metal/Oxide Stack Electrode with Low Sheet Resistance for Electrophysiological Measurements Yasutoshi Jimbo, Naoji Matsuhisa, Wonryung Lee, Peter Zalar, Hiroaki Jinno, Tomoyuki Yokota, Masaki Sekino, and Takao Someya ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b12802 • Publication Date (Web): 21 Sep 2017 Downloaded from http://pubs.acs.org on September 22, 2017

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ACS Applied Materials & Interfaces

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An Ultra-Flexible Transparent Oxide/Metal/Oxide

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Stack Electrode with Low Sheet Resistance for

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Electrophysiological Measurements

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Yasutoshi Jimbo,1 Naoji Matsuhisa,1 Wonryung Lee, 1 Peter Zalar, 1,2 Hiroaki Jinno, 1 Tomoyuki

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Yokota, 1,2 Masaki Sekino, 1,2 and Takao Someya*1,2

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*1

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Bunkyo-ku, Tokyo 113-8656, Japan; *2Exploratory Research for Advanced Technology, Japan

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Science and Technology Agency, Bunkyo-ku, Tokyo 113-8656, Japan

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KEYWORDs: transparent electrode, oxide/metal/oxide, neural recording, optogenetics,

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Electrical Engineering and Information Systems, The University of Tokyo 7-3-1 Hongo,

implantable device, indium tin oxide, ultra-thin metal, flexibility

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ACS Paragon Plus Environment

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ABSTRACT: Flexible, transparent electrodes are a crucial component for future implantable

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and wearable systems. For practical applications, conductivity and flexibility should be further

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improved to prevent signal attenuation, heat generation, and disconnection. Herein, we fabricate

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an ultra-flexible transparent electrode with low sheet resistance (8.6 Ω/sq) using an indium-tin-

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oxide/Au/indium-tin-oxide multilayer on a 1 µm-thick parylene substrate. The electrodes were

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foldable, and when compared to pristine ITO displayed greater mechanical robustness.

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Applicability for large area applications was confirmed through electrochemical impedance

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measurements, and the compatibility of electrode arrays for in vivo applications was

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demonstrated with an optogenetic experiment. As a result of the ultra-flexible transparent

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electrode’s excellent conformity to soft tissue, voltage signals induced by light stimulation

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directly below the electrode were successfully recorded on the moving muscle.

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１．Introduction １．

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Transparent electrodes are a crucial component in flexible optoelectronic applications such as

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displays,1 imagers,2 and sensors.3 Highly conductive electrodes are preferable for high resolution,

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large area matrices to suppress energy loss, heat generation, and unevenness of pixel

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characteristics caused by wire resistance.3 Therefore, owing to their conductivity and

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transparency, oxides such as indium-tin-oxide (ITO) have been widely used. Nowadays, aiming

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at broad applications, especially for wearable or implantable devices, various characteristics

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including flexibility and straightforward processing methods are required for transparent

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electrodes.

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Following the trend, significant research effort has been dedicated towards the development of

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new types of materials for transparent electrodes, such as conducting polymers,4 metal nanowire


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based hybrid composites,5 and graphene.6 One of the promising candidates is a kind of

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multilayered structure, which is often categorized as an oxide/metal/oxide (OMO) or

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dielectric/metal/dielectric (DMD) structure. It have been widely used for displays or

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photovoltaics, and attracted great interest due to a number of desirable properties: low sheet

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resistance,7,8 controlled cavity effect,9 tunability of work function,10 mild processing

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conditions,11 and mechanical robustness.12,13 Although their wearable3 and in vitro applications

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as plasmonic biosensors14,15 have already been shown, in vivo applications have yet to be

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demonstrated.

