Wearable Printed Temperature Sensors: Short Review on Latest Advances for Biomedical Applications

✅ 全文

可穿戴印刷温度传感器:生物医学应用最新进展的简要综述

作者 Sukhan Lee; Shawkat Ali; Arshad Khan; Amine Bermak 期刊 IEEE Reviews in Biomedical Engineering 发表日期 2021 ISSN 1937-3333 DOI 10.1109/rbme.2021.3121480 类型 原创研究 (Original Research)

📄 中文摘要 Chinese Abstract

中文
可穿戴生物传感设备因实时健康监测和慢性病早期检测的需求而快速发展。在众多生理参数中,温度是一项关键的生命体征,使得可穿戴温度传感器对于持续健康追踪至关重要。这些传感器通常采用印刷技术在柔性、生物相容性聚合物基底上制备,实现了低成本、大面积制造。功能纳米材料(如金属、导电聚合物和纳米复合材料)与柔顺基底的集成,使其能够共形贴附于人体皮肤,在日常活动中实现准确可靠的温度监测。

📋 英文结构化总结 English Structured Summary

全文整理

EN

Background:

Wearable biosensing devices are rapidly advancing due to the need for real-time health monitoring and early detection of chronic diseases. Among various physiological parameters, temperature is a critical vital sign, making wearable temperature sensors essential for continuous health tracking. These sensors are typically fabricated on flexible, biocompatible polymeric substrates using printing technologies, which enable cost-effective, large-area manufacturing. The integration of functional nanomaterials—such as metals, conductive polymers, and nanocomposites—with compliant substrates allows for conformal attachment to human skin, enabling accurate and reliable temperature monitoring during daily activities.

Methods:

This paper is a methodological review that synthesizes recent advances in printed wearable temperature sensors. It examines the design, materials, fabrication techniques (particularly solution-based printing methods such as inkjet, screen, aerosol jet, and transfer printing), and performance metrics of these sensors. The review compares different sensor architectures—including resistance temperature detectors (RTDs) and thermistors—and evaluates their sensitivity, linearity, response time, and stability. Key enabling technologies such as colloidal ink formulation, low-temperature sintering, and substrate compatibility are discussed in the context of scalable and wearable-friendly manufacturing.

Results:

Printed temperature sensors based on metallic conductors (e.g., Ag, Au), conductive polymers (e.g., PEDOT:PSS), and nanocomposites (e.g., rGO/PEDOT:PSS, CNT/PEDOT:PSS) demonstrate high sensitivity and stability across physiological temperature ranges (25–45 °C). Sensors using PEDOT:PSS show negative temperature coefficient (NTC) behavior with sensitivities up to 0.77%/°C, while Ag-based RTDs exhibit positive TCR values around 0.0029–0.06/°C. Nanocomposite-based sensors, especially those incorporating graphene or carbon nanotubes, achieve enhanced performance, with one reporting a sensitivity of 1.3%/°C. Unconventional designs such as Wheatstone bridge configurations and microfluidic liquid-metal sensors also show promise for improved accuracy and strain insensitivity.

Data Summary:

Reported TCR values range from 0.002778/°C (Au meander) to 1.3%/°C (PEDOT:PSS/CNT wide-line sensor). Inkjet-printed Ag sensors on biocompatible substrates achieve 0.06/°C sensitivity, while PEDOT:PSS-based thermistors reach 0.77%/°C. Nanocomposite sensors (e.g., rGO/PHB) show TCRs between 0.018 and 0.03/°C. Humidity and mechanical deformation tests indicate stable performance under varying environmental and physiological conditions, with minimal hysteresis and drift over extended use.

Conclusions:

Printed wearable temperature sensors have made significant progress in sensitivity, flexibility, and biocompatibility, enabling reliable real-time health monitoring. The combination of advanced nanomaterials with scalable printing techniques facilitates low-cost, large-area fabrication on flexible substrates. Key challenges remain in long-term stability, repeatability, resistance to environmental factors (e.g., humidity, oxidation), and integration into multifunctional wearable patches. Future work should focus on developing low-temperature sintering methods, improving material robustness, and enabling wireless, self-powered operation for clinical and remote healthcare applications.

Practical Significance:

These sensors are directly applicable in continuous health monitoring for patients with chronic conditions (e.g., fever, cardiovascular disease), post-surgical care, athletic performance tracking, and occupational safety in extreme environments. Their compatibility with wireless data transmission enables remote patient monitoring, supporting telemedicine and early intervention strategies in both clinical and home settings.

📋 中文结构化总结 Chinese Structured Summary

中文

背景:

可穿戴生物传感设备因实时健康监测和慢性病早期检测的需求而快速发展。在众多生理参数中,温度是一项关键的生命体征,使得可穿戴温度传感器对于持续健康追踪至关重要。这些传感器通常采用印刷技术在柔性、生物相容性聚合物基底上制备,实现了低成本、大面积制造。功能纳米材料(如金属、导电聚合物和纳米复合材料)与柔顺基底的集成,使其能够共形贴附于人体皮肤,在日常活动中实现准确可靠的温度监测。

方法:

本文为一篇方法学综述,综合了印刷可穿戴温度传感器的最新研究进展。文章考察了这些传感器的设计、材料、制备技术(特别是基于溶液的印刷方法,如喷墨印刷、丝网印刷、气溶胶喷射印刷和转移印刷)以及性能指标。综述比较了不同的传感器结构——包括电阻温度检测器(RTD)和热敏电阻——并评估了它们的灵敏度、线性度、响应时间和稳定性。讨论了关键使能技术,如胶体油墨配方、低温烧结和基底兼容性,重点关注可扩展且适用于可穿戴设备的制造工艺。

结果:

基于金属导体(如Ag、Au)、导电聚合物(如PEDOT:PSS)和纳米复合材料(如rGO/PEDOT:PSS、CNT/PEDOT:PSS)的印刷温度传感器在生理温度范围(25–45°C)内表现出高灵敏度和稳定性。使用PEDOT:PSS的传感器呈现负温度系数(NTC)特性,灵敏度高达0.77%/°C;而基于Ag的RTD则表现出约0.0029–0.06/°C的正TCR值。纳米复合材料传感器,特别是掺入石墨烯或碳纳米管的传感器,性能进一步提升,其中一种传感器灵敏度达到1.3%/°C。非常规设计,如惠斯通电桥结构和微流控液态金属传感器,在提高精度和抗应变干扰方面也展现出良好前景。

数据汇总:

已报道的TCR值范围从0.002778/°C(Au蛇形结构)到1.3%/°C(PEDOT:PSS/CNT宽线传感器)。在生物相容性基底上喷墨印刷的Ag传感器灵敏度为0.06/°C,而基于PEDOT:PSS的热敏电阻达到0.77%/°C。纳米复合材料传感器(如rGO/PHB)的TCR介于0.018至0.03/°C之间。湿度和机械变形测试表明,在不同环境和生理条件下传感器性能稳定,在长时间使用中迟滞和漂移极小。

结论:

印刷可穿戴温度传感器在灵敏度、柔性和生物相容性方面取得了显著进展,实现了可靠的实时健康监测。先进纳米材料与可扩展印刷技术的结合,促进了在柔性基底上的低成本、大面积制造。长期稳定性、重复性、抗环境因素(如湿度、氧化)能力以及集成到多功能可穿戴贴片等方面仍存在关键挑战。未来工作应聚焦于开发低温烧结方法、提升材料耐久性,并实现无线自供电运行,以服务于临床和远程医疗应用。

实际意义:

这些传感器可直接应用于慢性病患者(如发热、心血管疾病)的持续健康监测、术后护理、运动表现追踪以及极端环境下的职业安全防护。其与无线数据传输的兼容性支持远程患者监护,有助于在临床和家庭场景中实现远程医疗和早期干预策略。

📖 英文全文 English Full Text

EN

152 IEEE REVIEWS IN BIOMEDICAL ENGINEERING, VOL. 16, 2023

Wearable Printed Temperature Sensors: Short Review on Latest Advances for

Biomedical Applications Saleem Khan , Shaukat Ali , Arshad Khan

, and Amine Bermak , Senior Member, IEEE (Methodological Review)

Abstract—The rapid growth in wearable biosensing de- vices is driven by the strong desire to monitor the human health data and to predict the symptoms of chronic dis- eases at an early stage. Different sensors are developed for continuous monitoring of various biomarkers through wearable and implantable sensing patches. Temperature sensor has proved to be an important physiological pa- rameter amongst the various wearable biosensing patches.

This paper highlights the recent progresses made in print- ing of functional nanomaterials for developing wearable temperature sensors on polymeric substrates. A special focus is given to the advanced functional nanomaterials as well as their deposition through printing technologies.

The geometric resolutions, shape, physical and electrical characteristics as well as sensing properties using different materials are compared and summarized. Wearability is the main concern of these newly developed sensors, which is summarized by discussing representative examples. Fi- nally, the challenges concerning the stability, repeatability, reliability, sensitivity, linearity, ageing, and large-scale man- ufacturing are discussed with future outlook of the wear- able systems.

Index Terms—Biodegradable, nanomaterials, printing, temperature sensors, wearable Electronics.

I. INTRODUCTION W EARABLE sensors and transducers on polymeric foils have attracted significant attention and are growing rapidly with the fast advent in miniaturized thin film electron- ics and the need for medical practitioner to obtain real time data from their patients [1]–[5]. The unique properties such as mechanical flexibility, lightweight and in some cases biocom- patibility and biodegradability make them distinguished from silicon-based devices [6]–[9]. The conformal integration of thin polymeric substrates to nonplanar surfaces without significant

Manuscript received 5 April 2021; revised 12 September 2021; ac- cepted 16 October 2021. Date of publication 20 October 2021; date of current version 6 January 2023. This work was supported by NPRP from Qatar National Research Fund (a member of Qatar Foundation) under Grants PRP10-0201-170315 and NPRP11S-0110-180246, and by Qatar National Library. (Corresponding author: Saleem Khan.)

The authors are with the College of Science and Engineering, Hamad

Bin Khalifa University, Qatar Foundation, Doha 5825, Qatar (e-mail: sakhan3@hbku.edu.qa; shaali@hbku.edu.qa; arkhan4@hbku.edu.qa; abermak@hbku.edu.qa).

Digital Object Identifier 10.1109/RBME.2021.3121480 degradation in the sensor signals make them ideal for wearable biosensing related applications [4], [10], [11]. The lower cost of polymeric substrates as well as the functional nanomateri- als and their manufacturing through printing technologies en- hance the attractiveness for cost-effective portable and wearable sensing applications [12]–[16]. Printing is preferred on foils due to their incompatibility with higher temperatures in clean room processes. Printing enables position-specific deposition of functional materials that significantly reduces the materi- als wastage[14]. A number of interesting sensing devices and systems have been reported and the number still rising with a particular focus on wearable biosensing devices [9], [10], [17]–[19]. Among the list of various biosensors developed, temperature sensors are widely reported as standalone or part of a sensing patch that can be placed on human skin [19]–[24].

Temperature is a main vital physiological sign that is used to determine the heat exchanges occurring between the epidermal tissues and external environment. For human body, the tempera- ture monitoring on human skin is broadly explored as compared to the deep body temperature sensing [23], [25]–[27]. Human body suffers from the thermal stresses upon experiencing to a range of diseases, for instance normal fever to more chronic diseases such as cardiovascular, diabetic, pulmonological diag- nostics, cancer, and other syndromes etc. [28], [29]. The rise in skin as well as deep body temperatures are considered as preliminary indicator for a seriously developing disease, and continuous monitoring becomes essential in most of the cases [27], [28], [30], [31]. Therefore, wearable biosensing patches developed on biocompatible polymeric substrates are crucial for real-time monitoring of biomarkers that can send data wirelessly to the hospital facilities for expert observation and opinion of the physicians remotely [32]–[36]. Fig. 1 shows a broader overview of the wearable biosensing scenarios and potential biomarkers used for real time health monitoring.

Selection of the substrates is critical to the wearable tempera- ture sensors besides the materials properties, as the deployment onnonplanarsurfacessuchashumanskinrequiresgoodsensitiv- ity and accuracy at different orientations such as setting, moving, stretching, and bending etc. [37]–[39]. This can be achieved through various strategies by placing the sensors on places which are not subjected to physiological movements or make a good selection of all the materials for compliant integration to human

This work is licensed under a Creative Commons Attribution 4.0 License. For more information, see http://creativecommons.org/licenses/by/4.0/

KHAN et al.: WEARABLE PRINTED TEMPERATURE SENSORS: SHORT REVIEW ON LATEST ADVANCES

153 Fig. 1.

Overview of wearable electronics enablers and perpsective application areas of temperature sensing. Proof of concept devices are attached to human skin. [20], [13], [17], [69], [140], [145] [reproduced with permission]. skin, that can easily mitigate the unwanted noise signals [40]– [44]. Besides the good sensitivity and accuracy, the temperature sensorsaredesiredtohavegoodrepeatability,sensitivetominute changes as the temperature changing window is very small (i.e.,

25–40 °C), and lastly the robustness with enhanced stability against varying climatic conditions [45]–[48]. The stretchable interconnects play significant role and are therefore considered as the main complementary component for developing wearable biosensing patches, as the deformable interconnects can absorb the stresses with negligible effects on the central sensing devices [49]–[51]. Therefore, a good combination of soft lightweight substrates, advanced functional nanomaterials making soft, thin sensing films and stretchable interconnects [52], and most im- portantly a robust fabrication technique for processing these low Tg (glass transition temperature) materials at ambient conditions, are desired for development of reliable wearable sensing patches [9], [16], [53]–[55]. This paper highlights the latest developments made in geometric designs of the sensory cells, engineered nanomaterials (both inorganic and organic) and the fabrication methods particularly the solution-based printing technologies.

