Huacui Xianga,
Daniel Verricoc,
Taher Hafizc,
Enjian Hea,
Gary E. Wnekc,
Kun Hud,
Guojun Liu*b,
Yen Wei*a and
Jiujiang Ji*ac
aThe Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Department of Chemistry, Tsinghua University, Beijing, 100084, China. E-mail: weiyen@tsinghua.edu.cn
bSuzhou Institute for Advanced Research, University of Science and Technology of China, Suzhou 215123, China. E-mail: liuguojun@ustc.edu.cn
cMacromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH 44106, USA. E-mail: jjj.2021@tsinghua.org.cn
dSchool of Printing and Packaging Engineering, Beijing Institute of Graphic Communication, Beijing 102600, China
First published on 30th September 2025
With the accelerating advancement of wearable electronics, electronic skin (e-skin) has emerged as a promising technology for applications in health monitoring, prosthetics, and human–machine interfaces. Nonetheless, achieving simultaneous breathability, antibacterial properties, and high sensing fidelity presents a formidable challenge. In this study, we report a multifunctional electronic skin (e-skin) constructed from a modified Tecoflex (thermoplastic polyether-based polyurethane) electrospun nanofiber membrane (T-eNFM), integrating breathability, antibacterial activity, and high-fidelity sensing capabilities. The T-eNFM substrate promotes wearer comfort via its innate breathability while simultaneously inhibiting bacterial colonization through robust antimicrobial functionality. A composite of multi-walled carbon nanotubes (MWCNTs) and silver paste (Ag powder) was printed onto T-eNFM-3 to form a conductive, mechanically compliant sensing layer. The fabricated strain sensor exhibited a gauge factor of 5.81, while the multilayer pressure sensor displayed a sensitivity of 2.83 kPa−1, rendering it ideally suited for monitoring cardiovascular physiological signals. This work outlines a blueprint for next-generation electronic skin devices by addressing the critical challenges of comfort, safety and multifunctionality.
Electrospun nanofibrous membranes (eNFM), characterized by their high surface area, tunable porosity, flexibility, and ability to conform to complex curved surfaces, provide a versatile platform for applications in wearable sensors.17–19 Their nanoscale fiber diameters, interconnected pore networks and modifiable surface chemistry have drawn intense interest in the field of wearable, flexible sensing.20,21 However, the emergence of antimicrobial resistance has impeded the translation of eNFM into practical applications.22,23 Owing to their entangled micro/nanofibers, eNFM form highly porous three-dimensional networks with exceptional pore interconnectivity, making them ideal substrates for cell adhesion and proliferation.22 Simultaneously, the relentless emergence of drug-resistant bacteria has driven growing interest in endowing eNFM with intrinsic bactericidal properties, thereby obviating the need for antibiotic incorporation.24,25 Tecoflex is a thermoplastic polyurethane synthesized from methylenebis(cyclohexyl) diisocyanate, poly (tetramethylethylene glycol), and 1,4-butanediol, and is distinguished by its exceptional flexibility and processability. Electrospun Tecoflex EG-80A yields a highly flexible fabric that serves as a promising substrate for wearable device applications.26,27 However, driven by the demand for safer, more conformable materials, researchers are now focusing on integrating antibacterial functionality into skin-conformable electronics to prevent device fouling and mitigate infection risks during biomedical monitoring.28,29 The incorporation of antibacterial functionalities into skin-conformable electronic devices has emerged as a key strategy to prevent device contamination and mitigate infection risk. Accordingly, embedding antibacterial agents—including metallic nanoparticles (Ag, Au), metal-oxide (ZnO, CuO, TiO2) and metal-sulfide nanoparticles, and carbon-based nanomaterials—directly within fiber matrices, or grafting quaternary ammonium compounds, biguanides, and pyridine derivatives onto fiber surfaces, represents a highly promising strategies for infection control in both biomedical and environmental applications.30–34 Concurrently, the safe and efficient incorporation of fungicides into eNFM to bolster the antifungal performance of electronic sensors represents a critical frontier in safeguarding human health.35,36
In this work, we report a multifunctional electronic skin (e-skin) based on a modified Tecoflex electrospun nanofiber membrane (T-eNFM) that synergistically integrates intrinsic breathability with potent antibacterial activity, ensuring wearer comfort and effective inhibition of bacterial colonization. A composite ink of multi-walled carbon nanotubes (MWCNTs) and silver paste (Ag powder) was printed onto the T-eNFM-3 to yield an e-skin with exceptional electrical conductivity and mechanical compliance. The engineered wearable electronic skin (e-skin) features sensitive and stable pressure and strain sensors, enabling detection of human motion and monitoring of cardiovascular physiological signals via its micro-structured sensitive layer. By seamlessly integrating antibacterial functionality, breathability, and high-performance sensing within a unified structure, this e-skin design addresses limitations of conventional platforms and establishes a foundation for robust, translational applications.
