신축성 있고 착용 가능한 탄소 나노튜브 기반 전자 기술

학위논문 (박사) -- 서울대학교 대학원 : 공과대학 협동과정 바이오엔지니어링전공, 2020. 8. 김대형.Networks of carbon nanotubes (CNTs) are a promising candidate for use as a basic building block for next-generation soft electronics, owing to their superior mechanical and electrical properties, chemical stability, and low production cost. In particular, the CNTs, which are produced as a mixture of metallic and semiconducting CNTs via chemical vapor deposition, can be sorted according to their electronic types, which makes them useful for specific purposes: semiconducting CNTs can be employed as channel materials in transistor-based applications and metallic CNTs as electrodes. However, the development of CNT-based electronics for soft applications is still at its infant stage, mainly limited by the lack of solid technologies for developing high-performance deformable devices whose electrical performances are comparable to those fabricated using conventional inorganic materials. In this regard, soft CNT electronics with high mechanical stability and electrical performances have been pursued. First, wearable nonvolatile memory modules and logic gates were fabricated by employing networks of semiconducting CNTs as the channel materials, with strain-tolerant device designs for high mechanical stability. The fabricated devices exhibited low operation voltages, high device-to-device uniformity, on/off ratios, and on-current density, while maintaining its performance during ~30% stretching after being mounted on the human skin. In addition, various functional logic gates verified the fidelity of the reported technology, and successful fabrication of non-volatile memory modules with wearable features has been reported for the first time at the time of publication. Second, the networks of semiconducting CNTs were used to fabricate signal amplifiers with a high gain of ~80, which were then used to amplify electrocardiogram (ECG) signals measured using a wearable sensor. At the same time, color-tunable organic light-emitting diodes (CTOLEDs) were developed based on ultra-thin charge blocking layer that controlled the flow of excitons during different voltage regimes. Together, they were integrated to construct a health monitoring platform whereby real-time ECG signals could be detected while simultaneously notifying its user of the ECG status via color changes of the wearable CTOLEDs. Third, intrinsically stretchable CNT transistors were developed, which was enabled by the developments of thickness controllable, vacuum-deposited stretchable dielectric layer and vacuum-deposited metal thin films. Previous works employed strain-tolerant device designs which are based on the use of filamentary serpentine-shaped interconnections, which severely sacrifice the device density. The developed stretchable dielectric, compatible with the current vacuum-based microfabrication technology, exhibited excellent insulating properties even for nanometer-range thicknesses, thereby enabling significant electrical performance improvements such as low operation voltage and high device uniformity/reproducibility, which has not been realized in the most advanced intrinsically stretchable transistors of today.탄소 나노튜브는 뛰어난 전기적, 화학적, 그리고 기계적 특성을 갖고 있어 차세대 유연 전자소자의 핵심 소재 중 하나로 각광을 받고 있으나, 아직까지 이를 이용한 실용적인 유연 전자소자의 개발은 실현되지 않고 있다. 이는 탄소 나노튜브의 전기적 특성대로 완벽히 분류해 낼 수 있는 기술, 탄소 나노튜브를 소자의 원하는 위치에 정확히 원하는 양만큼 네트워크 형태 혹은 정렬된 형태로 증착하는 기술, 그리고 유연 전자소자를 구성하는 다른 물질들의 개발 기술의 부재 때문이다. 지난 10여년간 해당 기술들은 광범위하게 연구되어지고 있으나, 탄소 나노튜브를 활용한 우수한 유연 전자소자 개발을 위한 핵심 기술들의 발전은 아직 초기 단계에 있다. 따라서 이 논문을 통해 탄소 나노튜브를 유연 전자소자에 적용시킬 수 있는 새로운 기술을 소개하고자 한다. 첫번째로 탄소 나노튜브와 유연 전자소자의 소자 디자인을 이용하여 피부위에 증착 가능한 비휘발성 메모리 소자를 제작하였고, 해당 기술을 이용하여 피부위에서 안전하게 동작할 수 있는 다양한 기초 회로들을 구현하였다. 탄소 나노튜브 기반 메모리 전자 소자 및 회로는 다양한 외부 응력이 가해져도 안정적으로 동작을 하였고, 개발된 기술을 통해 보다 실용적인 탄소 나노튜브 기반 유연 전자 소자의 제작 조건을 확립할 수 있었다. 두번째로 위에 개발된 기술을 바탕으로, 보다 복잡한 탄소 나노튜브 기반 유연 회로 및 구동전압에 따라 발광색이 변환하는 색변환 소자를 제작하여 해당 소자들이 피부위에 부착되어 잘 작동되도록 구현하였다. 그리고 이 두 가지 웨어러블 전자소자를 통합하여 실시간으로 심전도를 측정하여 탄소 나노튜브 기반 전자소자를 통해 해당 신호를 증폭시키고, 신호의 상태를 색변환 소자로 나타낼 수 있는 심전도 모니터 시스템을 구현하였다. 세번째로 진공 증착이 가능한 유연 절연체를 개발하여, 기존의 유연 전자소자들이 가지고 있던 극명한 한계를 극복하였다 (높은 구동 전압, 낮은 집적도, 대면적 소자 선능 균일도 등). 기존의 액상 기반 증착을 위주로 한 유연 전자 소자들은 무기물질 기반 전자소자 대비 극심한 성능 저하를 보여주었는데, 이를 해결하기 위해 새로운 절연물질을 개발하고 탄소 나노튜브 기반 유연 전자소자에 적용하여 그 가능성을 보여주었다.Chapter 1. Introduction 1 1.1 Discovery of CNTs and their benefits for soft electronic applications 1 1.2 Electrical sorting of CNTs 5 1.3 Deposition methods of solution-processed semiconducting CNTs 7 1.4 Conclusion 23 1.5 References 24 Chapter 2. Stretchable Carbon Nanotube Charge-Trap Floating-Gate Memory and Logic Devices for Wearable Electronics 32 2.1 Introduction 32 2.2 Experimental section 34 2.3 Results and discussion 36 2.4 Conclusion 62 2.5 References 63 Chapter 3. Wearable Electrocardiogram Monitor Using Carbon Nanotube Electronics and Color-Tunable Organic Light-Emitting Diodes 67 3.1 Introduction 67 3.2 Experimental section 70 3.3 Results and discussion 73 3.4 Conclusion 97 3.5 References 98 Chapter 4. Medium-Scale Electronic Skin Based on Carbon Nanotube Transistors with Vacuum-Deposited Stretchable Dielectric Film 102 4.1 Introduction 102 4.2 Experimental section 106 4.3 Result and discussion 111 4.4 Conclusion 135 4.5 References 136Docto