II. WEARABLE TEMPERATURE SENSORS: DESIGNS AND STATE OF THE ART

Temperature sensing is one of the central physiological parameters used to determine the human body temperature with particular emphasis on patients suffering from prolonged chronic diseases, normal fewer, unconscious, and injured pa- tients undergoing a surgical treatment and for the health status of the medical staff [56]–[58]. Wearable temperature sensing finds its attractions not only in the medical related field, but in general it is also useful for monitoring and tracing the body tem- perature of healthy people doing extensive outdoor activity [59], [60]. Besides the heavy workout for fitness activities of athletes and sportsmen, wearable temperature sensor is very useful for laborers working in very harsh environmental conditions. The rising levels of climatic conditions particularly the temperature and humidity, lead to dehydrating the individuals and causes fatigue and many other serious implications towards their health.

Therefore, developing wearable temperature sensors not only to monitor the human health, but observing the local ambient environment is equally important. Fig. 2 shows schematic of the wearable sensing models employing temperature sensor accompanied with the wireless data transmission models.

A. Temperature Sensors Conventionallytemperaturesensorsaredevelopedindifferent geometric structures depending on the application, materials processability as well as the manufacturability in the desired shape [23], [61]–[63]. These various structures are distinguished by the temperature sensing mechanism through certain changes and upon physical interaction with the hot surfaces. The two broad categories of temperature sensors are based on contact andnon-contact-basedsensingmechanism.Contacttypesensors are used to monitor a wide range of surfaces including solids, liquids and gaseous phases. However non-contact-based sensor can sense remotely the thermal irradiations emitted from the hot surfaces. The prominent temperature sensors include ther- mostats, thermistors, resistive temperature detectors (RTDs), thermocouples, negative temperature co-efficient thermistors (NTC) and silicon-based sensors etc. Details of the working principle of these sensors are provided in [64], [65]. Among these, the bulk resistance changes of a RTD (resistance tem- perature detector), thermally sensitive resistors (thermistors), the commonly used mercury-based thermometers, optical and handheld infrared monitoring sensors etc. are few of the com- monly used types of temperature sensors. Each type of the sensor proposes advantages over other, however certain limitations for the wearable related applications restrict the use of specific type of sensors to be adopted. RTDs and thermistors are usually adopted in many applications in general due to their reliable and fast response, structural stability, good accuracy and lastly their ease in manufacturing make them ideal for batch produc- tion at much depreciated costs [66]–[68]. The thermal IR and optical sensors on the other hand are commonly used in the indoor medical facilities, but these are developed on wafer-based substrates and the signal conditioning circuits too embedded on rigid PCBs (printed circuit boards) making it challenging for lightweight, portable, and wearable related applications. The conformal attachment of the sensors to human skin directly needs all the contributing materials to be flexible or stretchable enough to absorb the stresses caused by the deformations due to human physical activity [23], [67], [69]. For this particular case, thelargeareacoverageofthesensorsplayssignificantrolewhich is enabled specifically by the RTD and thermistor geometric approaches. Fig. 3. shows designs of the proposed geometric structures ideal for such situations. Key performance factors de- sired for the wearable sensors are sensitivity, accuracy, detection at lower temperature ranges, reliability, and repeatability upon

154 IEEE REVIEWS IN BIOMEDICAL ENGINEERING, VOL. 16, 2023

Fig. 2.

Big picture of a wireless monitoring system and wireless data transmission model. Biosensors embedded in a wearable gadget with installed signal processing board and wireless communication. Model also shows proposed schematic for real-time monitoring, where the recorded data is transmissted to the control-station via bluetooth and data sent to the cloud, which is accesible remotly to the medical experts.

Fig. 3.

Schematic of teh printed temperature sensors, (a) Schematic of a RTD, (b) Inkjet printed RTD placed on a human skin, (c) Schematic of a thermistor, (d) Printed thermistor with Ag IDEs and temperature sensing layer of carbon nanocomposite. wearing these sensors on non-planar surfaces. A linear response in the sensitivity leads to increased accuracy, which is highly demanding especially for human body temperature sensing. The sensing ranges of the temperature is a key parameter, and selec- tion of suitable material which is very sensitive to the minute changes occurring in the human body [61], [70]. Response time of the sensor is another key parameter, which plays significant role in detection of the thermal variations. Early detection of the symptoms helps in timely diagnosis and treatment. Real-time monitoring is dependent on various important parameters such as response time, stability, and hysteresis etc. of the sensor.

Resolution refers to the measurement of the smallest amount of changes measured by the sensor and therefore, becomes an important parameter, when it comes to wearable tempera- ture sensors. Lastly, for wearability, the sensors require to be developed on biocompatible substrates, having lightweight and beconformableontonon-planar surfaces without significant loss in the sensor response [61], [70], [71].

III. TEMPERATURE SENSING MATERIALS Materials’ selection is the crucial and main enabling factor in developing wearable biosensing applications. The materials used for developing wearable biosensors are desired to have matching properties both with the underlying substrate as well as other constituent materials making the sensor structure. Gen- erally, the materials are required to be biocompatible, portable, lightweight, soft, flexible/stretchable as well as conforming to the non-planar surface without significant degradation both physically as well as in the sensing response [28], [34], [72]. As the wearable sensors are attached directly on the human skin, the sensors are desired not to pose any health or medical risk.

In this scenario, biocompatibility is highly desired for wearable and implantable sensing devices. This includes biocompatibility of the substrate as well the deployed materials for construction of the sensing device. Various biosensors such as multi-function brain sensor, implantable pressure-strain sensor etc. have been reported which are developed completely on biocompatible sub- strates as well as utilized the similar sensing materials [73], [74].

These fabrication methods however have distinguished benefits as well as critical limitations. Among these, the temperature sensors developed through printing technologies require certain properties which are distinctive for each fabrication type. Con- ventionally the materials used for printing are in colloidal or nanocomposite form, where the rheological properties of the solutionistunedspecifictotheprintingtechnology.Forinstance, solution viscosity, surface tension, work of adhesion, spreading co-efficient and nanoparticles concentration in the solution are some of the main characteristics considered, when choosing a printing technique. Printed wearable temperature sensors are

KHAN et al.: WEARABLE PRINTED TEMPERATURE SENSORS: SHORT REVIEW ON LATEST ADVANCES

155 developed either in the form of RTD or thermistors, therefore intrinsic conducting materials as well temperature sensing con- ductor/semiconductor are used in construction of the sensor structure. A wide variety of materials are developed with the desired solution properties for different printing technologies.

This section highlights few of the broad categories of printing materials used specifically for developing wearable temperature sensors utilizing printing technologies.

A. Metallic Conductors The change in electrical resistance of metallic conductors with the corresponding temperature variations is linked to the intrinsic thermal co-efficient resistance (TCR) of the material [46], [66]. These resistance change caused by the phononic interactions are central to the utilization of these materials for temperature sensors. Higher TCR values (either positive or negative) are the key selection criterion for using these metal- lic conductors for a specific range of temperature variations.

Pure metals such as Gold (Au), Copper (Cu), Platinum (Pt),

Nickel (Ni), Aluminum (Al) and silver (Ag) are commonly used for the temperature sensing applications [61], [62], [75].

The structures are developed in the form of wires, thin solid films as well as in the liquid form contained in a closed flow channel. The advanced manufacturing techniques especially the thin film deposition at high resolution patterning of few of these metallic conductors have attracted significant interest. The colloidal solutions made from the nanoparticles suspensions and processed through controlled deposition techniques such as additive manufacturing play a major role in reducing the material wastage and thus contribute a lot in minimizing the overall manufacturing cost [76], [77]. The colloids are made by mixing metallic nanoparticles in suitable solvents exhibiting properties in between a solution and suspension. The mixture formed is a mostly heterogenous having dispersive properties at tunable scattering phases depending on the nanoparticles’ sizes [77], [78]. The average nanoparticle sizes as well as the aspect ratios are kept in close ranges to facilitate uniform dispersion.

Further additives in the form of surfactants are added for tuning the rheological properties such as viscosity and surface tension etc. as well as enhancing the solution stability and prolonged shelf-life [79]–[81]. These metallic conductors are patterned as independent transducer layers such as RTD as well as constituent layersofthinfilmdevices.Nickel(Ni)basedtemperaturesensors have widely been reported due to its attractive features such as higher sensitivity, linearity, high reference point of resistance, wide sensing range (0-100 °C) and above all its availability in the market at lower prices compared to other metallic conductors [28], [68], [82]–[84]. Some of these metallic conductors are prone to oxidation particularly Cu and Ag, therefore multilayer coatingintheformofananocompositeisfabricated.Highlyther- mal sensitive material i.e., Ni is coated with a more stable layer of Pt as protective covering [82]–[85]. Most of these depositions however occur at very controlled conditions by using clean room processes. To simplify the manufacturing process and accessible for exploration in ambient conditions, deposition of colloids of these metallic nanoparticles through wet processing technology is more attractive. Au nanoparticles solution has been explored extensively and stabilized inks are developed at commercial- ized grade by several groups. Au is more stable, having linear response, resilient to environmental impacts, and above all it is biocompatible [28], [68], [86]. Currently, Au based patterning is practiced on thermally stabilized polyimide substrates due to its relatively higher sintering temperatures i.e., 250 °C [62], [86]. This challenge needs to be addressed and ideal sintering temperature of within 150 °C would enable the Au patterning on a wide range of polymeric substrates.

B. Inorganic/Organic Conducting Materials Organic conductors are the polymeric materials that produce electrical conducting properties similar to metallic or inorganic semiconductors [13], [87]–[89]. The chemical structure of these intrinsic conducting polymers can be tuned in controlled clean room environments to get the desired electrical, chemical, and mechanical properties [89]. Initial work on the p-doped or- ganic conductor was reported which led to the development of many similar types afterwards. Few of the commonly used polymeric conductors include but not limited to, are polyacety- lene, polypyrrol, polyphenylene, poly (p-phenylene vinylene), polythiophene polyaniline, polyaniline doped with camphor sul- fonic acid and PEDOT:PSS (3, 4-polyethylenedioxythiopene- polystyrene sulfonic acid), graphene etc. [90]–[92]. Among the list, PEDOT-PSS and graphene have attracted significant interest, due to their abundant availability, easy processing, good electrical, chemical, and mechanical properties [87], [93], [94].

The easy manufacturing and processing techniques especially the wet fabrication routes have contributed significantly to the extensive research on these materials. Many exciting appli- cations have been explored and are particularly explored for temperature related applications. The microstructure of poly- meric materials especially the PEDOT-PSS is responsible for the thermal sensing properties [95]. The core-shell structure is formed by the EPDOT-PSS nanocrystal, where the PEDOT remains at the core of the grain and PSS surrounds the core.

The bulk resistivity of PEDOT-PSS layer is mainly influenced by the insulating PSS part of the material. Effective bound- ary size reduces as a result of smaller number of particles boundaries at higher temperatures, this influences the overall electrical resistance. the electrons do not have sufficient thermal energy to surpass these boundaries at lower temperatures, and therefore the electrical resistance increases [96]. The strong mechanical properties of PEDOT-PSS also make it an ideal candidate for wearable related applications, as it retains the strong adhesion with the substrates upon bending at very low deflection angles. Similarly, the carbon-based nanomaterials and solutions are also explored extensively for temperature related sensing applications. Carbon nanotubes in its pristine form as well in a nanocomposite have been deployed as thermistors on polymeric substrates. Graphene in the carbonaceous family has outperformed many metals and CNTs in terms of electri- cal and thermal properties and is therefore adopted for many thermal management and energy storage related applications.

The monolayers of graphene sheets and very strong physical

156 IEEE REVIEWS IN BIOMEDICAL ENGINEERING, VOL. 16, 2023 structure at nanoscale produce excellent thermal properties. The strong linear relationship between electrical conductance and temperature makes graphene a promising competitor compared to the commonly used metallic conductors as RTDs. Deposi- tion of monolayer graphene sheets are mostly done in clean room processes through CVD (chemical vapor deposition) on electronic grade silicon wafers. To deploy on large areas of polymeric substrates and make the deposition process simple and cost-effective, recued graphene oxide in solution form has been reported widely.

C. Organic-inorganic Hybrid and Nanocomposite Materials

Hybrid organic-inorganic materials is an interesting filed of engineered materials and the exciting properties of both the material complement each other to produce extra-ordinary prop- erties. For instance, the electrical conductivity offered by inor- ganic metallic conductors, when mixed by organic elastomers produce advanced stretchable and flexible composites that are ideal for wearable sensing applications. Beyond the electrical properties, these hybrid materials also exhibit enhanced physical characteristics including good optical, luminescence, chemical inertness, selectivity in chemical as well as biochemical sensing environments. A wide variety of sensing applications have been developed utilizing these hybrid materials covering almost all the fields of physical, chemical, electrical and electrochemical sensors. A wide variety of organic-inorganic hybrid materials, their synthesis and applications are reviewed extensively [97], [98]. The hybrid organic-inorganic materials are broadly divided into two categories depending on the bonding strengths. Weak

Vander Waals, electrostatic or hydrogel bonding occur in one type, whereas in the second type, covalent or ionic bonds are formed between the molecules. A number of synthesis tech- niques are adopted, among which sol-gel, hydrothermal and solvothermal processes are commonly used. Hybrid nanocom- posites are tailored materials synthesized with tuned physical, electrical and mechanical properties ideally required for a spe- cific application [87], [89], [99], [100]. Metallic nanoparticles either in the powdered form or mixed in a solvent are dispersed in polymeric matrix, that develops into a uniform and stable mix- ture. Nanoparticles within the matrix form conducting networks within the bulk of nanocomposite. For the metallic conductors, materials are deposited as nanocomposite thin layer successively to enhance adhesion, prevent the underlying materials from oxidation and other environmental impacts [101], [102]. To make nanocomposites deployable on larger areas using additive manufacturingtechnologies,nanoparticlesofthesemetalliccon- ductors are mixed in polymeric matrix materials in various ratios targeting the desired application [13], [21], [103]. A uniform dis- persion of conducting fillers is highly desired to achieve repeat- able processing and testing results. Different mixing techniques such as mechanical stirring and ball milling are used for uniform dispersion followed by functionalization of the nanofillers in some cases [104], [105]. The mixing ratios of fillers and matrix materials are determined based on the percolation threshold, where a certain level of electrical conduction is achieved by reaching the optimal combination percentages. These conduct- ing nanocomposites are key to the development of a wide range of sensing devices, for instance pressure, temperature, humidity, and proximity sensors etc. [105] Nanocomposite materials are made by mixing both metallic and organic conducting fillers.