To enable sensing functionality, a composite of multi-walled carbon nanotubes (MWCNTs) and silver paste (Ag powder) was deposited onto the T-eNFM surface via screen printing to form a conductive layer. As shown in Fig. 2a, conductive ink of optimized viscosity was screen-printed onto the T-eNFM surface. The microstructure of the resulting conductive layer was characterized via scanning electron microscopy (SEM). The MWCNTs and Ag paste were stacked and interlaced with each other to form a dense conductive layer. To prepare a conductive layer with a microstructure, as shown in Fig. 2b, the viscosity of the screen-printed ink was adjusted by the content of thickener carboxymethyl cellulose (CMC), and a microstructure was formed on the printed conductive layer. Upon separation from the screen, the high-viscosity ink exhibited reduced surface tension that inhibited capillary-driven smoothing, yielding persistent net-hole imprints and an array of microscopic protrusions across its surface. Screen-printed Ag electrodes revealed stacked silver flakes forming layered architectures (Fig. 2b and c). Upon incorporation of CMC into the conductive ink and subsequent screen printing (Fig. 2d), a grid-like microarchitecture emerges, characterized by interlocking nanotubes and silver flakes that coalesce into a densely packed conductive network (Fig. 2e and f). Energy-dispersive X-ray spectroscopy (EDS) revealed a uniform dispersion of carbon and silver across the electrode surface, with pronounced stacking within the microstructured domains (Fig. 2g). Elemental mapping of carbon (Fig. 2h) and silver (Fig. 2i) further confirmed the homogeneous distribution and structural integrity of the printed conductive layer.
The thermogravimetric analysis (TGA) was used to measure the thermal stability of T-eNFM materials. As shown in Fig. 3b, all samples undergo two distinct stages of thermal degradation. The initial stage corresponds to the decomposition of the hard segments in Tecoflex, followed by further degradation of the macromolecular structure within the soft segments. The onset decomposition temperature (T5%), defined as the temperature at which 5% weight loss occurs, serves as a critical indicator of polymer thermal stability. Notably, the T5% decreases progressively with increasing DOQA content, suggesting that DOQA incorporation compromises the thermal stability of Tecoflex. This reduction likely arises from the weaker thermal stability of bonds formed between Tecoflex and the hydroxyl groups at the DOQA termini compared to Tecoflex's intrinsic bonding. This may also contribute to the development of helical morphology in T-eNFM-3 spun fibers. The incorporation of DOQA modulates the internal molecular interactions within Tecoflex, generating contraction forces that ultimately result in the helical configuration of the fabricated fibers. Furthermore, the differential scanning calorimeter (DSC) curve was depicted in Fig. 3c. The melting temperature (Tm) of the hard segments reflects the degree of aggregation inside the modified Tecoflex. As the DOQA mass fraction increased, the Tm rose from 38.88 °C to 41.95 °C, indicating that DOQA disrupts the ordered aggregation of hard segments in Tecoflex and generates more loosely packed hard domains. These less ordered domains enhance chain mobility in the hard-segment phase and thereby amplify the overall phase separation of Tecoflex. Furthermore, the stress–strain