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In vivo sensors, which employed graphene or ITO to enable optical stimulation and imaging

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while sensing, have been previously reported.16–18 They are fabricated on flexible plastic films to

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reduce the mechanical damage and inflammation of the tissue.19 Moreover, thinner substrates

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provide more conformal contact.20 The advantage of graphene is due to its flexibility and broad

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transmittance spectrum.16 The feasibility of simultaneous imaging, stimulation, and

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electrochemical measurement has been demonstrated using graphene electrode arrays.17 This

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multilayered graphene showed a sheet resistance of 76 Ω/sq and a transmittance of ~90%. On the

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other hand, ITO provides higher conductivity. One technique to avoid the high temperature

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process, which is not compatible with plastic substrates, is DC sputtering with a pre-oxidation

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step. It results in a low resistance of 10-50 Ω/sq and a transmittance of 80-90%18,21 without

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annealing. This method is preferable for removing the effect of wire resistance in sensor arrays.

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The feasibility of in vivo interface was demonstrated using transparent neural electrode arrays

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vertically integrated with LED chips.18 This research also revealed the environmental stability of

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parylene/ITO electrode through a 25-day soak test in saline solution.


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However, it is still difficult to realize transparent electrode with both enough conductivity and

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mechanical durability for large scale (~10 cm) transparent sensing arrays. Under certain

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condition, ITO can be disconnected irreversibly under strains below 1%,22 so that long readout

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made from ITO can be broken while sensing or processing.23 Graphene is stable up to ~10%

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strain and can recover from severe bending stress,6 but its sheet resistance is significantly higher

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than that of ITO (several tens to hundreds of ohms per square).17 Therefore, opaque metal wiring

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is usually employed to connect each cell.18,23 It covers a large portion of the area except for the

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contact via so that optical stimulation and imaging can still be performed, although in a limited

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manner.

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In this report, we fabricate an ITO/Au/ITO stack on a 1 µm-thick parylene substrate as an ultra-

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flexible transparent electrode with lower sheet resistance (8.6 Ω/sq) and better mechanical

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robustness than that of pristine ITO. ITO, Au, and parylene are known as stable materials in

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saline solution, and they have been used in the previous reports.18,24 Owing to the ultra-thin

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parylene substrate and encapsulation, this electrode was highly flexible and even foldable. The

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feasibility of large area, high resolution electrode arrays compatible with in vivo conditions was

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demonstrated by an electrochemical impedance measurement and an in vivo optogenetic

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experiment: neural signals from a mouse’s gracilis muscle induced by light stimulation directly

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under the electrode were successfully recorded.

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2. Experimental

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2.1 Device Structure and Fabrication


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Figure 1a shows a schematic of the structure of the multilayered electrode, consisting of an

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ITO/Au/ITO multilayer stack deposited on a 1 µm-thick parylene substrate. For materials

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selection, we took conductivity, transmittance, stability in saline solution, and processability into

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account. Parylene provides a smooth surface on supporting substrates, and it has been used for

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numerous in vivo devices because of its flexibility, low permeability, and biocompatibility.18,25,26

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ITO is also known as a promising transparent conductor because it has been used for versatile in

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vivo experiments owing to its high conductivity and transparency. Also, its behavior when

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interfaced with bio tissues has been well studied.18,24 Au is employed as an ultra-thin metal layer

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in order to obtain high conductivity. Whereas other highly conductive metals such as Ag or Cu

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are usually not stable in saline solution14,27 and sometimes cytotoxic,28,29 Au itself is a stable

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material. Because the thickness of the Au layer was only 14 nm, the multilayer electrode

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appeared transparent (Figure 1b).

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The fabrication process starts with a parylene dix-SR (Daisan Kasei Co. Ltd.) deposition using

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chemical vapor deposition (CVD) by a LABCOATER PDS2010 (Specialty Coating Systems) on

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a supporting glass substrate. The glass was cleaned and coated by spincoating (2000 rpm) with a

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fluorinated polymer, a mixture of NOVEC (3M Company) 1700 and 7100 in 1:6 volume ratio,

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which acts as a release layer for the device. Both the top and bottom ITO layers were deposited

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using RF sputtering by a SH-250-T04 (ULVAC Co. Ltd.) without heating the substrate.