Temperature sensing is recorded mostly in the form of elec- trical resistance variation in the bulk of nanocomposite layer as against the thermal gradient. Theoretically, the conducting fillers forming a network of connected threads within the poly- meric matrix are responsible for resistivity variations making it sensitive to the temperature changes. Multiple conducting nanofillers are explored for the nanocomposite synthesis that are used for temperature sensing and monitoring [106]–[109].

For instance, a nanocomposite of graphite mixed in PDMS is applied for making a large area sensing patch containing 64 sensors, each with an area of 4 × 4 cm2 [106]. Cu based inter- digital electrodes developed on a PI substrate are also applied to monitor the conductivity changes in a nanocompite based layer. A detail comparative study is conducted on the thermal sensing performance of Carbon and Ag mixed in PDMS sepa- rately at a temperature range of 25–150 °C [110]. Carbon based nanocomposite exhibited clearer response and dependance on temperature upto 150 °C, whereas Ag based nanocomposite produced best response at 120 °C. The different configurations and geometric structures could easily be explored with using nanocomposites as the thermal sensing layer particularly in the shape of a discrete resistor as well in a wheatstone bridge design [111].

IV. SUBSTRATES The interesting features such as flexibility, bendability, lightweight and wearability etc. of the polymeric substrates that provides a supporting ground for the low-cost fabrication of large area devices [12], [112], [113]. The bendability at small angular deflections makes them ideal for fast speed pro- duction through Roll-to-roll manufacturing [114]. The flexible substrates are desired to have stable properties comparable to the standard planar rigid substrates [115]. The three different types of flexible substrates developed largely so far are thin glass [116], [117], thin metallic foils [118], [119] and polymer basedplasticssheets[120].Amongtheseplasticbasedsubstrates are more suitable for low-cost wearable related applications, as the thin brittle glass is expensive as well as prone to breaking.

Similarly, thin metal foil-based substrates are relatively heavy and require extensive surface treatments to make it suitable for thin film deposition of functional nanomaterials. In this scenario, plastic based polymeric substrates offer reasonable tradeoffs concerning the physical, mechanical, and chemical inertness etc.

One main hindrance in using plastic based substrates is about its low glass transition temperatures (Tg), usually within the range of 250 °C. This however covers the range for biocompatible substrates required for most of the wearable and implantable devices [120], [121]. Biocompatibility of the substrate material is central to the development of wearable biosensors. Biocom- patibility is termed an important factor which is responsible for the safe interface between living cells/tissues and the sensing

KHAN et al.: WEARABLE PRINTED TEMPERATURE SENSORS: SHORT REVIEW ON LATEST ADVANCES

157 Fig. 4.

Key enablers for realizing a flexible and wearable sensing device. Electronic functional inks in the form of colloids and nanocomposites having organic-inorganic hybrids combined with suitable cost-effective additive manufacturing i.e., printing technologies. Large area flexible substartes are used as supporting layers and enable the wearability an dfoldability of the developed structures. module without causing any harm to the deployed surface. As the substrates are in intimate contact with human skin or with the tissues, air permeability and biocompatibility is strictly required to avoid any medical risk or complications [122], [123]. Bio- compatibility need to be assessed both for in-vitro and in-vivo applications particularly focusing on the toxicity to the cells, cell attachment, leachates and cell culturing. Mismatch properties or non-biocompatibility can lead to cell damage as well as inflammatory issues and immune system disorder [122]. Various substrates have been developed considering the biocompatibility aspects, that include SU-8, air permeable membrane, carbonized silk fibers, cotton fabric, cellulose based and most importantly polymer based biomaterials [32]. Among the list of potential polymeric substrates, PDMS is ideal for wearable electronics.

The viscoelastic properties and biocompatibility make it more suitable for deployment on nonplanar surfaces. The recently developed cellulose based substrates are also used, however the porosity and liquid absorption capacity of the substrate make it challenging for human body worn biosensing applications [124], [125]. Polyurethane is commonly reported substrate used to ex- ploit the biocompatibility [126]. The semipermeable membrane allows a certain amount of humidity and oxygen desired for the normal functioning of living cells and tissues. One major challenge with most of the biocompatible substrates is its limited upper processing temperature. As the metallic conductors, for instance Au require higher temperatures (i.e., ∼250 °C), which is beyond the Tg of these substrates. Therefore, to IR or flashlight sintering techniques are used to address this issue. In flashlight sintering, only the top surface of the thin film gets heated with tuned light intensity and power without damaging the underlying substrate. Flashlight sintering too has certain limitations i.e., transparency of the substrates as well as deformation of the upper contacting surface with the sintered pattern. Therefore, further research in developing biocompatible substrates and reliable sintering technique offering low temperature operation and producing higher instantaneous temperatures are highly desired.

V. KEY ENABLING WEARABLE SENSING TECHNOLOGIES Development of electronic devices and sensors that are suit- able for deployment on nonplanar surface, require all the con- stituent materials to be in perfectly matching in terms of their processability, mechanical and electromechanical properties etc. [2], [3], [32] Key enablers for such devices are the synthesizing colloidal solutions of functional nanomaterials with suitable rheological properties for the specific printing technology and its compliant integration on a polymeric based flexible substrate [12], [62]. Fig. 4 depicts the key enablers desired for making flexible and wearable sensing devices.

A. Printing Technologies Printing is an important key enabler for patterning func- tional materials on diverse substrates at ambient conditions.

The cost-effective manufacturing through printing and covering processing areas larger than wafer scale are the main attractions.

Printing technologies can be used both for high resolution pat- terning as well as coating larger areas in a much simpler way as compared to the conventional clean room processing [12], [27]. Depositing materials on demand at specified location in a controlled fashion make printing technologies distinguished from other manufacturing techniques due to the reduced material wastage. The materials wastage is lowered as printing is done in a single step as against the many steps involved in the clean room processes that use several subtractive steps for patterning structures [114], [128]. Various printing technologies have been adopted as well as modified rendering the expertise from con- ventional text printing techniques. Few of the prominent printing technologies used include but not limited to, are gravure, offset, flexography, inkjet, screen, aerosol, transfer and micro-contact printing etc. All the techniques have specific set of requirements and produce results based on their capabilities. Rheological properties of the solutions and nanocomposites come at first place when choosing a printing technique. For instance, inkjet,

158 IEEE REVIEWS IN BIOMEDICAL ENGINEERING, VOL. 16, 2023 slot-dies, and aerosol jet printing requires materials in the vis- cosity range of 5-12 cPS, however higher viscosities are desired for screen as well as gravure and offset printing techniques.

Similarly,thepatternresolutionandfilmthicknessesachievedon the substrate depends on the selection of the printing technique.

Screen and offset printing produce thick films (in the range of

0.2-0.8 µm), while inkjet and aerosol are used to print thin films (in the range of (.01-.2 µm). Film thickness is tuned by multiple printing cycles depending on the desired thicknesses. Printing speed is another important parameter considered for selection of a specific printing technique. Gravure, offset and flexography are famous for their high-speed production, as they are easy to be installed on a roll-to-roll printing system. Speeds as high as ∼

150 m/min can be achieved with these systems at repeatable and reproducible film formation. Whereas inkjet, screen and aerosol jet printing are low speed processes and are mostly adopted for producing prototypes or installed at research lab facilities for evaluation.

Besides printing technologies, selection of suitable mate- rials also plays significant role in determining the key fac- tors of a temperature sensor. Fabrication processes to deposit organic/inorganic materials in a patterned or in the form of thin films is determined by the rheological properties of the nanoparticle solutions. For wearable electronics and devices’ development on flexible substrates, the materials and processing techniques need to respect all the limitations. In standard manu- facturing processes, the different combination steps of photore- sist coating, exposure to sensitive light, etching, target material depositionfollowedbylift-offetc.makethemanufacturingcom- plicated and very expansive as significant amount of material is wasted. This also adds to the budget of electronic and material pollution directly or indirectly. On the other hand, the compli- cated and sophisticated processes restrict the manufacturing to certaingroupswhocanacquireandmaintaintheprocessingcosts of such manufacturing facilities. Thus, solution based additive manufacturing offers significant advantages when it comes to low-cost manufacturing at less capital investments. Therefore, besides the development of other electronic devices, temper- ature sensors are also developed using printing technologies [30], [82], [129].

Printing has evolved as an attractive approach for rapid manu- facturing of thin film electronics. Chemical solutions or colloids of the functional nanomaterials are stabilized with the help of additives and surfactants are used for printing [130]–[132].

Properties and material content are tuned according to the set requirements of a specific printing process and target function- ality to be achieved. The controlled deposition and dispensing parameters are adjusted collectively by the materials properties as well as the actuation mechanism parameters [133]. The most important solution properties influencing the actuation mech- anism are viscosity, surface tension, particle content, average nanoparticle sizes and solvents’ vaporization point etc. [130], [134]. Substrate surface conditions also play major role and contribute significantly to the final shape of the printed structures and resolution. Surface properties such as the hydrophilicity, surface energy, lower contact angles, higher work of adhesion etc. are required to be at moderate levels in achieving good

Fig. 5. (a). Schematic of the multi-layer thermistor, (b) Chemcial com- position of PEDOT-PSS and its linkages with GOPS, (c). Schematic of step-by-step manufacturing of tehrmistor, (d) Patterned IDEs and sensing material using inkjet printing technolgy. [20] [reproduced with permission] . printingresults[135],[136].Thetwotypesoftemperaturesensor considered in this review are RTDs and thermistor, which em- ploy printing technologies capable of patterning high resolution conducting structures as well as deposition a uniform thermal sensing layer.

B. Printed Temperature Sensors Printed RTDs work on the principle of changing resistance as against the temperature rise and therefore, the thermal co- efficient of resistance (TCR) is used to determine the corre- sponding temperature variations [137]–[139]. The all-printing method of fabrication in the shapes of meander, spiral or circular make the manufacturing simple and cost-effective. For RTDs, the sensor is completed in a single step by printing the desired structure using conducting nanoparticle ink only. The same type of ink is used for the interconnects as well as for the contacting pads. Therefore, the process of making RTD is straight forward and making it through printing technology in a single step is much advantageous. On the other hand, thermistor is made of two different materials and therefore, two printing cycles are executed to complete the manufacturing process. Interdigital electrodes (IDEs) are the first layer of the device, which is printed using metallic ink [13]. Inter digital spacing between the consecutive electrodes, play significant role in sensing response.

Therefore, various studies have been performed to optimize the spacingwiththecorrespondingthermallysensitivematerial. The second printing cycle uses thermally sensing material deposited in the active area covered by IDEs, either using printing or a thin film coating technology. Significant progress has been made in exploring both the approach of RTDS and thermistors in recent years by investigating different materials and manufacturing processes. Mixture of conducting polymer composites made by combination of reduced graphene oxide (rGO) and poly- hydroxybutyrate (PHB) for making both RTD and thermistor structures. Ag based electrodes are used and direct printing technique as well as drop casting is used to pattern and deposit ink respectively [13]. Fig. 5 shows schematics and printed model of a new type of thermistor, where the temperature sensing material is patterned rather than complete filling of the effective area surrounded by the IDEs. The type of sensor is claimed to be

KHAN et al.: WEARABLE PRINTED TEMPERATURE SENSORS: SHORT REVIEW ON LATEST ADVANCES

159 much effective to the conventional thermistors where the whole sensing layer is deposited as a thin film.

High resolution Ag patterning in meander is done with inkjet printingtechnologyonacellulosebasedbiocompatiblesubstrate [30], [140]. An all-printing approach for patterned deposition of PEDOT-PSS and carbon ink is used to design a whetstone bridge [20], [141]. Similarly, inkjet printed sensors fabricated from mixture of carbon and PEDOT:PSS to have TCR value of around 0.25% /°C. Inkjet printing of graphene/PEDOT:PSS ink is developed on top on skin mountable polyurethane plas- ter (adhesive bandage). A new addition in the RTD design is implemented, where Ag based conducting stripes are added in the pathway inkjet printed graphene/PEDOT:PSS [67]. A small wearable patch comprising multiple sensory cells such as acceleration, ECG and temperature sensor are developed mainly by using an inkjet printing technology. For temperature sensor, PEDOT:PSS and CNTs were mixed to obtain an ink compatible with inkjet printing technology [142]. An efficient skin mountable temperature sensor is reported as part of a multisensory patch used for wearable health monitoring ap- plication. An inkjet printable ink was synthesized by mixing

CNT ink and PEDOT:PSS in a 3:1wt% ratio for development of skin based temperature sensor [69]. A similar type of wearable temperature sensor is reported made in the shape of a band for human wrist. Inkjet printing of PEDOT:PSS is used to developthistemperaturesensor[143],[144].Screenprintingofa nanocomposite of PEDOT:PSS, Ag nanoparticles and graphene ink is used to impregnate a stretchable fabric for development of wearable self-powered temperature sensor. This type of sensor is claimed to offer very attractive features such as ultra-thinness, light weight, high flexibility, and stretchability etc. enabling the sensor to conformally contact with the human skin [35]. A highly stretchable but strain-insensitive sensor is developed by using different mixtures of SWCNTs, MWCNTs and AgNps. The synthesized ink is mixed in certain ratios which is compatible with using Microplotter ink printing system [145].