behavior of various T-eNFM materials was evaluated in Fig. 3d. T-eNFM-3 demonstrated a tensile strength of 12.25 MPa and an elongation at break of 680%, marking a 1.84-fold improvement in tensile strength compared to T-eNFM-0 (370%). Owing to the uniform helical architecture of the T-eNFM-3 mat, stress–strain were measured both along and perpendicular to the helical structure as shown in Fig. S6. The helical architecture of the T-eNFM-3 mat significantly enhances its tensile performance, thereby substantially widening its elastic range compared with other samples. However, as the DOQA content increases, the tensile strength of the material declines due to the disruption of the helical fiber structure generated during electrospinning. Notably, the fiber structure of T-eNFM-5 extends to several hundred micrometers, substantially compromising its mechanical integrity (Fig. S4). As shown in Fig. S7, the correlation between spinning parameters and helical structure of T-eNFM-5 was further examined. The helical structure of T-eNFM-3 is highly sensitive to spinning temperature: increasing the temperature enhances the fluidity of the spinning solution, which in turn disrupts the fiber's helical configuration. Additionally, the rotational speed of the fiber collector directly influenced spinning uniformity; speeds above 350 rpm leaded to a noticeable deterioration in fiber uniformity.
The hydrophilicity and hydrophobicity of electrospun fiber membranes play a critical role in determining wearing comfort. As depicted in Fig. 3e, the hydrophilicity of T-eNFM increases with rising DOQA content, decreasing the water contact angle from 94 ± 2.8° (T-eNFM-0) to 18 ± 1.5° (T-eNFM-5). This improvement is attributed to the strong affinity of quaternary ammonium cations for water molecules. Enhanced hydrophilicity is anticipated to promote wearing comfort in flexible wearable electronics. Additionally, the breathability and moisture permeability of the base material used in wearable devices are critical factors influencing user comfort and dermatological health. Prolonged adhesion of a substrate to skin can induce thermophysiological discomforts such as dampness, desiccation and inflammation. Consequently, besides exceptional sensing performance, electronic skin (e-skin) demands a highly breathable substrate (Fig. 3f). Compared with polyimide (PI) and polydimethylsiloxane (PDMS) films, T-eNFM-3 demonstrated an air permeability of 26.2 ± 1.3 mm s−1 and a moisture vapor transmission rate of 142.1 ± 5.2 g m−2 day−1, markedly surpassing those of conventional flexible films used in wearable electronics (Fig. 3i).
As shown in Fig. 3g, the inhibition rate of colony-forming units (CFUs) on agar plates was employed to evaluate the antibacterial efficacy of the coating surface. Relative to the blank control, antibacterial activity of the T-eNFM surfaces increased with higher DOQA content. The surfaces of T-eNFM-3, T-eNFM-4 and T-eNFM-5 exhibited antibacterial rates up to 99.9% against E. coli and S. aureus (Fig. 3h). To further assess the antibacterial activity of the coatings, SYTO 9/propidium iodide staining was performed to evaluate the viability of Escherichia coli and Staphylococcus aureus recovered from the coating surfaces. On T-eNFM-3, T-eNFM-4 and T-eNFM-5, nearly all cells were co-stained with SYTO 9 (live/dead) and PI (dead), indicating that incorporation of DOQA confers potent bactericidal properties.