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Sputtering was performed in a mixture of gas flow (Ar: 5 sccm, O2: 0.05 sccm). Before the

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introduction of gas, the pressure inside the chamber was reduced below 2 × 10-3 Pa. Au was

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thermally evaporated by an EX-200 (ULVAC Co. Ltd.) under vacuum conditions (< 5 × 10-4 Pa)

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and the deposition rate was 0.1 ± 0.005 nm/s. It is important to note that properties of ultra-thin

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Au is strongly affected by deposition conditions, especially by the deposition rate.30 Some


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samples, such as ones used for animal experiments, had a 1-µm thick parylene encapsulation

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layer deposited by the same process used for the substrate. Access to the electrode was prepared

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using a RIE-10NR (Samco Inc.) with O2 gas and a polyimide shadow mask to remove the

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parylene above the sensing area (Figure 1a). No specific damage to the ultra-thin substrate was

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observed with these process conditions. After all layers were deposited, the completed device

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was peeled off from the supporting substrate without any change in resistance. To test

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mechanical durability, several samples were fabricated on 125 µm-thick polyethylene

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naphthalate (PEN) films or laminated onto soft elastomers. The structures of the devices used for

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each experiment are all listed in Table S1.

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2.2 Device Characterization Equipment

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The sheet resistance measurement was performed with a four-point probe measurement system

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(Model Σ-5+, NPS Inc.). Transmittance spectra were measured with a spectrometer (ARM

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500N, JASCO Co.). An x-ray diffraction system (Smart Lab, Rigaku Co.), atomic force

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microscope (AFM, NanoScope IIIa, Veeco Instruments), and scanning electron microscope

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(SEM, S4800, Hitachi High-Technologies Co.) were all employed to closely examine film

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condition. Electrochemical impedance was measured using a material characterization cell (EC

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Frontier Co., Ltd.) and a precision LCR meter (4284A, Agilent Technologies). The thickness of

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ITO was controlled by deposition time; that of parylene was controlled by the amount of loaded

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material; and that of Au was controlled by the quartz crystal microbalance attached to the

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evaporator. All were calibrated with the use of a stylus surface profiler (Dektak XT, Bruker Co.).

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2.3 Mechanical Durability Tests


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To test the intrinsic mechanical durability of the ITO/Au/ITO multilayer stack, simple bending

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tests were performed using 125 µm-thick PEN substrates instead of the 1 µm-thick parylene

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substrates in order to apply precise tensile strain on the electrodes. They were patterned in 300

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µm × 300 µm, and 70 nm-thick Au was employed as a readout. While it was bent from 10 mm to

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5 mm of bending radius, the profile remained circular and no irreversible deformation of PEN

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substrate itself was observed.

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Due to the difficulty of fitting a 1 µm-thick film electrode to a circle with ~1 mm or less

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bending radius, we performed crumple tests of the ultra-thin film electrodes to compare the

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mechanical durability of each structure against severe stress. The samples fabricated on 1 µm-

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thick parylene substrates were laminated onto 1 mm-thick elastomers (Ecoflex 00-30, Smooth-

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On Inc.) by adhesive tape. The elastomer was pre-stretched and fixed to the stage, and then it

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was released slowly after the ultra-thin film was laminated on it. While it was being released the

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laminated film was crumpled, resulting in many tiny wrinkles and severe mechanical stress on

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the film. The samples were patterned with a length of 23 mm and a width of 3 mm, and 70 nm-

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thick Au was also employed as interconnects. During the cyclic test, the stretching and relaxation

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speed were kept at 5 %/s and a 5 second rest interval was observed after each motion (both

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stretching and relaxation) using a high precision mechanical system (AG-X, SHIMADZU Co.).