Aerosol jet printing has recently been produced exciting re- sults leading the field of printed electronics for high resolution patterning as much less efforts. In this scenario, a Cu-CuNi tem- perature sensor is reported on Kapton substrate. The nanopar- ticles are deposited using aerosol jet printing followed by laser sintering at lower powers respecting the thermal properties of the

Kapton substrate [82]. Besides the solidified sensing structures of the temperature sensors, liquid based metallic conductor are also used in a 3D printed microchannels as reported in.

Biocompatible polylactic acid material is used as substrate for the microfluidic channel made by 3D printer and filled with liquid metal (Galinstan, Rotometal). The sensor is deployed on human ear and is used detect core body temperatures [146].

Transfer printing is used to develop ultra-flexible and biocom- patible temperature sensor following a meander structure made of Au/Cr. The temperature sensitive material is integrated in a polyurethane substrate using transfer printing approach. Ini- tially the Au based microstructures are developed using pho- tolithography techniques on a PI (polyimide) coated Si wafer [33]. Table I summarizes few of the representative designs, the sensing materials, substrates, the fabrication method as well as the encapsulation materials used to cover the sensing layers by providing further mechanical strength and protection from the varying climatic conditions.

VI. TEMPERATURE SENSING PERFORMANCE BASED ON DIFFERENT MATERIALS AND STRUCTURES

Printed temperature sensors work on the principle of re- sistance change against corresponding temperature rise, and therefore the TCR is mostly considered as the measurement parameter for sensitivity [57], [129], [147]. For wearable tem- perature sensors, the body temperature varies in an effort to transfer heat between living cells and the external environ- ment [148], [149]. This heat is dissipated through the skin or respiratory system. Real-time monitoring is enabled by the wearable temperature sensors to determine the instantaneous changes occurring in the body under various conditions [150].

Accurate measurement is important in recording the real time data regardless of the motion or motion-less state of the body.

Although the conformal interface and deployment of flexible sensors offer the possibility to detect these minute changes in real-time [151]–[153]. They still require a good combination of sensitivity, rapid response, hysteresis-free, robustness against varying conditions and stability during normal physiological movement [154], [155]. As the sensors are used to monitor the human health condition and the data would be used to make a decision on emergency basis, therefore a reliable sensing data is of prime importance [156], [157]. To improve the sensitivity and reliability, a wide range of functional nanomaterials in pristine form as well nanocomposites are used to achieve better performance [61], [72], [158]–[160].

A. Performance of Conducting Materials-Based Sensors

Various interesting researches have been conducted recently withafocusonaddressingthenumerousaspectsofperformance, reliability, wearability, and biocompatibility etc. In this scenario, an ultrathin temperature sensor produced by embedding the Au meander structure in a semipermeable polyurethane membrane through transfer printing [33]. The sensor has been tested 24/7 and also calibrated during water bath. The sensor has presented a TCR value of 0.002778 /°C by placing at multiple body locations such as underarm, forearm and comparable perfor- mance to mercury-based sensors are claimed to be achieved.

The development of sensor on biocompatible, breathable, and stretchable substrate is interesting, as it permeates the water and air without causing any significant degradation to the sensor performance [33]. Ag is the commonly used printed materials in the form of RTD, where the bulk resistance variation of the printed patterns is corelated with the change in temperature [31], [66], [161], [162].

A high-resolution printed Ag meander structure is developed on a bacterial nanocellulose substrate, which is biocompatible and biodegradable. The sensor exhibited a positive co-efficient resistance (PTC) by producing sensitivity of 0.06 /°C [140].

Inkjet printing of a large area Ag printed meander using inkjet technology exhibited a TCR value of .0029/ °C in the tem- perature range of 20–60 °C [30]. PEDOT:PSS is reported by

160 IEEE REVIEWS IN BIOMEDICAL ENGINEERING, VOL. 16, 2023

TABLE I SUMMARY OF DESIGN, MATERIALS AND FABRICATION METHODS OF SOME LATEST REPRESENTATIVE RESEARCH most of the research for developing temperature sensors, be- sides the metallic conductor [95], [163], [164]. Being a poly- mer and highly conductive, the intrinsic flexibility makes it an attractive candidate especially when it comes to electrically conducting structures on polymeric substrate [58], [93], [126].

A PEDOT:PSS based temperature sensor has been reported on Kapton and cotton fabric substrates, which are suitable for wearable related applications [30]. The sensor is claimed to be highly stable and sensitive towards small changes in the temperature and can detect a variation down to 0.1 °C [144].

Cross-linked PEDOT-PSS is used for developing thermistor- based temperature sensor where, IDEs were inkjet printing using

Ag nanoparticles-based ink and the sensing area is covered with PEDOT-PSS in a meander patterned configuration. Fig. [5] shows the schematic and printed sensor using this architecture.

The sensor showed NTC and a higher sensitive of 0.77% /°C is reported. Sensitivity of the PEDOT:PSS is enhanced by mixing with GOPS [20].

B. Performance of Nanocomposites-Based Sensors Metallic and polymeric-based nanocomposites are also ex- tensively explored for a wide range of biosensing applications [94], [165], [166]. For temperature sensor, rGO [137], [166] and its nanocomposite especially with PEDOT:PSS and PHB are exploited both for the RTD and thermistor configurations [56], [87], [167]. Ag based IDEs are used for the thermistor,

KHAN et al.: WEARABLE PRINTED TEMPERATURE SENSORS: SHORT REVIEW ON LATEST ADVANCES

161 Fig. 6.

Sensitivity and temperature responses of (i), Thermistor using rGO/PEDOT-PSS, testing under different temperature and humidity conditions, (ii) Sensor develoepd based on Seebeck co-efficient by using nanocomposites of MWCNTs/AgNWs, SWCNTs/AGNWs and MWC- NTS/SWCNTs. (iii) Temperature response of nanocomposite of PEDOT:PSS/AgNPs thermocouple. [20], [145], [35] [reproduced with permission]. and a printing mechanism is adopted for the tuned nanocom- posite solutions. The sensors are reported to have NTC both for the rGO and rGO/PHB nanocomposites. TCR values in the range of 0.018-0.03 is reported minimum for the rGO and maximum for the mixing ratio of 12 wt.% [13], [144]. A skin mountable polyurethane adhesive bandage is used to develop temperature sensor. An inkjet printable nanocomposite solution is prepared by mixing graphene/PEDOT:PSS and patterned as meander shape through inkjet printing technology. Sensor re- sponse is enhanced by printing Ag stripes in the pathways of graphene/PEDOT-PSS patterns to mitigate the chances of signal degradation. The sensor is responsive and tested in the temper- ature ranges suitable for human health monitoring i.e., 35–45

°C. The graphene/PEDOT:PSS behave as NTC while recording a TCR value of 0.006/°C in the operating range of temperatures [67]. A temperature sensor in a straight wider line is reported to have higher sensitivity i.e., 1.3%/°C. The wide sensing pattern is developed by printing a nanocomposite solution of PEDOT:PSS and CNTs, connected with Ag based interconnects [69], [144].

Fig. 6 gives some representative sensitivities responses at dif- ferent humidity and temperature conditions. The graph shows data for two different devices i.e., thermistor and thermocouple, where the sensor response is measured as resistance for the thermistor and Seebeck co-efficient is used to determine the varying temperature values.

C. Sensors’ Performance Based on Un-Conventional Architectures

Further developments in the field of wearable sensing ap- plication are proposed by exploiting some un-conventional ar- chitectures and materials. For instance, a wheatstone bridge configuration is designed and produced using an all-printed approach. The sensors are made of carbon nanoparticles ink and a mixture of PEDOT:PSS with DMSO (dimethyl sulfoxide) and evaluated the TCR as positive and negative co-efficient respectively. The TCR is evaluated also a function of mixing ratios of PEDOT:PSS and DMSO at 0.3 wt.% and 3 wt.% which resulted in the range of 0.009 /°C to 0.0025/°C respectively.

Carbon based ink produced a positive TCR i.e., 0.0022/°C [141].

Another interesting alternative proposed for monitoring of core body temperature by monitoring inside the human ear rather than placing the sensor on top of skin. The sensor is developed through 3D printing and is able to be worn on a human ear to record the core body temperature from the tympanic membrane.

An infrared sensor is developed through 3D printing of liquid

162 IEEE REVIEWS IN BIOMEDICAL ENGINEERING, VOL. 16, 2023

TABLE II SUMMARY OF THE PRINTED SENSORS RESPONSES metal in a wearable module and is connected with wireless communication system for real-time monitoring [146]. Textile based temperature sensors are very attractive, as the intrinsic wearability and stretchability features comply with most of the sensor requirements. Thermoelectric approach is used to determine the temperature response by developing the sensor in a scalable way using nanocomposites of Ag, PEDOT:PSS and graphene [168]. Mixtures of this ultrasensitive materials is printed through stencil coating. An output voltage of 1.1mV is generated for a temperature difference of 100 K, with a high durability up to 800 cycles of 20% strain. The sensor is also explored for the dependency on stretching direction and has exhibited corresponding temperature-sensing properties [35].

Another interesting development is proposed about exploit- ing the Seebeck effect to mitigate the strain-related noise that might occur in the temperature sensing data. Three different nanomaterials i.e., SWCNTs, MWCNTs and AgNWs are used in different composition and printed using high resolution Mi- croplotter technology. Main idea behind this development is that the difference the Seebeck coefficients generate a voltage which is proportional to the difference of cold and hot points of the junction. A large array of sensor is developed and de- ployed on a human hand. The Seebeck coefficient from the mixing nanocomposite of SWCNTs/AgNWs could reach up to 37mV/°C. Similarly, the MWCNTs/SWCNTs produced See- beck coefficient of 23mV/°C, lower than the SWCNTs/AgNWs combination. Both the combination resulted in good linearity and reproducibility of the sensors’ outcome [64], [101]. An- other similar approach for exploiting the Seebeck response of

CU and CuNi films deposited by using an aerosol jet print- ing. A higher Seebeck coefficient is achieved i.e., 40 µV/°C, claimed to be the highest sensitivity reported so far for sensor developed on polymeric substrates. The stability tests were performed after bending the sensors for 200 cycles at different deflection angles, reported a negligible variation within 2.5% of the Seebeck coefficient [82]. Table II summarizes the re- sponses of representative devices by including the designs, TCR, temperature ranges, sensitivity and wearability spots on the human body.

The fluorinated polymer CYTOP (CTX-809A) was chosen as the passivation layer, due to its low water vapor permeability and good adhesion on the substrate

KHAN et al.: WEARABLE PRINTED TEMPERATURE SENSORS: SHORT REVIEW ON LATEST ADVANCES

163 Fig. 7.

Sensor responses with applying encapsulations. Sensor is encapsulated with water repellant layer. (a) Cross sectional view of the covering film. (b) Comparison and effect on the sensitivity with and without encapsulation. [33], [20] [reproduced with permission] .

VII. ENCAPSULATION MATERIALS Covering the printed structures is important to protect the sensing layer as well the complementary signal readout in- terconnections from the environmental impacts. Encapsulation is important not only for the organic based materials, which are more prone to climatic condition, but metallic based RTDs especially made of Cu and Ag are prone to oxidation. Physical, electrical, and mechanical properties of the encapsulant layer need to be in matching with the underlying sensing and metallic layers. A very thin layer of insulation, which is sufficient enough to block any penetrating air or humidity. Localized deposition of the encapsulant layer is usually deposited especially at the active sensing area. Whole area of the substrate does not need to be covered for the wearable sensing patches. The substrates are usu- ally biocompatible and sometime with microporous substrates are selected to maintain the normal environmental conditions on the human skin. Therefore, most of the wearable temperature sensors reported so far always have applied a suitable encapsu- lant at the effective sensing area and selecting a biocompatible substrate at the same time.

A semipermeable membrane is used as encapsulant layer for developing a breathable and stretchable temperature sensor. The membrane covers multiple underlying films used to develop the sensor that provides a strong base simultaneously to maintain the planarity and neutrality of the base sensing layer [33]. A

UV-epoxy based encapsulant is applied on a spray coated CNT layer and evaluated against non-encapsulated sensors [169].

The encapsulated sensors produced much linear response with minimal hysteresis as compared to the unencapsulated sensors.

A fluoropolymer (CYTOP) CTX-809A is applied as passivation layer on a printed PEDOT:PSS sensing layer [20]. A drop casting technique is applied to produce a thin layer with thickness of about 10µm. Sufficient passivation against humidity as well as strengthenstheunderlyingsensinglayerisreported.Fig.7shows schematic of a sensor with and without encapsulant layer and their sensivity responses. Stability in an all-printed sensor is observed by comparing the performance of an encapsulated and nonencapsulated sensing film. Inkjet printed PEDOT:PSS and

DMSO are used as NTC (negative thermal coefficient) tempera- ture sensors, and a barrier foil is used as top encapsulant. A damp heat accelerated lifetime test was performed for 400 hours at

65 °C and 85% RH. Encapsulant materials not only influences physical properties but improved the electrical characteristics of the film as well. Electrical resistance of encapsulated sensor increased by 10% relative to the base resistance. However, a 13% increaseinthebaseresistancewasobservedwithunencapsulated sensor, showing more stability in the sensor performance [141].