The conductive layers prepared by printing different proportions of MWCNTs and Ag inks were used to fabricate sensors, and their sensing performances were investigated. As shown in Fig. 4d, the strain sensor is fabricated by screen printing. The strain sensor made of pure Ag paste has very low sensitivity. Ag is a highly conductive metal, but the silver sheet layer is relatively rigid and has poor flexibility. On the flexible antibacterial breathable membrane substrate, the silver conductive layer is dense and stable, but when subjected to strain, it is prone to cause the separation of the membrane due to the deformation of the substrate, resulting in a sudden interruption of the conductive path and unstable resistance change, thus causing the sensor to have low sensitivity (GF = 2.36) and poor repeatability. With the addition of MWCNTs, these nanotubes serve as a flexible framework that bridges dispersed silver sheets by leveraging their high aspect ratio. This forms a continuous network of silver sheets and MWCNTs, enabling synchronous deformation with the substrate and allowing fine-tuning of the conductive layer's electrical properties. At the same time, the presence of a certain amount of silver sheets can enhance the structural strength of the electrode, avoiding irreversible fractures of the MWCNTs network due to excessive deformation. When the ratio of MWCNTs to Ag paste is 1:
2 and 1
:
1, the sensor exhibits different sensing sensitivities within different strain ranges of 0–150%, 150–250%, and 250–650%. As the content of MWCNTs increases, the sensor's sensitivity also increases. When the content of MWCNTs further increases to 2
:
1, the content of MWCNTs is sufficient to support the framework, and the content of the Ag is moderate, not prone to agglomeration. In the conductive path, three contact forms, “Ag – Ag”, “Ag – MWCNTs”, and “MWCNTs – MWCNTs”, coexist. Under the action of strain, the distance changes and contact area changes at the contact points are more significant, resulting in a greater change in the resistance rate of the sensor and higher sensitivity. The sensor has GF = 5.81, 3.85, and 0.94 in the strain ranges of 0–150%, 150–250%, and 250–650%, respectively. Pure MWCNTs sensors have excellent flexibility and aspect ratio, and are easy to form into a network structure, but their conductivity is much lower than silver. In the pure MWCNTs network, the main conductive paths between tubes mainly rely on point contact, and the contact resistance is relatively high; moreover, a high proportion of MWCNTs may cause the network to be too dense due to agglomeration, resulting in a smaller change in the path during deformation, and the resistance changes rapidly at small strains (0–100%) but quickly reaches the limit, resulting in a smaller sensing range. When there is a large strain, the resistance change rate is low, and the sensitivity is insufficient. It was also verified that the micro-structured strain sensor by screen printing exhibited significantly enhanced sensing performance compared to the sensor without microstructure (Fig. 4e). In the case of the unstructured sensor, during repeated stretching deformation, the sensitive material is prone to crack or fall off due to stress concentration, especially at the interface with the substrate, resulting in rapid performance degradation. The porous microstructure can buffer the stress, disperse it, and reduce the generation of cracks within the material, enabling the sensor to maintain stable performance after cycling while maintaining high flexibility (able to adapt to complex curved surfaces, such as human skin and robot joints).
Further tests were conducted on the sensing performance of the strain sensor, as shown in Fig. 4f. Under a 10% cyclic strain condition, the strain sensor exhibited a stable and repetitive current signal. One of the cycles in Fig. 4f was enlarged to obtain Fig. 5g. The response time and recovery time of the sensor were 50 ms and 30 ms respectively. Additionally, this strain sensor can detect stable repetitive sensing signals under different frequencies of strain cycles (Fig. 4h). When applying different strains to the sensor, as shown in Fig. 4i, the sensor still showed stable sensing signals during the cyclic changes of 20% and 30% strain. These indicate that the fabricated strain sensors possess stable and reliable sensing performance. The long-term stability of the sensor is an important factor. To verify whether the strain sensor can be used stably for a long time, we conducted 10000 strain cycling tests on the prepared strain sensor (Fig. S8a–c). The test results showed that the strain sensor exhibited excellent stability. After repeating the strain application, the current change rate did not show significant attenuation, indicating that this sensor has reliable stability.