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2.4 Electrophysiological Measurements

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A rat (W-Tg(Thy1-COP4-YFP*)4Jfhy, the National Bio Resource Project of the Rat in Japan,

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male, 12-weeks-old) was genetically modified to express channelrodopsin-2 (ChR2) in its motor

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nerves and their terminals. It was anesthetized using 2%–2.5% isoflurane mixed with air, and the

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skin was incised to expose the gracilis muscle of its left hind limb. Local muscle movement was


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induced by light stimulation using a blue laser (wavelength: 473 nm, frequency: 2 Hz, duration:

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5 ms, diameter: 500 µm, intensity: 40 mW), whose position was guided by an optical fiber. The

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stimulation target on the motor nerve bundle was identified by optical stimulation before

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laminating the film device. The readout wire of the electrode laminated on the muscle was

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connected to an amplifier system marketed for medical use (Neuropack µ, MEB-9104, Nihon

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Kohden Co.) to measure the voltage signal. A ground electrode (V-040M4, Nihon Kohden Co.)

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was attached to the skin on the contralateral limb.26,31 All animal-based experiments were

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approved by the Ethics Committee of the University of Tokyo (KA12-1-1). (a)

(b)

Electrode

5mm

Figure 1. (a) Schematic structure of the ITO/Au/ITO multilayered electrode. (b) An image of the ITO/Au/ITO multilayered electrode patterned on parylene substrate, showing its visual transparency. The thickness of each layer is the same for the device used in the optogenetic experiment. 153 154 155


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3. Results and Discussions

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3.1 Electrical and Optical Characteristics

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Figure 2a shows the relationship between the thickness of Au and the sheet resistance of the

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ITO/Au/ITO electrodes when the thickness of the top/bottom ITO was fixed to 48 nm. The

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electrodes with a 14 nm thick Au layer showed a sheet resistance of 8.6 Ω/sq, although that of 96

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nm thick pristine ITO was 60 Ω/sq. The sheet resistance of the electrodes showed an inverse

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relationship with the thickness of Au. When the thickness is less than 8 nm, the sheet resistance

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increased drastically. This is due to the formation of island-like structures when it is thinner than

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8 nm.8,30,32 This island-like thin film growth was confirmed by scanning electron microscope

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(SEM) images (Figure S1) and x-ray diffraction (XRD) (Figures S2). The sheet resistance of ITO

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(48 nm) / Au (≤ 6 nm) / ITO (48 nm) became higher than that of a single ITO layer (96 nm). This

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result is consistent with previous reports.8,33 On the other hand, the thickness of ITO did not

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affect the sheet resistance as much as Au did because of the high conductivity of Au. The sheet

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resistances of ITO / Au (14 nm) / ITO were 8.9 ± 0.5 Ω/sq and 7.9 ± 0.3 Ω/sq when the ITO

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thicknesses were 16 and 64 nm, respectively. The surface roughness of ITO (48 nm) / Au (14

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nm) / ITO (48 nm) (Ra = 4.1 nm) was rather smaller than that of the parylene substrate (Ra = 5.7

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nm). Atomic force microscopy (AFM) images are available in Figure S3.

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Figure 2b shows transmittance spectra of both ITO (48 nm) / Au (14 nm) / ITO (48 nm)

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(without encapsulation) electrodes fabricated on a parylene substrate as well as ITO on a

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parylene substrate. The periodic wavy shapes appeared due to light interference with the thin

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parylene substrate. In the long wavelength range (>500 nm), the transmittance of ITO/Au/ITO is

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compatible with that of ITO. Indeed, the transmittance for shorter wavelengths becomes lower,

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yet the transmittance at a wavelength of 473 nm is as high as 69%. This value is sufficient in the


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latter optogenetic applications. Figure 2c shows further investigation of the transmittance as a

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function of Au thickness. The thickness of each ITO layer was fixed to 48 nm. By increasing the

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thickness of Au from 6 nm to 10 nm, the transmission peak shifted towards longer wavelengths

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because of absorption due to the localized surface plasmon resonance.30 When it reached 14 nm,

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transmittance was slightly decreased in the entire visible range because of the absorption and

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reflectance by the Au layer. In addition, the thicknesses of the top and bottom ITO layers were

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varied (Figure S4). The thickness of the bottom ITO did not affect optical transmittance except

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for the shift of the periodic interference peak. On the other hand, the top ITO layer affected the

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transparency, and the highest average transparency was obtained when the thickness was 48 nm.