Ultrahigh areal number density solid-state on-chip microsupercapacitors via electrohydrodynamic jet printing

Microsupercapacitors (MSCs) have garnered considerable attention as a promising power source for microelectronics and miniaturized portable/wearable devices. However, their practical application has been hindered by the manufacturing complexity and dimensional limits. Here, we develop a new class of ultrahigh areal number density solid-state MSCs (UHD SS-MSCs) on a chip via electrohydrodynamic (EHD) jet printing. This is, to the best of our knowledge, the first study to exploit EHD jet printing in the MSCs. The activated carbon-based electrode inks are EHD jet-printed, creating interdigitated electrodes with fine feature sizes. Subsequently, a drying-free, ultraviolet-cured solid-state gel electrolyte is introduced to ensure electrochemical isolation between the SS-MSCs, enabling dense SS-MSC integration with on-demand (in-series/in-parallel) cell connection on a chip. The resulting on-chip UHD SS-MSCs exhibit exceptional areal number density [36 unit cells integrated on a chip (area = 8.0 mm x 8.2 mm), 54.9 cells cm(-2)] and areal operating voltage (65.9 V cm(-2))

Printed Spiral Coil Design, Implementation, And Optimization For 13.56 MHz Near-Field Wireless Resistive Analog Passive (WRAP) Sensors