In another test, a nanocomposite of graphene/PEDOT:PSS is evaluated with and without encapsulation [67]. An electronic grade coating (EGC) material was drop casted on the printed area of the sensor in argon environment and dried at room tem- perature. The resistance response after repeated cyclic and accel- erated tests confirm the stable resistance response of the covered sensor, however the uncoated sensor diverged significantly from the initial base resistance. The resistance vs. temperature slope reversed from negative (NTC) to positive (PTC) while testing in ambient condition accompanied with prominent hysteresis.

The environmental variation specially humidity caused serious implications to the performance of the sensor when not coated with proper encapsulant [67]. Applying a low-moisture perme- able membrane is another approach used to make the sensor waterproof. These materials come in solution form and can be printed deterministically at the desired sensing area [69]. Lami- nation of a dry photoresist film on thermally sensitive material is arapidalternativeforapplyingencapsulationlayers[170],[171].

An aluminum encapsulation layer is deposited on a PEDOT:PSS layer using atomic layer deposition (ALD) technique [172] as a protection against humidity for temperature sensors. PDMS is a commonly used and readily available biocompatible encap- sulant, which is inert to chemical etchants and environmental variations etc. The easy processing and deposition/coating make

164 IEEE REVIEWS IN BIOMEDICAL ENGINEERING, VOL. 16, 2023

Fig. 8.

Representaive examples of the wearable sensing patches deployed at different spots on a human body, (a-b) Fully printed PEDOT:PSS temperature sensor with flexible PCB circuit, (c) Stretchable sensor fabricate dform polymer nanocomposite and mounted on foreahd, (d-e) multisensor patch made of conventional rigid sensor and embedded in a flexible substrate, (f) ECG and tempearture sensor mounted on human skin with gelss-less approach, (g) high resolution RTD tempearture sensor mounted on human finger, (h) Highly stretchable and ultrasensitive tempartrue sensor, simulated an dtested on human skin. [20], [13], [17], [69], [140], [145] [reproduced with permission]. it attractive to be used in any experimental investigations [13], [145]. To make the sensor suitable for implantable applications, thickness of the encapsulant needs to be minimized. Therefore, for ultrflexible sensors, parylene C coating (∼1µm thick) layer is commonly practiced [61].

VIII. WEARABILITY DESIGNS AND PLACEMENT PREFERENCES ON HUMAN BODY

The sensor patches need to be deployed in a conformal way on the human skin, such that the noise generated by the physio- logical movements and or by the chemical analytes excreted by the human body are avoided. Therefore, selection of the most feasible location in the human body to detect the signal easily is of prime importance. For continuous monitoring, the system needs to be light-weight and not to interrupt the daily routine activities of the individual. With the fast advancements in miniaturized microelectronics, it has become possible to deploy these sensor patches on human body seamlessly. Fig. 8 shows some representative examples, where wearable sensing patches are attached to human body at different body spots to determine various biomarkers. To develop a full system, a hybrid approach towards utilizing both printed sensors and Si based signal conditioning circuits. Different designs are pur- sued depending on the type of sensors and target biological or physiological analytes. Here we focus mainly on the de- signs specific to temperature sensing. For the sensor developed on ultra-flexible substrate, a biocompatible adhesive based on hypoallergenic polyvinylethylether is used. This adhesive is biocompatible and can stay for longer period as 7 days without causing any irritation to human skin. This is complemented by the breathable substrate, which contains semipermeable mem- brane that allows to maintain the normal climatic conditions on the human skin [33]. These types of sensors are developed without firm integration of the electronic circuitry and attaching the senor patch to human skin does not qualify completely for the wearable systems. A biopatch is implemented by using

NFC (near field communication) technique. The biopatch can detect, save, and transmit the recorded temperature to a nearby receiver wirelessly. Besides the temperature sensor, the biopatch comprises a microcontroller (RF430FRL152H) for running the

NFC communication standard as well as a non-volatile memory for saving the recorded temperature values [173].

A surfaces mount BLE module for wireless communication has presented very promising results. The overall thin module is capable of integration to the human skin as well as tried on

KHAN et al.: WEARABLE PRINTED TEMPERATURE SENSORS: SHORT REVIEW ON LATEST ADVANCES

165 Fig. 9.

Wearable temperature sensor for monitoing of deep body temperature using an IR detector, (a) design of the earable smart device with communication model and tools, (b) Image of wearing the smart device and circuitry within the device (c) Detection mechanism of temperature in the IR sensor and output voltage of the thermistor vs. ambient, (d) Output voltage of IR sensor as a function of time by increasing temperature and calibrated output voltage as a function of the temperature difference. [146] [reproduced with permission]. several other nonplanar surfaces [20]. Multilayer integration on a reusable kirigami structured substrate is proposed by plac- ing ECG, acceleration, and temperature sensors. The kirigami structure in base substrate allows the slight deformations caused by the physiological movements of the human body parts. The sensor is attached to the human chest using a bi-adhesive tape.

This is a major discrepancy and using bi-adhesive tape could be detrimental to human skin for longer use [144], [174]. A large area sensor patch employing both ECG and temperature sensors are reported by mounting on a human chest without using a gel usually required for the ECG electrodes. A new gel-less approach is developed made by mixing biocompatible

PDMS and PEIE, which upon curing are become sticky and provide a firm conformal contact with human skin [69]. The sensor response is in acceptable range both for the ECG and temperature, however serious issue with this design is the data readout through wired connections. A more compact wearable sensor is presented for measuring ECG, PPG, and body temper- ature. The sensor patch is developed using a central board for data acquisition and processing, powering board and batteries, all attached to the human chest [17]. A relatively easy approach is the integration temperature sensors in a wearable band. The miniaturized and compact electronic components are easy to be packaged in band and transmit data through BLE module in a nearby connected device [143].

Other than the skin temperature, wearable devices for mea- suring core-body temperature are also investigated as shown in Fig. 9. A smart 3D earable package is developed used to determine the core body temperature. The sensor is based on infrared sensor. All the data processing circuits, and wireless modules are embedded in a single package and mounted on a

3D printed designed gadget to be worn on human ear [146].

Another similar approach by making a foam-based Y-shaped sensor is developed, equipped with temperature sensors and electronics, and focuses on ergonomic aspect. This type of sensor is ideal for continuous monitoring of core-body tem- perature especially for the mobile patients [25]. Monitoring the temperature of a diabetic patient especially in the scenario of diabetic foot ulcers (DFU) is an interesting application. A personalized temperature sensor equipped shoe is developed to monitor the foot temperature of a diabetic patient. The tem- perature rise time at the wearable plantar surface could be a potential indicative biomarker for differences in soft tissue biomechanics and vascularization during diabetes onset and progression.

IX. CHALLENGES AND FUTURE OUTLOOK Despite the fact that significant progress has been made to- wards realizing wearable sensors in general and particularly the temperature sensors. There are many technological challenges before it is widely accepted by the masses at large. Biocompat- ibility: Most of the devices and design reported here are based on placing the polymeric substrate directly on the human skin or using a bi-adhesive tape as a temporary solution for deploying as wearable module. This however is faced with challenges of biocompatibility, covering large area of the skin may cause irri- tation and toxicity of the some of the metallic conductors etc. [1], [123], [175], [176]. Other than skin related incompatibilities, the analytical procedure, reliability of the sensor data, real-time ac- quisition and decision-making protocols, security and powering the devices using batteries need a significant amount of research.

Putting hazardous and somehow carcinogenic materials on or near the human skin for long term need extensive investigation and finding alternative powering devices that are compatible with human skin, need to be explored. Signal readout: Making interconnections with the printed devices and circuits is another challenging task. Conducting epoxies have been in practice

166 IEEE REVIEWS IN BIOMEDICAL ENGINEERING, VOL. 16, 2023 commonly for making connections to printed pads, however due to the lower glass transition temperatures of biocompatible substrates, these epoxies cannot be applied. Making a normal physical contact would be feasible for laboratory level tests, however for real time applications, reliable interconnections need to be explored. The contact resistance needs to be in negligible, otherwise the minor variations due to inappropriate contacts with the pads could lead to incorrect data especially in the case of human body temperature generated data. Further, interconnect lines and electrical connections between contacting pads and the signal processing circuits make the system less reliable due to the noise factor occurring during physiological movements as well as by varying contact resistances. This will require tremendous work on the electronic circuit side by incorporating onboard filters to mitigate the noise and unwanted errors adding to the temperature detection signal. The human body temperature varies in a very close range, and therefore, a minor deviation from the actual values will result in a misleading situation.

Majority of the reported sensors are deployed and directly interfaced with human forearm/wrist, forehead or on the chest.

As, these parts of the body are always exposed to external environmental conditions, and a proper encapsulation with ac- ceptable working conditions of the sensors are highly desired.

The biocompatible materials as well as breathable substrates are more challenging especially for the wearable sensing ap- plication. The interface between human skin or tissue and the mounting sensing materials is difficult to predict as several biological reactions are occurring in the human body and the materials can interact differently. The use of natural biomaterials would lead to address the issues, of biocompatibility, however reproducing the similar sensing performance obtained with conventional materials would be much challenging. To reduce the materials waste, development of bioresorbable sensors is another interesting approach, but that too needs the whole set of constituent materials to be biodegradable. Surface mount integration of thin films maintain the lightweight, miniaturized electronic circuitry and wireless communication modules are at the center of further developments in the field of wearable temperature sensors. Spots to place sensors on the human body are to be properly selected and the areas that produce significant thermal signals are to be selected for sensor mounting. The supporting substrates as well as the complementary materials making the sensor geometry are preferred to be sufficiently stretchable for accommodating the deformations occurring due to the physiological movements. Incorporating such materials that allow stretchability also produce relatively low sensitivities as well as nonlinearity in the sensor response. Therefore, a good combination of compliant materials and substrates is a major challenge for producing sensors with reliable responses, good sensitivity range, hysteresis-free and lower time of detections.

Majority of the reported flexible and wearable sensors are fab- ricated using the newly emerging additive manufacturing tech- nologies by utilizing solution based functional nanomaterials.

Inkjet printing is the most popular manufacturing technique reported so far and has commonly applied for deposition of the temperature sensing layer. These manufacturing techniques are claimed to be cost-efficient due to the ease in manufacturing by localized deposition of materials as well as less materials wastage. The accessibility of such manufacturing tool in com- mon research labs and easy processing steps make it ideal for low-cost fabrication. However, the high throughput and batch manufacturing by roll-to-roll fabrication is the ultimate solution towards cost-effective systems. Currently, the standalone system such as inkjet printing are mostly reported, which are ideal for proof-of-concept devices and making prototypes through discrete deposition steps. Making an integrated manufacturing process flow for patterned deposition of metal lines, sensing layers, interconnects as well as encapsulants could possibly provide a solution towards large scale fabrication at lowers costs.

Similarly, few important features of the printed devices such as stability, repeatability, mismatch, sensitivity accuracy, long term reliability and lastly the large-scale fabrication at depre- ciated costs are considered to be the most challenging aspects for successful development wearable electronic systems. Being developed from solution-based nanomaterials, the temperature limitations of biocompatible substrates restrict the higher ther- mal annealing of the printed patterns. This is very crucial for the stability of the devices as incomplete sintering may lead to inconsistent sensor responses as well as it may cause the delamination of the printed structures at lower bending angles.

The printed materials are mostly in their amorphous form, that makes it less attractive when it comes to accurate responses at insignificant instantaneous changes especially when triggered by the human body temperatures. The layers could possibly crack with physiological movements or in some cases localized delamination occurs when subjected to higher stresses, which changes the base resistance and have significant bearing on the repeatability and reliability of the sensor. This has been observed in the reported literature that sensors performance is degraded after certain bending cyclic tests. Therefore, investigating such materials which are compliant to the polymeric substrates and produce signals repeatedly in the same operating window with minimal deviations even after indefinite bending cycles, are critically needed. Ageing effect of the organic materials is another serious challenge that need to be considered critically.

Encapsulationispreferredinsuchscenariostoprotecttheprinted sensing layers which are prone to varying climatic conditions, however materials and sufficiently thin coating is required that does not influence the performance of the temperature sensing.

Repeatability of the sensors’ response in close ranges with insignificant variations need to be guaranteed. Also, the sensors need to be tested in diverse climatic conditions and calibrated according to the set environment. The different type of sen- sor based on their deployability on the human skin such as body-wornsensorpatches,hand-bands,orimplantablescenarios need to be properly evaluated and compared based on their performance, acceptability from the users, data reliability and reproducibility and after all the ease in using and manipulating the whole wearable system. A realistic approach towards, a clinically viable, robust, user-friendly and acceptable design of the wearable sensory system is needed.