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It can be attributed to the different scale of reflections on the ITO/Air interface and the

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parylene/ITO interface. (b)

(c)

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100

100

100 80

ITO (96 nm)

60 40 20 0

4

6 8 10 12 14 Au Thickness [nm]

80 60

Parylene ITO 40 ITO/Au/ITO (Front Side) 20 ITO/Au/ITO (Back Side) 0 400 500 600 700 800 Wavelength [nm]

Transmittance [%]

(a)

Transmittance [%]

Sheet Resistance [Ω/sq]

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80 60 40 20 0

Au

6 nm 10 nm 14 nm

400 500 600 700 800 Wavelength [nm]

Figure 2. Resistivity and transparency of ITO/Au/ITO electrodes. (a) Sheet resistance of ITO (48 nm) /Au/ ITO (48 nm) electrodes with Au layers of various thicknesses.

(b) Transmittance of a bare

parylene substrate, ITO (96 nm), and ITO /Au / ITO (48/14/48 nm) electrode. The spectrum was identical for light entering from the front side (ITO) and the back side (parylene substrate). (c) Transmittance spectrum of ITO (48 nm)/Au/ITO (48 nm) electrodes with various Au layer thicknesses.

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3.2 Mechanical Characteristics

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The high conductivity of ITO/Au/ITO multilayers under tensile strain was demonstrated by a

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bending durability test. Figure 3a shows the measurement setup. 125-µm thick PEN substrates

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were used for precisely applying tensile strain to the multilayer. For comparison, a single ITO

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layer and ITO/Au/ITO with different thicknesses were also tested. Strain applied to the electrode

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is given by ε = ⁄2 , where and stand for the thickness of film and bending radii,

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respectively,34 assuming the effect of ITO and Au is negligible because they are far thinner than

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PEN substrate. Figure 3b shows the sheet resistance-bending radius (tensile strain)

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characteristics. ITO (48 nm) /Au (14 nm) /ITO (48 nm) multilayers showed a lower sheet

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resistance than that of 96-nm thick ITO against various tensile strains. The wire resistance of

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both the ITO and the ITO/Au/ITO electrode started increasing drastically at a certain strain, and

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finally reached a highly resistive state. It is known that this critical strain corresponds to crack

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initiation and propagation on the film.12,22 Here we define the critical strain as the strain where

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resistance goes above twice that of its original value. The critical strain of each electrode is listed

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in Table S2. The critical strain of the multilayer and ITO were similar: 0.93% for ITO/Au/ITO

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and 0.90% for ITO, respectively. Even lower resistance and higher critical strain (1.03%) were

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obtained in ITO (16 nm) / Au (14 nm) / ITO (16 nm), and the improvement in critical strain was

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also observed in ITO with a thickness of 32 nm (1.11%). The thickness dependence of crack

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propagation in ITO can possibly be attributed to this trend.22 After it reached a highly resistive

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state, the resistance remained stable for both ITO and ITO/Au/ITO during this bending test. At

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bending radii less than 5 mm the PEN substrate deforms irreversibly, causing either the ITO or

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the ITO/Au/ITO to disconnect. In addition, resistance recovery after bending with a 5 mm

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bending radius was significantly improved by the presence of Au layers (Table S3). ITO/Au/ITO


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multilayer samples returned to their initial sheet resistance regardless of the thickness of the ITO

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layers. In contrast, ITO remains in the highly resistive state. This could be attributed to the

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difference in crack size and formation due to either the ductility of Au or weak adhesion between

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Au and ITO (SEM images are available in Figure S5).

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The improved mechanical robustness of an ITO/Au/ITO multilayer was also confirmed when

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fabricated on a 1 µm-thick parylene substrate. Severe mechanical stress was applied to the

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samples by stretching crumpled samples on elastomers. The crumples were made by first

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laminating onto pre-stretched elastomers and then releasing the strain (Figure 3c). The

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deformation of samples on elastomers was already studied and modeled.35 Samples with an ITO

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(48 nm) /Au (14 nm) /ITO (48 nm) multilayer and ITO (96 nm) were laminated on 15 % pre-

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stretched elastomers and the strain was subsequently released, resulting in a resistance change.