Noroozi, Babak. Ph.D. The University of Memphis. June 2020. Printed Spiral Coil Design, Implementation, and Optimization for 13.56 MHz Near-Field Wireless Resistive Analog Passive (WRAP) Sensors. Major Professor: Dr. Bashir I. Morshed.Monitoring the bio-signals in the regular daily activities for a long time can embrace many benefits for the patients, caregivers, and healthcare system. Early diagnosis of diseases prior to the onset of serious symptoms gives more time to take some preventive action and to begin effective treatment with lower cost. These health and economy benefits are achievable with a user-friendly, low-cost, and unobtrusive wearable sensor that can easily be carried by a patient with no interference with the normal life. The easy application of such sensor brings the smart and connected community (SCC) idea to existence. The spread of a designated disease, like COVID-19, can be studied by collecting the physiological signals transmitted from the wearable sensors in conjunction with a mobile app interface. Moreover, such a comfortable wearable sensor can help to monitor the vital signals during fitness activities for workout concerns. The desire of such wearable sensor has been responded in many researches and commercial products such as smart watch and Fitbit. Wireless connection between the sensor on the body and the scanner is the key and common factor of all convenient wearables. This essential feature has been currently addressed by the costly techniques which is the main impediment to be widely applicable. The existing wireless methods including WiFi, Bluetooth, RFID, and NFC impose cost, complexity, weight, and extra maintenance including battery replacement or recharging, which drove us to propose a low-cost, convenient, and simple technique for wireless connection suitable for battery-less fully-passive sensors. Using a pair of coils connected by the near-field magnetic induction has been copiously used in wireless power transfer (WPT) for medical and industrial applications. However, near field RFID and NFC rely on this technique with active circuits. In contrast, we have proposed a wireless resistive analog passive (WRAP) sensor in which a resistive transducer at the secondary side, affects the primary quality factor (Q) through the inductive connection between a pair of square-shaped Printed Spiral Coils (PSC). The primary 13.56 MHz (ISM band) signal is modulated in response to the continuous change of bio-signal and the amount of response to the unit change in transducer resistance is defined as sensitivity. A higher sensitivity enables the system to respond to the smaller bio-signals and increases the coils maximum relative mobilities. The PSCs specifications and circuit components determine the sensitivity and its tolerance to the coils displacements. We first define and formulize the objective function for coil and components optimization to achieve the maximum sensitivity. Although the optimization methods do not show much different results, due to the speed and simplicity, the Genetic Algorithm (GA) technique is chosen as an advanced method. Then in second optimization stage, the axial and lateral distances that affect the mutual inductance are introduced to the optimization process. The results as a pair of PSCs profiles and the associated circuit components are obtained and fabricated that produced the maximum sensitivity and misalignment tolerance. For the sake of patient comfort, the secondary coil size is fixed at 20 mm and the primary coil is optimized at 60 mm with the maximum (normalized) sensitivity 1.3 m for 16 mm axial distance. If the Read-Zone is defined as the space in which the center of secondary coil can move and the sensitivity keeps at least half of its maximum value, the best Read-Zone has a conical shape with the base radius 22.5 mm and height 14 mm. The analytical results are verified by the measurement results on the fabricated coils and circuits

Microwave Devices for Wearable Sensors and IoT

The Internet of Things (IoT) paradigm is currently highly demanded in multiple scenarios and in particular plays an important role in solving medical-related challenges. RF and microwave technologies, coupled with wireless energy transfer, are interesting candidates because of their inherent contactless spectrometric capabilities and for the wireless transmission of sensing data. This article reviews some recent achievements in the field of wearable sensors, highlighting the benefits that these solutions introduce in operative contexts, such as indoor localization and microwave sensing. Wireless power transfer is an essential requirement to be fulfilled to allow these sensors to be not only wearable but also compact and lightweight while avoiding bulky batteries. Flexible materials and 3D printing polymers, as well as daily garments, are widely exploited within the presented solutions, allowing comfort and wearability without renouncing the robustness and reliability of the built-in wearable sensor

Study on conductive hydrogels in flexible and wearable triboelectric devices towards energy-harvesting and sensing applications (エネルギーハーベスティングおよびセンシングに向けたフレキシブルでウェアラブルな摩擦発電デバイスにおける導電性ハイドロゲルに関する研究)

信州大学(Shinshu university)博士（工学）この博士論文は、次の学術雑誌論文を一部に使用しています。 / ACS Applied Materials Interfaces 14(7) :9126-9137(2022); doi:10.1021/acsami.1c23176 / Advanced Fiber Materials 4(6) :1486-1499(2022); doi:10.1007/s42765-022-00181-4 / Chemical Engineering Journal 457 :141276(2023); doi:10.1016/j.cej.2023.141276ThesisDONG, LI. Study on conductive hydrogels in flexible and wearable triboelectric devices towards energy-harvesting and sensing applications (エネルギーハーベスティングおよびセンシングに向けたフレキシブルでウェアラブルな摩擦発電デバイスにおける導電性ハイドロゲルに関する研究). 信州大学, 2023, 博士論文. 博士（工学）, 甲第802号, 令和05年03月20日授与.doctoral thesi

A Multifunctional Integrated Circuit Router for Body Area Network Wearable Systems