KHAN et al.: WEARABLE PRINTED TEMPERATURE SENSORS: SHORT REVIEW ON LATEST ADVANCES

167 X. CONCLUSION Wearable electronics are foreseen to revolutionize the health- care system by providing an easy alternative to clinical diag- nostics and early detection of various chronic diseases through continuous monitoring of human body fluids and physiological parameters. Temperature sensing is one of the prime physiologi- cal biomarkers, which is used to monitor and determine the heat exchanges occurring between the inner body tissues and external environment. The fast developments in thin film manufacturing technology are expected to provide solutions for replacing bulky and rigid electronics, that could easily and fully integrate onto nonplanar surfaces, particularly on the human body. The large area manufacturing enabled by the high througput printing tech- nologies is ideal for development of wearable sensing modules, as covering wider surface of the skin is desired for getting reliable data regardless of the large physiological deformations occurring due to movements. This review highlights the latest developments made in the advancements of wearable tempera- ture sensors. Remarkable efforts have been made towards realiz- ing flexible and biocompatible temperature sensors concerning the new geometric designs, utilizing functional nanomaterials in their pristine form as well as exploring strategies to make suitable nanocomposites that are more suitable for temperature sensing applications in real time. Flexible temperature sensor is reported either in the RTD or thermistor geometries, which are easily achievable to fabricate through additive manufacturing approaches. Metallic conductors are mostly adopted for the

RTD structure, however a more focus on the PEDOT:PSS and carbonaceous materials is observed to be reported in the latest developments. Printing is the broadly adopted manufacturing technique especially the inkjet printing technology that used these functional materials in their solution form with respec- tive rheological properties. A comparative study based on the processability through printing, suitable materials, biocompat- ibility, stability, sensitivity, and reproducibility of results is performed. It is observed that certain nanocomposites partic- ularly mixtures of graphene and PEDOT:PSS could achieve higher sensitivities. Despite the fact that all printed devices have been realized on flexible substrates, it is still challenging to maintain the reproducible sensing response in the suitable range of temperature sensing suitable for wearable applications. Few of the challenges are highlighted faced by the development of wearable sensors related to the material, geometry, interfacing with the signal conditioning circuits, attachment of the sensors to human body using biocompatible interfaces or adhesive, compact wireless communication modules and a user-friendly design of the wearable gadget.

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中文

# 可穿戴印刷温度传感器:生物医学应用的最新进展综述

Saleem Khan, Shaukat Ali, Arshad Khan, Amine Bermak(IEEE高级会员)

(方法学综述)

**摘要**——可穿戴生物传感设备的快速增长源于人们对监测人体健康数据以及早期预测慢性疾病症状的强烈需求。各种传感器被开发出来,用于通过可穿戴和可植入传感贴片对多种生物标志物进行持续监测。在各种可穿戴生物传感贴片中,温度传感器已被证明是一项重要的生理参数。本文重点介绍了在聚合物基底上利用功能纳米材料印刷制备可穿戴温度传感器的最新进展。特别关注了先进功能纳米材料及其通过印刷技术的沉积方法。对不同材料的几何分辨率、形状、物理和电学特性以及传感性能进行了比较和总结。可穿戴性是这些新开发传感器的主要关注点,本文通过讨论代表性实例进行了总结。最后,讨论了有关稳定性、重复性、可靠性、灵敏度、线性度、老化和大规模制造方面的挑战,并对可穿戴系统的未来进行了展望。

**关键词**——可生物降解,纳米材料,印刷,温度传感器,可穿戴电子学。

## I. 引言

聚合物箔片上的可穿戴传感器和换能器引起了广泛关注,并随着微型化薄膜电子学的快速发展以及医疗从业者从患者处获取实时数据的需求而迅速增长[1]-[5]。机械柔性、轻量化以及在某些情况下的生物相容性和可生物降解性等独特特性使其有别于硅基器件[6]-[9]。薄聚合物基底与曲面的保形集成不会导致传感器信号的显著退化,这使其成为可穿戴生物传感相关应用的理想选择[4],[10],[11]。聚合物基底以及功能纳米材料的低成本,加上通过印刷技术进行制造,增强了其在高性价比便携式和可穿戴传感应用中的吸引力[12]-[16]。由于聚合物基底与洁净室工艺中的高温不兼容,因此更倾向于在箔片上进行印刷。印刷能够实现功能材料的定点沉积,从而显著减少材料浪费[14]。已有大量有趣的传感器件和系统被报道,且数量仍在持续增长,其中特别关注可穿戴生物传感设备[9],[10],[17]-[19]。在已开发的各类生物传感器中,温度传感器被广泛报道为独立器件或可贴附于人体皮肤的传感贴片的一部分[19]-[24]。温度是一项重要的生命生理体征,用于确定表皮组织与外部环境之间发生的热交换。对于人体而言,与深部体温传感相比,人体皮肤温度的监测得到了更广泛的探索[23],[25]-[27]。人体在经历各种疾病时会遭受热应激,例如从普通发热到更严重的慢性疾病,如心血管、糖尿病、肺部诊断、癌症及其他综合征等[28],[29]。皮肤温度和深部体温的升高被认为是严重疾病发展的初步指标,在大多数情况下,持续监测变得至关重要[27],[28],[30],[31]。因此,在生物相容性聚合物基底上开发的可穿戴生物传感贴片对于实时监测生物标志物至关重要,这些生物标志物可以通过无线方式将数据传输至医院设施,供医疗专家远程观察和诊断[32]-[36]。图1展示了可穿戴生物传感场景及用于实时健康监测的潜在生物标志物的更广泛概述。

除了材料特性外,基底的选择对于可穿戴温度传感器至关重要,因为部署在人体皮肤等曲面上需要在不同方向(如静置、移动、拉伸和弯曲等)下具有良好的灵敏度和准确性[37]-[39]。这可以通过多种策略实现,例如将传感器放置在不受生理运动影响的位置,或者精心选择所有材料以实现与人体的顺从性集成,从而轻松减轻不必要的噪声信号[40]-[44]。除了良好的灵敏度和准确性外,温度传感器还需要具有良好的重复性、对微小变化的敏感性(因为温度变化范围非常小,即25-40°C),以及在不同气候条件下具有增强稳定性的鲁棒性[45]-[48]。可拉伸互连线发挥着重要作用,因此被视为开发可穿戴生物传感贴片的主要互补组件,因为可变形互连线可以吸收应力,而对中央传感器件的影响可忽略不计[49]-[51]。因此,开发可靠的可穿戴传感贴片需要软质轻质基底、先进功能纳米材料(用于制备软质薄膜传感层)和可拉伸互连线[52]的良好组合,最重要的是需要一种稳健的制造工艺,用于在环境条件下加工这些低Tg(玻璃化转变温度)材料[9],[16],[53]-[55]。本文重点介绍了传感单元几何设计、工程化纳米材料(无机和有机)以及特别是基于溶液的印刷技术制造方法的最新进展。

## II. 可穿戴温度传感器:设计与最新技术

温度传感是用于确定人体温度的核心生理参数,特别适用于患有长期慢性疾病、普通发热、昏迷和正在接受手术治疗的患者以及医护人员的健康状况监测[56]-[58]。可穿戴温度传感不仅在医疗相关领域受到关注,而且对于监测和追踪进行大量户外活动的健康人群的体温也非常有用[59],[60]。除了运动员和运动人士的剧烈运动外,可穿戴温度传感器对于在非常恶劣环境条件下工作的劳动者也非常有用。气候条件特别是温度和湿度的升高会导致个体脱水,并对其健康造成疲劳和许多其他严重影响。因此,开发可穿戴温度传感器不仅用于监测人体健康,而且对于监测当地周围环境同样重要。图2展示了采用温度传感器并配合无线数据传输模型的可穿戴传感模型示意图。

### A. 温度传感器

传统上,温度传感器根据不同的几何结构进行开发,具体取决于应用、材料的可加工性以及以所需形状进行制造的可行性[23],[61]-[63]。这些不同的结构通过温度传感机制来区分,该机制通过某些变化以及与热表面的物理相互作用来实现。温度传感器的两大类基于接触式和非接触式传感机制。接触式传感器用于监测包括固体、液体和气相在内的各种表面。然而,非接触式传感器可以远程感测热表面发出的热辐射。主要的温度传感器包括恒温器、热敏电阻、电阻温度检测器(RTD)、热电偶、负温度系数热敏电阻(NTC)和硅基传感器等。这些传感器的工作原理详见[64],[65]。其中,RTD(电阻温度检测器)的体电阻变化、热敏电阻(热敏电阻器)、常用的水银温度计、光学和手持式红外监测传感器等是几种常用的温度传感器类型。每种类型的传感器都具有优于其他类型的优势,然而,可穿戴相关应用的某些限制限制了特定类型传感器的采用。RTD和热敏电阻通常被广泛应用于许多应用中,因为它们具有可靠的快速响应、结构稳定性、良好的准确性,最后其易于制造使其非常适合以大幅降低的成本进行批量生产[66]-[68]。另一方面,热红外和光学传感器通常在室内医疗设施中使用,但它们是在晶圆基底上开发的,信号处理电路也嵌入在刚性PCB(印刷电路板)上,这对轻量化和便携式可穿戴应用提出了挑战。传感器与人体皮肤的保形附着直接要求所有贡献材料具有足够的柔性或可拉伸性,以吸收由人体物理活动引起的变形所产生的应力[23],[67],[69]。对于这种情况,传感器的大面积覆盖发挥着重要作用,这特别通过RTD和热敏电阻的几何方法实现。图3展示了适用于此类情况的理想几何结构设计。可穿戴传感器所需的关键性能指标包括灵敏度、准确性、在较低温度范围内的检测能力、可靠性和重复性。

灵敏度方面的线性响应可以提高准确性,这在人体体温传感中尤其重要。温度传感范围是一个关键参数,需要选择对人体微小变化非常敏感的材料[61],[70]。传感器的响应时间是另一个关键参数,在检测热变化方面发挥着重要作用。症状的早期检测有助于及时诊断和治疗。实时监测取决于响应时间、稳定性和滞后等各种重要参数。分辨率是指传感器可测量的最小变化量,因此在可穿戴温度传感器中成为一个重要参数。最后,对于可穿戴性,传感器需要在生物相容性基底上开发,具有轻量化特性,并且能够在曲面上保形附着,而不会导致传感器响应的显著损失[61],[70],[71]。

## III. 温度传感材料

材料选择是开发可穿戴生物传感应用的关键和主要使能因素。用于开发可穿戴生物传感器的材料需要与底层基底以及构成传感器结构的其他成分材料具有匹配的特性。通常,材料需要具有生物相容性、便携性、轻量化、柔性/可拉伸性,并且能够在曲面上保形附着,而不会在物理和传感响应方面出现显著退化[28],[34],[72]。由于可穿戴传感器直接贴附在人体皮肤上,因此期望传感器不会对健康或医疗造成任何风险。在这种情况下,对于可穿戴和可植入传感设备而言,生物相容性是非常理想的要求。这包括基底以及用于构建传感设备的材料的生物相容性。各种生物传感器,如多功能脑传感器、可植入压力-应变传感器等,已被报道完全在生物相容性基底上开发,并使用了类似的传感材料[73],[74]。然而,这些制造工艺既有显著的优势,也有关键的限制。其中,通过印刷技术开发的温度传感器需要某些对每种制造类型而言独特的特性。传统上,用于印刷的材料呈胶体或纳米复合材料形式,其中溶液的流变特性针对特定印刷技术进行调整。例如,溶液粘度、表面张力、粘附功、铺展系数和溶液中纳米颗粒浓度是选择印刷技术时考虑的一些主要特性。可穿戴印刷温度传感器以RTD或热敏电阻的形式开发,因此在传感器结构的构建中使用本征导电材料以及温度传感导体/半导体。已经开发出具有适用于不同印刷技术的所需溶液特性的多种材料。本节重点介绍专门用于利用印刷技术开发可穿戴温度传感器的几大类印刷材料。

### A. 金属导体

金属导体的电阻随相应温度变化的变化与材料的固有热电阻系数(TCR)相关[46],[66]。由声子相互作用引起的这些电阻变化是将这些材料用于温度传感器的核心。较高的TCR值(正或负)是将这些金属导体用于特定温度变化范围的关键选择标准。纯金属如金(Au)、铜(Cu)、铂(Pt)、镍(Ni)、铝(Al)和银(Ag)通常用于温度传感应用[61],[62],[75]。这些结构以导线、固体薄膜以及包含在封闭流动通道中的液体形式开发。先进的制造技术,特别是这些金属导体在高分辨率图案化方面的薄膜沉积,引起了广泛关注。由纳米颗粒悬浮液制成的胶体溶液,通过增材制造等受控沉积技术进行加工,在减少材料浪费方面发挥着重要作用,从而为降低整体制造成本做出了很大贡献[76],[77]。胶体通过将金属纳米颗粒混合在合适的溶剂中制成,呈现出介于溶液和悬浮液之间的特性。形成的混合物大多为异质性的,根据纳米颗粒尺寸具有可调散射相的分散特性[77],[78]。纳米颗粒的平均尺寸和纵横比保持在较窄范围内以促进均匀分散。此外,以表面活性剂形式添加添加剂,用于调节流变特性如粘度和表面张力等,以及增强溶液稳定性和延长保质期[79]-[81]。这些金属导体被图案化为独立的换能器层(如RTD)以及薄膜器件的组成层。镍(Ni)基温度传感器因其吸引人的特性而被广泛报道,例如更高的灵敏度、线性度、高电阻基准点、宽传感范围(0-100°C),以及最重要的是与其他金属导体相比,它在市场上以较低的价格供应[28],[68],[82]-[84]。其中一些金属导体容易氧化,特别是Cu和Ag,因此以纳米复合材料的形式制造多层涂层。高导热敏感材料Ni被更稳定的Pt层涂覆作为保护覆盖层[82]-[85]。然而,大多数这些沉积发生在通过使用洁净室工艺控制的条件下。为了简化制造过程并使其可在环境条件下进行探索,通过湿法加工技术沉积这些金属纳米颗粒的胶体更具吸引力。金纳米颗粒溶液已被广泛探索,多个团队已开发出商业级稳定油墨。金更稳定,具有线性响应,对环境影响的抵抗力强,最重要的是它具有生物相容性[28],[68],[86]。目前,金基图案化在热稳定的聚酰亚胺基底上进行,因为其相对较高的烧结温度,即250°C[62],[86]。这一挑战需要得到解决,理想的烧结温度在150°C以内将能够在多种聚合物基底上进行金基图案化。