A multi-layer structure pressure sensor was constructed by using printed Ag paste finger-type electrodes and a MWCNTs/Ag paste composite conductive electrode. As shown in Fig. 4j, when the electrodes are pure Ag paste, due to the rigid collision between the Ag, the conductive path is easily saturated quickly. This pressure sensor has low sensitivity. The initial resistance of pure Ag paste is very low. Even if ΔR changes due to pressure, the sensitivity may still be low; moreover, when the Ag part is in the dominant contact state, the path changes are mostly step-like transitions between open and closed, resulting in poor response linearity. When MWCNTs are added and the sensor is under pressure deformation, the contact area between the Ag part and MWCNTs increases, and the resistance decreases. After removing the pressure, the elastic recovery force of MWCNTs causes the contact area to decrease, resulting in an increase in resistance. This “compression – recovery” reversibility is more significant at a 2:
1 ratio. The sensor has a sensitivity S = 2.83 kPa−1 in the pressure range of 0–120 kPa and 0.85 kPa−1 in the range of 120–180 kPa. The silver sheet provides rigid support, and MWCNTs provide elastic recovery. The initial resistance of the pure MWCNTs pressure sensor is high, and the network is dense. The contact points quickly reach saturation within a small pressure range of 0–50 kPa. As the pressure increases, the amplitude change of ΔI is small, resulting in low sensitivity. In addition, compared to the pressure sensor composed of Ag and finger electrodes, the micro-structured electrodes by screen printing have significantly improved sensing performance compared to the pressure sensor without microstructure (Fig. 4k). For the MWCNTs and Ag paste composite electrodes, the amplification of local deformation directly leads to more drastic changes in the conductive path at the contact points of MWCNTs and Ag paste, resulting in a significant increase in the rate of current change and thus an improvement in sensitivity. In the planar structure of screen printing, the contact points between the MWCNTs and Ag part are evenly distributed but have a lower density, with most being large-area bonded strong contact points. When subjected to external force, only a few contact points separate or approach, and the resistance change range is relatively small.
Further verification of the sensing performance of the pressure sensor. Fig. 4l shows the stable electrical signal generated by the pressure sensor during the 100 kPa pressure cycle. Meanwhile, the local magnified Fig. 4l indicates that the response time of the pressure sensor is 280 ms and the recovery time is 160 ms. At the same time, the pressure sensor exhibits stable and reliable current signals under different pressures ranging from 20 to 120 kPa (Fig. 4m). Additionally, the pressure sensor also generates stable and cyclic sensing signals at different frequencies (Fig. 4n). These data confirm that the pressure sensor composed of the micro-structured electrodes printed by screen printing has reliable and stable sensing performance. The long-term stability of the pressure sensor was further verified. As shown in Fig. S8d–f, the pressure sensor was subjected to 10000 pressure cycle tests. The test results still demonstrated excellent stability, and the current change rate did not show any significant attenuation, indicating that this pressure sensor has long-term stability.
The human body's electrophysiological signals, as an important vital sign, are very common and routine in current clinical examinations since they contain a variety of health information about the human body. Thanks to its excellent flexibility and stretchability, the multi-layer structure pressure sensor can perfectly fit the irregular human skin and serve as a skin biosensor to detect the physiological electricity on the human epidermis. As shown in Fig. 5h, the pressure sensor can achieve continuous monitoring of the heartbeat, accurately perceive the weak pulse fluctuations of the human body, and detect the pulsation signals of the carotid artery and radial artery, etc. This is mainly attributed to its excellent mechanical properties, conductivity, and better adhesion and contact with the skin. Satisfactory results indicate that the pressure sensor can accurately detect and identify different action electromyographic signals, which means that its application in human–computer interaction and health assessment is feasible. Moreover, the sensor has good antibacterial and biocompatibility, which indicates that it has broader applicability and superior reliability in monitoring high-fidelity electrophysiological signals.
We compared the prepared multifunctional electronic skin with the electronic skins that have been reported in previous studies, as shown in Table S2. The comparison was made in terms of the preparation materials, preparation methods, whether they possess antibacterial and breathable properties, and the multifunctionality of the sensors. The electronic skin prepared in this work has obvious advantages in overall performance.
This journal is © The Royal Society of Chemistry 2025 |