A multifunctional router IC to be included in the nodes of a wearable body sensor network is described and evaluated. The router targets different application scenarios, especially those including tens of sensors, embedded into textile materials and with high data-rate communication demands. The router IC supports two different functionality sets, one for sensor nodes and another for the base node, both based on the same circuit module. The nodes are connected to each other by means of woven thick conductive yarns forming a mesh topology with the base node at the center. From the standpoint of the network, each sensor node is a four port router capable of handling packets from destination nodes to the base node, with sufficient redundant paths. The adopted hybrid circuit and packet switching scheme significantly improve network performance in terms of end-to-end delay, throughput and power consumption. The IC also implements a highly precise, sub-microsecond one-way time synchronization protocol which is used for time stamping the acquired data. The communication module was implemented in a 4-metal, 0.35 μm CMOS technology. The maximum data rate of the system is 35 Mbps while supporting up to 250 sensors, which exceeds current BAN applications scenarios.This work was supported in part by the Fundação para a Ciéncia e a Tecnologia (FCT) (Portuguese Foundation for Science and Technology) under Project PROLIMB PTDC/EEAELC/103683/2008 and through the Ph.D. Grant SFRH/BD/75324/2010, and in part by the CREaTION, FCT/MEC through national funds and co-funded by the FEDER-PT2020 partnership agreement under Project UIDB/EEA/50008/2020, Project CONQUEST (CMU/ECE/030/2017), Project COST CA15104, and ORCIP. (Corresponding author: Fardin Derogarian Miyandoab.)info:eu-repo/semantics/publishedVersio

Ultrasensitive Piezoresistive and Piezocapacitive Cellulose-Based Ionic Hydrogels for Wearable Multifunctional Sensing

Tactile sensors, namely, flexible devices that sense physical stimuli, have received much attention in the last few decades due to their applicability in a wide range of fields like the world of wearables, soft robotics, prosthetics, and e-skin. Nevertheless, achieving a trade-off among stretchability, good sensitivity, easy manufacturability, and multisensing ability is still a challenge. Herein, an extremely flexible strain sensor composed of a cellulose-based hydrogel is presented. A natural biocompatible carboxymethylcellulose (CMC) hydrogel endowed with ionic conductivity by sodium chloride (NaCl) was used as the sensitive part. Both the sensible layer and electrodes were investigated with an innovative approach for wearable sensor applications based on electrochemical impedance spectroscopy to find the best device configuration. The sensor, exploitable both as a piezoresistor and as a piezocapacitor, presents high sensitivity to external stimuli, together with an extreme stretchability of up to 600%, showing the best strain and temperature sensitivity among the ionic conductive hydrogel-based devices presented in the literature. The very high strain sensitivity enables the hydrogel to be implemented in wearable strain sensors to monitor different human motions and physiological signals, representing a valid solution for the realization of transparent, easily manufacturable, and low-environmental-impact devices

Ultrasensitive Piezoresistive and Piezocapacitive Cellulose-Based Ionic Hydrogels for Wearable Multifunctional Sensing

Tactile sensors, namely, flexible devices that sense physical stimuli, have received much attention in the last few decades due to their applicability in a wide range of fields like the world of wearables, soft robotics, prosthetics, and e-skin. Nevertheless, achieving a trade-off among stretchability, good sensitivity, easy manufacturability, and multisensing ability is still a challenge. Herein, an extremely flexible strain sensor composed of a cellulose-based hydrogel is presented. A natural biocompatible carboxymethylcellulose (CMC) hydrogel endowed with ionic conductivity by sodium chloride (NaCl) was used as the sensitive part. Both the sensible layer and electrodes were investigated with an innovative approach for wearable sensor applications based on electrochemical impedance spectroscopy to find the best device configuration. The sensor, exploitable both as a piezoresistor and as a piezocapacitor, presents high sensitivity to external stimuli, together with an extreme stretchability of up to 600%, showing the best strain and temperature sensitivity among the ionic conductive hydrogel-based devices presented in the literature. The very high strain sensitivity enables the hydrogel to be implemented in wearable strain sensors to monitor different human motions and physiological signals, representing a valid solution for the realization of transparent, easily manufacturable, and low-environmental-impact devices

Human Body–Electrode Interfaces for Wide-Frequency Sensing and Communication: A Review

Several on-body sensing and communication applications use electrodes in contact with the human body. Body–electrode interfaces in these cases act as a transducer, converting ionic current in the body to electronic current in the sensing and communication circuits and vice versa. An ideal body–electrode interface should have the characteristics of an electrical short, i.e., the transfer of ionic currents and electronic currents across the interface should happen without any hindrance. However, practical body–electrode interfaces often have definite impedances and potentials that hinder the free flow of currents, affecting the application’s performance. Minimizing the impact of body–electrode interfaces on the application’s performance requires one to understand the physics of such interfaces, how it distorts the signals passing through it, and how the interface-induced signal degradations affect the applications. Our work deals with reviewing these elements in the context of biopotential sensing and human body communication