### B. 无机/有机导电材料

有机导体是产生类似于金属或无机半导体的导电特性的聚合物材料[13],[87]-[89]。这些本征导电聚合物的化学结构可以在受控的洁净室环境中进行调整,以获得所需的电学、化学和机械特性[89]。关于p型有机导体的开创性报道随后开发出了许多类似类型的材料。常用的聚合导体包括但不限于聚乙炔、聚吡咯、聚苯撑、聚(对苯撑乙烯)、聚噻吩、聚苯胺、用樟脑磺酸掺杂的聚苯胺以及PEDOT:PSS(3,4-聚乙二氧噻吩-聚苯乙烯磺酸)、石墨烯等[90]-[92]。在这些材料中,PEDOT:PSS和石墨烯因其丰富的可用性、易加工性、良好的电学、化学和机械特性而引起了广泛关注[87],[93],[94]。简便的制造和加工技术,特别是湿法制造路线,为这些材料的广泛研究做出了重要贡献。许多令人兴奋的应用已被探索,特别是与温度相关的应用。聚合物材料特别是PEDOT:PSS的微观结构负责热传感特性[95]。EPDOT:PSS纳米晶体形成核壳结构,其中PEDOT保持在晶粒核心,PSS围绕核心。PEDOT:PSS层的体电阻率主要受材料的绝缘PSS部分影响。随着温度升高,颗粒边界数量减少导致有效边界尺寸减小,这影响了整体电阻。在较低温度下,电子没有足够的热能来越过这些边界,因此电阻增加[96]。PEDOT:PSS的强机械特性也使其成为可穿戴相关应用的理想候选材料,因为它在极低偏转角下弯曲时能保持与基底的强粘附力。同样,碳基纳米材料和溶液也被广泛探索用于温度相关的传感应用。原始形式以及纳米复合材料形式的碳纳米管已被部署在聚合物基底上作为热敏电阻。石墨烯在碳质家族中,在电学和热学性能方面优于许多金属和CNT,因此被广泛应用于热管理和能量存储相关应用。石墨烯单层和纳米尺度上非常强的物理结构产生了优异的热学特性。电导率与温度之间的强线性关系使石墨烯成为常用金属导体作为RTD的有前途的替代品。石墨烯单层的沉积主要通过CVD(化学气相沉积)在洁净室工艺中在电子级硅晶圆上完成。为了在聚合物基底的大面积上部署并使沉积过程简单且成本效益高,溶液形式的还原氧化石墨烯已被广泛报道。

### C. 有机-无机杂化和纳米复合材料

有机-无机杂化材料是工程材料的一个有趣领域,两种材料的令人兴奋的特性相互补充,产生非凡的特性。例如,当无机金属导体与有机弹性体混合时,会产生先进的可拉伸和柔性复合材料,非常适合可穿戴传感应用。除了电学特性外,这些杂化材料还表现出增强的物理特性,包括良好的光学、发光、化学惰性以及对化学和生化传感环境的选择性。利用这些杂化材料已经开发出广泛的传感应用,涵盖了几乎所有物理、化学、电学和电化学传感器领域。有机-无机杂化材料、其合成和应用已被广泛综述[97],[98]。有机-无机杂化材料根据键合强度大致分为两类。一种类型发生弱的范德华、静电或水凝胶键合,而第二种类型在分子之间形成共价键或离子键。采用了多种合成技术,其中溶胶-凝胶法、水热法和溶剂热法是常用的方法。杂化纳米复合材料是合成的定制材料,具有针对特定应用理想所需的调节物理、电学和机械特性[87],[89],[99],[100]。金属纳米颗粒以粉末形式或混合在溶剂中分散在聚合物基质中,形成均匀稳定的混合物。基质内的纳米颗粒在纳米复合材料体中形成导电网络。对于金属导体,材料作为纳米复合材料薄层依次沉积,以增强粘附力,防止底层材料氧化和其他环境影响[101],[102]。为了使纳米复合材料能够通过增材制造技术部署在更大的面积上,这些金属导体的纳米颗粒以各种比例混合在聚合物基质材料中,针对目标应用[13],[21],[103]。为了实现可重复的加工和测试结果,高度期望导电填料的均匀分散。使用不同的混合技术如机械搅拌和球磨来实现均匀分散,在某些情况下随后对纳米填料进行功能化[104],[105]。填料和基质材料的混合比例基于渗流阈值确定,在渗流阈值处通过达到最佳组合百分比实现一定水平的导电性。这些导电纳米复合材料是开发广泛传感器件的关键,例如压力、温度、湿度和接近传感器等[105]。纳米复合材料通过混合金属和有机导电填料制成。温度传感主要记录为纳米复合材料层体中电阻随热梯度的变化。理论上,在聚合物基质内形成连接网络的导电填料负责电阻率变化,使其对温度变化敏感。多种导电纳米填料已被探索用于纳米复合材料的合成,用于温度传感和监测[106]-[109]。例如,将石墨与PDMS混合的纳米复合材料用于制造包含64个传感器的大面积传感贴片,每个传感器面积为4×4 cm²[106]。在PI基底上开发的Cu基叉指电极也被应用于监测纳米复合材料层的导电性变化。在25-150°C的温度范围内,对碳和Ag分别与PDMS混合的热传感性能进行了详细的比较研究[110]。碳基纳米复合材料在高达150°C时表现出更清晰的响应和温度依赖性,而Ag基纳米复合材料在120°C时产生最佳响应。使用纳米复合材料作为热传感层可以轻松探索不同的配置和几何结构,特别是以离散电阻器或惠斯通电桥设计的形式[111]。

## IV. 基底

聚合物基底的有趣特性如柔性、可弯曲性、轻量化和可穿戴性等,为大面积器件的低成本制造提供了支撑基础[12],[112],[113]。在小角度偏转下的可弯曲性使其非常适合通过卷对卷制造进行高速生产[114]。期望柔性基底具有与标准平面刚性基底相当的稳定特性[115]。迄今为止开发的三种不同类型的柔性基底是薄玻璃[116],[117]、薄金属箔[118],[119]和聚合物基塑料片[120]。其中,塑料基底更适合低成本可穿戴相关应用,因为薄而脆的玻璃价格昂贵且容易破裂。同样,基于薄金属箔的基底相对较重,需要大量的表面处理以使其适合功能纳米材料的薄膜沉积。在这种情况下,塑料基聚合物基底在物理、机械和化学惰性等方面提供了合理的折衷。使用塑料基底的一个主要障碍是其低玻璃化转变温度(Tg),通常在250°C以内。然而,这涵盖了大多数可穿戴和可植入设备所需的生物相容性基底范围[120],[121]。基底材料的生物相容性对于开发可穿戴生物传感器至关重要。生物相容性被称为一个重要因素,负责活细胞/组织与传感模块之间的安全界面,而不会对部署表面造成任何损害。由于基底与人体皮肤或组织亲密接触,为了避免任何医疗风险或并发症,严格需要透气性和生物相容性[122],[123]。需要评估体外和体内应用的生物相容性,特别关注对细胞的毒性、细胞附着、浸出物和细胞培养。特性不匹配或非生物相容性可能导致细胞损伤以及炎症问题和免疫系统紊乱[122]。已经开发出考虑生物相容性方面的各种基底,包括SU-8、透气膜、碳化蚕丝纤维、棉织物、纤维素基材料,最重要的是聚合物基生物材料[32]。在潜在的聚合物基底中,PDMS是可穿戴电子学的理想选择。粘弹性和生物相容性使其更适合部署在曲面上。最近开发的纤维素基基底也被使用,然而基底的孔隙率和液体吸收能力使其对于人体佩戴的生物传感应用具有挑战性[124],[125]。聚氨酯是常用的报道基底,用于利用生物相容性[126]。半透膜允许一定量的湿度和氧气,这是活细胞和组织正常功能所必需的。大多数生物相容性基底的一个主要挑战是其有限的上限加工温度。由于金属导体例如Au需要更高的温度(即~250°C),这超过了这些基底的Tg。因此,采用闪光灯烧结技术来解决这个问题。在闪光灯烧结中,只有薄膜的顶层被调节的光强度和功率加热,而不会损坏底层基底。然而,闪光灯烧结也有一定的局限性,即基底的透明度以及与烧结图案接触的上表面的变形。因此,开发生物相容性基底和提供低温操作并产生更高瞬时温度的可靠烧结技术是非常理想的研究方向。

## V. 可穿戴传感的关键使能技术

开发适合部署在曲面上的电子器件和传感器,要求所有组分材料在可加工性、机械和机电特性等方面完美匹配[2],[3],[32]。此类器件的关键使能因素是合成具有适合特定印刷技术的流变特性的功能纳米材料胶体溶液,并将其顺从性地集成在聚合物基柔性基底上[12],[62]。图4展示了制造柔性和可穿戴传感器件所需的关键使能因素。

### A. 印刷技术

印刷是在环境条件下在各种基底上图案化功能材料的重要关键使能因素。通过印刷实现的成本效益制造以及超过晶圆尺度的加工面积是其主要吸引力。与传统洁净室加工相比,印刷技术可用于高分辨率图案化以及以更简单的方式涂覆更大面积[12],[27]。以受控方式在指定位置按需沉积材料,使印刷技术因减少材料浪费而区别于其他制造技术。由于印刷以单步完成,而洁净室工艺涉及多个减法步骤来图案化结构,因此材料浪费降低[114],[128]。各种印刷技术已被采用和修改,借鉴了传统文字印刷技术的专业知识。使用的几种主要印刷技术包括但不限于凹版印刷、胶印、柔版印刷、喷墨印刷、丝网印刷、气溶胶印刷、转移印刷和微接触印刷等。所有技术都有特定的要求,并根据其能力产生结果。溶液和纳米复合材料的流变特性在选择印刷技术时排在首位。例如,喷墨印刷、槽模印刷和气溶胶喷射印刷需要粘度在5-12 cPS范围内的材料,而丝网印刷以及凹版印刷和胶印技术则需要更高的粘度。同样,在基底上实现的图案分辨率和薄膜厚度取决于印刷技术的选择。丝网印刷和胶印产生厚膜(在0.2-0.8 µm范围内),而喷墨和气溶胶印刷用于打印薄膜(在0.01-0.2 µm范围内)。通过多次印刷循环调节薄膜厚度,取决于所需的厚度。印刷速度是选择特定印刷技术时考虑的另一个重要参数。凹版印刷、胶印和柔版印刷以其高速生产而闻名,因为它们易于安装在卷对卷印刷系统上。这些系统可实现高达~150 m/min的速度,形成可重复和可再现的薄膜。而喷墨印刷、丝网印刷和气溶胶喷射印刷是低速工艺,主要用于生产原型或安装在研究实验室设施中进行评估。

除了印刷技术外,选择合适的材料在确定温度传感器的关键因素方面也发挥着重要作用。沉积有机/无机材料以图案化或薄膜形式的制造工艺由纳米颗粒溶液的流变特性决定。对于柔性基底上的可穿戴电子学和器件开发,材料和加工技术需要尊重所有限制。在标准制造工艺中,光刻胶涂层、敏感光照射、蚀刻、目标材料沉积随后剥离等不同的组合步骤使制造变得复杂且非常昂贵,因为大量材料被浪费。这也直接或间接地增加了电子和材料污染的预算。此外,复杂和精密的工艺将制造限制在能够获取和维护此类制造设施加工成本的特定群体中。因此,当涉及低资本投资的低成本制造时,基于溶液的增材制造提供了显著的优势。因此,除了其他电子器件的开发外,温度传感器也使用印刷技术开发[30],[82],[129]。

印刷已成为薄膜电子学快速制造的一种有吸引力的方法。功能纳米材料的化学溶液或胶体在添加剂和表面活性剂的帮助下稳定,用于印刷[130]-[132]。根据特定印刷工艺的要求和要实现的目标功能调整特性和材料含量。受控沉积和分配参数由材料特性以及驱动机制参数共同调节[133]。影响驱动机制的最重要溶液特性是粘度、表面张力、颗粒含量、平均纳米颗粒尺寸和溶剂蒸发点等[130],[134]。基底表面条件也发挥重要作用,并对印刷结构的最终形状和分辨率有显著贡献。表面特性如亲水性、表面能、低接触角、高粘附功等需要处于适中水平,以实现良好的印刷结果[135],[136]。本综述中考虑的两种温度传感器是RTD和热敏电阻,它们采用能够图案化高分辨率导电结构以及沉积均匀热传感层的印刷技术。

### B. 印刷温度传感器

印刷RTD的工作原理是电阻随温度升高而变化,因此使用热电阻系数(TCR)来确定相应的温度变化[137]-[139]。以蛇形、螺旋形或圆形形式的全印刷制造方法使制造简单且成本效益高。对于RTD,传感器仅使用导电纳米颗粒油墨通过印刷所需结构一步完成。相同类型的油墨用于互连线以及接触垫。因此,制造RTD的过程很简单,通过印刷技术以单步制造非常有利。另一方面,热敏电阻由两种不同的材料制成,因此需要两次印刷循环来完成制造过程。叉指电极(IDE)是器件的第一层,使用金属油墨印刷[13]。连续电极之间的叉指间距在传感响应中发挥重要作用。因此,已经进行了各种研究来优化间距与相应热敏材料的关系。第二次印刷循环使用热敏材料沉积在IDE覆盖的有源区域中,使用印刷或薄膜涂层技术。近年来,通过探索不同的材料和制造工艺,在RTD和热敏电阻方法方面取得了显著进展。由还原氧化石墨烯(rGO)和聚羟基丁酸酯(PHB)组合制成的导电聚合物复合材料混合物用于制造RTD和热敏电阻结构。使用Ag基电极,直接印刷技术和滴涂法分别用于图案化和沉积油墨[13]。图5展示了一种新型热敏电阻的示意图和印刷模型,其中温度传感材料被图案化,而不是完全填充IDE围绕的有效面积。这种类型的传感器被认为比整个传感层作为薄膜沉积的传统热敏电阻更有效。