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The resistance of the ITO devices increased from 0.46 ± 0.04 kΩ to 4.7 ± 2.2 kΩ. On the other

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hand, that of ITO/Au/ITO devices showed a much smaller change from 66 ± 2 Ω to 106 ± 43 Ω.

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These changes are in the same order with the above mentioned resistance recovery after severe

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bending stress (bending radii = 5 mm) with PEN substrates.

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The mechanical durability of the crumpled samples were further investigated by cyclical 10%

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strain tests (Figure 3d). For both ITO and ITO/Au/ITO, the resistance of multiple samples was

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evaluated after 100 stretch cycles. For both structures, the graph displays the sample that showed

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the lowest resistance after the 100th cycle. The resistance went up when the samples were

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stretched, even though the crumples on the film device disappeared. This implies that not all

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strain was consumed to remove the wrinkles on the film, but on stretching of the film itself. This

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could be caused by uneven wrinkle formations. ITO devices showed a larger resistance change

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than ITO/Au/ITO multilayer devices. The baseline resistance slowly increased after the


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completion of each full stretch/relax cycle. This effect may be caused by the viscoelasticity of

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the elastomer layer. At the 100th cycle, the relative resistance change between the stretched state

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and the relaxed state (

⁄ ) was 6.6 for ITO, whereas it was 1.4 for the

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ITO/Au/ITO multilayer.

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In spite of the improved flexibility of the ITO/Au/ITO electrode, it no longer shows high

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conductivity after lamination onto a 25 % pre-stretched elastomer (Figure S6). It is known that a

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larger pre-stretch results in both wrinkles with smaller bending radius, and more severe

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mechanical stress.36,37 The radius of curvature which may contribute to the crack formation is

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estimated at several tens of micrometers based on behavior observed on PEN substrates. The

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histogram in Figure S7 indicates that the radius of curvature decreased for samples on elastomers

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with a higher degree of pre-stretching. Higher mechanical durability is achievable by employing

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a rational encapsulation strategy which places the ITO/Au/ITO layer on the neutral mechanical

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plane position in a film.38 By encapsulating the ITO/Au/ITO electrode with parylene of the same

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thickness as used for the substrate, it can endure stress on a 100 % pre-stretched elastomer. Even

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when laminated on a 200 % pre-stretched elastomer, the resistance increased only by 17%.


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(a)

(b)

(c)

(d)

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Figure 3. (a) Photograph of a bending test. A PEN film was pinched by parallel stages and deformed along the red circle. (b) Resistance change of ITO and ITO/Au/ITO electrodes during bending tests described in (a). Each data point and error bar indicates the geometric mean and geometric standard deviation of the samples. (c) Schematic illustration of the process for laminating a film onto an elastomer. (d) 10 % cyclic stretching test for an electrode laminated on a 15 % pre-stretched elastomer as described in (c). The samples were patterned with a length of 23 mm and a width of 3 mm. The samples which showed the lowest resistance after 100 cycles were plotted for both ITO and ITO/Au/ITO. 253


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3.3 Electrophysiological Measurements

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The practical feasibility of ITO/Au/ITO electrodes was successfully demonstrated by

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electromyogram (EMG) measurements using optogenetic stimulation. For this demonstration, an

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ITO/Au/ITO electrode was encapsulated with a 1 µm-thick parylene layer (except for a sensing

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area with a diameter of 500 µm). The low sheet resistance of the ITO/Au/ITO layer enabled

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sensing independent from the wire resistance. Figure 4a shows the electrochemical impedance of

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an ITO/Au/ITO electrode and ITO in saline solution. The effect of wire resistance on

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electrochemical impedance was investigated by preparing samples with four different wire

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lengths (L) and fixed width (W) (300 µm). The detailed design is available in Table S1 and

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Figure S8. At low frequency (10 kHz), the impedance was dominated by the wire resistance.

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Because of the low sheet resistance, the impedance for EMG (

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