在纤维素基生物相容性基底上,通过喷墨印刷技术制备了高分辨率Ag蛇形图案[30],[140]。采用全印刷方法图案化沉积PEDOT-PSS和碳油墨来设计惠斯通电桥[20],[141]。同样,由碳和PEDOT:PSS混合物制成的喷墨印刷传感器具有约0.25%/°C的TCR值。在可贴附皮肤的聚氨酯膏药(创可贴)上开发石墨烯/PEDOT:PSS油墨的喷墨印刷。RTD设计中的一项新改进是在石墨烯/PEDOT:PSS图案的通路中添加Ag基导电条带[67]。主要使用喷墨印刷技术开发了包含多个传感单元(如加速度、ECG和温度传感器)的小型可穿戴贴片。对于温度传感器,混合PEDOT:PSS和CNT以获得与喷墨印刷技术兼容的油墨[142]。作为用于可穿戴健康监测应用的多感官贴片的一部分,报道了一种高效的可贴附皮肤温度传感器。通过将CNT油墨和PEDOT:PSS以3:1 wt%的比例混合合成可喷墨印刷的油墨,用于开发基于皮肤的温度传感器[69]。报道了一种类似类型的可穿戴温度传感器,制成带状用于人体手腕。使用PEDOT:PSS的喷墨印刷来开发这种温度传感器[143],[144]。PEDOT:PSS、Ag纳米颗粒和石墨烯油墨的纳米复合材料的丝网印刷用于浸渍可拉伸织物,以开发可穿戴自供电温度传感器。这种类型的传感器被认为提供了非常有吸引力的特性,如超薄、轻量化、高柔性和可拉伸性等,使传感器能够与人体皮肤保形接触[35]。通过使用SWCNT、MWCNT和AgNps的不同混合物开发了一种高可拉伸但应变不敏感的传感器。合成的油墨以特定比例混合,与Microplotter喷墨印刷系统兼容[145]。

气溶胶喷射印刷最近取得了令人兴奋的成果,在印刷电子学领域以较少的努力实现了高分辨率图案化。在这种情况下,在Kapton基底上报道了一种Cu-CuNi温度传感器。使用气溶胶喷射印刷沉积纳米颗粒,然后在尊重Kapton基底热特性的较低功率下进行激光烧结[82]。除了温度传感器的固化传感结构外,液态金属导体也被用于3D打印微通道中。使用生物相容性聚乳酸材料作为3D打印机制造的微流控通道的基底,并填充液态金属(Galinstan,Rotometal)。传感器部署在人耳上,用于检测核心体温[146]。转移印刷用于开发超柔性和生物相容性温度传感器,采用Au/Cr制成的蛇形结构。温度传感材料使用转移印刷方法集成在聚氨酯基底中。最初使用光刻技术在PI(聚酰亚胺)涂覆的硅晶圆上开发Au基微结构[33]。表I总结了一些代表性设计、传感材料、基底、制造方法以及用于覆盖传感层以提供额外机械强度和免受变化气候条件的封装材料。

## VI. 基于不同材料和结构的温度传感性能

印刷温度传感器的工作原理是电阻随相应温度升高而变化,因此TCR通常被视为灵敏度的测量参数[57],[129],[147]。对于可穿戴温度传感器,体温会因活细胞与外部环境之间的热量传递而变化[148],[149]。这种热量通过皮肤或呼吸系统散发。通过可穿戴温度传感器实现实时监测,以确定在各种条件下身体发生的变化[150]。无论身体处于运动还是静止状态,准确测量对于记录实时数据都很重要。尽管柔性传感器的保形界面和部署提供了实时检测这些微小变化的可能性[151]-[153]。它们仍然需要灵敏度、快速响应、无滞后、在不同条件下的鲁棒性以及在正常生理运动期间的稳定性的良好组合[154],[155]。由于传感器用于监测人体健康状况,数据将用于紧急决策,因此可靠的传感数据至关重要[156],[157]。为了提高灵敏度和可靠性,使用了多种功能纳米材料,包括原始形式和纳米复合材料,以实现更好的性能[61],[72],[158]-[160]。

### A. 导电材料基传感器的性能

最近进行了各种有趣的研究,重点关注性能、可靠性、可穿戴性和生物相容性等多个方面。在这种情况下,通过转移印刷在半透聚氨酯膜中嵌入Au蛇形结构制备了一种超薄温度传感器[33]。该传感器经过24/7测试,并在水浴中进行校准。传感器在多个身体部位(如腋下、前臂)放置时表现出0.002778 /°C的TCR值,声称其性能可与水银基传感器相媲美。在生物相容性、透气性和可拉伸基底上开发传感器很有趣,因为它在不会导致传感器性能显著降解的情况下透过水和空气[33]。Ag是RTD中常用的印刷材料形式,其中印刷图案的体电阻变化与温度变化相关[31],[66],[161],[162]。

在细菌纳米纤维素基底上开发了一种高分辨率印刷Ag蛇形结构,该基底具有生物相容性和可生物降解性。传感器表现出正电阻系数(PTC),灵敏度为0.06 /°C[140]。使用喷墨技术的大面积Ag印刷蛇形结构在20-60°C的温度范围内表现出0.0029/°C的TCR值[30]。PEDOT:PSS被大多数研究报道用于开发温度传感器,除了金属导体[95],[163],[164]。作为聚合物和高导电性,其固有的柔性使其成为在聚合物基底上制作电导结构的有吸引力的候选材料[58],[93],[126]。在Kapton和棉织物基底上报道了一种基于PEDOT:PSS的温度传感器,适用于可穿戴相关应用[30]。该声称传感器对温度微小变化高度稳定和敏感,可以检测到低至0.1°C的变化[144]。交联PEDOT-PSS用于开发基于热敏电阻的温度传感器,其中IDE使用Ag纳米颗粒基油墨进行喷墨印刷,传感区域以蛇形图案配置覆盖PEDOT-PSS。图5展示了使用这种架构的示意图和印刷传感器。传感器表现出NTC,报道了0.77%/°C的更高灵敏度。通过与GOPS混合提高了PEDOT:PSS的灵敏度[20]。

### B. 纳米复合材料基传感器的性能

金属和聚合物基纳米复合材料也被广泛探索用于广泛的生物传感应用[94],[165],[166]。对于温度传感器,rGO[137],[166]及其纳米复合材料,特别是与PEDOT:PSS和PHB的纳米复合材料,被用于RTD和热敏电阻配置[56],[87],[167]。Ag基IDE用于热敏电阻,采用印刷机制来沉积调整过的纳米复合材料溶液。据报道,传感器对rGO和rGO/PHB纳米复合材料均表现出NTC。据报道,rGO的最小TCR值在0.018-0.03范围内,12 wt.%混合比例的最大值[13],[144]。使用可贴附皮肤的聚氨酯膏药来开发温度传感器。通过混合石墨烯/PEDOT:PSS制备可喷墨印刷的纳米复合材料溶液,并通过喷墨印刷技术图案化为蛇形。通过在石墨烯/PEDOT-PSS图案的通路中印刷Ag条带来增强传感器响应,以减轻信号退化的可能性。传感器在适用于人体健康监测的温度范围(即35-45°C)内具有响应性。石墨烯/PEDOT:PSS表现为NTC,在操作温度范围内记录到0.006/°C的TCR值[67]。据报道,直线宽线的温度传感器具有更高的灵敏度,即1.3%/°C。宽传感图案通过印刷PEDOT:PSS和CNT的纳米复合材料溶液开发,与Ag基互连线连接[69],[144]。图6展示了在不同湿度和温度条件下的一些代表性灵敏度响应。图表显示了两种不同器件(即热敏电阻和热电偶)的数据,其中热敏电阻的传感器响应测量为电阻,塞贝克系数用于确定变化的温度值。

### C. 基于非常规架构的传感器性能

通过利用一些非常规架构和材料,提出了可穿戴传感应用领域的进一步发展。例如,采用全印刷方法设计和制造了惠斯通电桥配置。传感器由碳纳米颗粒油墨和PEDOT:PSS与DMSO(二甲基亚砜)的混合物制成,分别评估TCR为正和负系数。TCR还评估为PEDOT:PSS和DMSO在0.3 wt.%和3 wt.%混合比的函数,结果分别为0.009 /°C至0.0025/°C。碳基油墨产生正TCR,即0.0022/°C[141]。另一个有趣的替代方案是通过监测人体内部而非皮肤表面来监测核心体温。传感器通过3D打印开发,能够佩戴在人耳上以从鼓膜记录核心体温。通过3D打印液态金属在可穿戴模块中开发红外传感器,并连接无线通信系统进行实时监测[146]。基于织物的温度传感器非常有吸引力,因为固有的可穿戴性和可拉伸性特性符合大多数传感器要求。通过开发可扩展的传感器,使用Ag、PEDOT:PSS和石墨烯的纳米复合材料采用热电方法确定温度响应[168]。这种超敏感材料的混合物通过模板涂覆印刷。对于100 K的温差产生1.1 mV的输出电压,在20%应变的800次循环中具有高耐久性。传感器还探索了对应变方向的依赖性,并表现出相应的温度传感特性[35]。

另一个有趣的进展是利用塞贝克效应来减轻温度传感数据中可能发生的应变相关噪声。三种不同的纳米材料,即SWCNT、MWCNT和AgNw,以不同的组合使用,并通过高分辨率Microplotter技术印刷。这一进展背后的核心思想是塞贝克系数的差异产生与结冷热点差异成正比的电压。开发了大量传感器阵列并部署在人体手上。SWCNT/AgNw混合纳米复合材料的塞贝克系数可达37mV/°C。同样,MWCNT/SWCNT产生23mV/°C的塞贝克系数,低于SWCNT/AgNw组合。两种组合都产生了良好的线性和传感器结果的可重复性[64],[101]。另一种类似的方法利用通过气溶胶喷射印刷沉积的CU和CuNi薄膜的塞贝克响应。实现了更高的塞贝克系数,即40 µV/°C,声称是在聚合物基底上开发的传感器中报道的最高灵敏度。在200次弯曲循环后,在不同偏转角下进行稳定性测试,塞贝克系数的变化在2.5%以内,可忽略不计[82]。表II总结了代表性器件的响应,包括设计、TCR、温度范围、灵敏度和人体上的可穿戴位置。

选择含氟聚合物CYTOP(CTX-809A)作为钝化层,因其具有低水蒸气渗透性和与基底的良好粘附性。

## VII. 封装材料

覆盖印刷结构对于保护传感层以及互补的信号读出互连线免受环境影响非常重要。封装不仅对于更易受气候条件影响的有机基材料很重要,而且对于由Cu和Ag制成的金属基RTD也很重要,因为它们容易氧化。封装层的物理、电学和机械特性需要与底层传感和金属层匹配。一层非常薄的绝缘层足以阻挡任何渗透的空气或湿气。封装层的局部沉积通常特别沉积在有源传感区域。对于可穿戴传感贴片,不需要覆盖基底的整个面积。基底通常是生物相容性的,有时选择多孔基底以维持人体皮肤的正常环境条件。因此,迄今为止报道的大多数可穿戴温度传感器总是在有效传感区域施加合适的封装层,同时选择生物相容性基底。

使用半透膜作为封装层来开发透气和可拉伸的温度传感器。该膜覆盖用于开发传感器的多个底层薄膜,同时提供坚固的基础以保持基础传感层的平面性和中性[33]。在喷涂CNT层上施加基于UV-环氧的封装层,并与未封装的传感器进行评估[169]。封装的传感器与未封装的传感器相比,产生了更线性的响应和最小的滞后。氟聚合物(CYTOP)CTX-809A作为钝化层施加在印刷的PEDOT:PSS传感层上[20]。采用滴涂技术产生厚度约10µm的薄层。报道了足够的防潮钝化以及增强底层传感层。图7展示了有和没有封装层的传感器示意图及其灵敏度响应。通过比较封装和未封装传感膜的性能,观察到全印刷传感器的稳定性。喷墨印刷的PEDOT:PSS和DMSO用作NTC(负温度系数)温度传感器,阻挡箔用作顶部封装层。在65°C和85% RH下进行400小时的湿热加速寿命测试。封装材料不仅影响物理特性,还改善了薄膜的电学特性。封装传感器的电阻相对于基极电阻增加了10%。然而,未封装的传感器在基极电阻中观察到13%的增加,显示出传感器性能的更大稳定性[141]。在另一项测试中,评估了有和没有封装的石墨烯/PEDOT:PSS纳米复合材料[67]。电子级涂层(EGC)材料在氩气环境中滴涂在传感器的印刷区域上,并在室温下干燥。在重复循环和加速测试后的电阻响应确认了覆盖传感器的稳定电阻响应,然而未涂覆的传感器与初始基极电阻显著偏离。电阻与温度斜率从负(NTC)反转为正(PTC),同时在环境条件下测试伴随着显著的滞后。特别是当未涂覆适当的封装层时,环境变化特别是湿度对传感器性能造成了严重影响[67]。施加低湿气渗透膜是另一种使传感器防水的方法。这些材料以溶液形式存在,可以在所需的传感区域确定性地印刷[69]。在热敏材料上层压干膜光刻胶是施加封装层的快速替代方案[170],[171]。使用原子层沉积(ALD)技术在PEDOT:PSS层上沉积铝封装层[172],作为温度传感器防潮的保护层。PDMS是常用的易获取的生物相容性封装层,对化学蚀刻剂和环境变化等呈惰性。简便的加工和沉积/涂覆使其在