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Self Healing PDF
Self Healing PDF
https://doi.org/10.1038/s41928-019-0235-0
Biological systems have the powerful ability to self-heal. Human skin can, for example, autonomously heal from wounds of vari-
ous degrees, allowing it to restore its mechanical and electrical properties. In contrast, human-made electronic devices degrade
over time due to fatigue, corrosion or damage incurred during operation, leading to device failure. Self-healing chemistry has
emerged in recent years as a promising method for constructing soft electronic materials that are mechanically robust and can
self-repair. Here we review the development of self-healing electronic materials and examine how such materials can be used
to fabricate self-healing electronic devices. We explore the potential new functionalities of self-healing electronic systems
that would not typically be possible with conventional electronic systems and discuss the current challenges in delivering self-
healing soft electronics for practical applications.
E
lectronic devices, which were once heavy and cumbersome, are contrast, intrinsic self-healing materials do not require the addition
now compact and mobile. Flexible and stretchable electronic of healing reagents and the wounded regions are able to repeatedly
devices are now also emerging1–3, which have potential applica- heal (even at ambient conditions in some cases) through the reor-
tions in health monitoring, artificial skins and implantable bioelec- ganization of the polymer matrix. During this process, the poly-
tronics, and could allow electronics to be seamlessly integrated into mer matrix is rebuilt from the regeneration of dynamic covalent or
our everyday lives1–8. These devices have been developed through non-covalent bonds and the entanglement of polymer chains at the
various design approaches, including strain engineering6, ultrathin damaged interfaces (Fig. 2b). These intrinsically healable materi-
nanomembranes9,10 and intrinsically soft polymers11,12. However, als are usually soft (that is, they have a low elastic modulus) and
the approaches are not resistant to unexpected mechanical damage deformable. As a result, intrinsically self-healable polymer mate-
caused by repeated wear and tear and accidental cutting or scratch- rials have drawn significant attention in the development of self-
ing, which are the main causes of device failure6,10. As a result, healable soft electronics.
researchers have looked to create electronic devices that can self- In this section, we focus on progress in the creation of intrinsic
heal, and thus, like human skin1, can repair unexpected internal or self-healing polymers. Intrinsic self-healing capabilities in poly-
external damages and recover critical functions. meric systems are based on two important features: the diffusion of
In recent years, considerable progress has been made in the polymer chains and the reformation of broken dynamic bonds. An
development of self-healable electronic materials13–16, which has led intrinsically self-healing polymeric system typically has a low glass
to their successful integration into functional electronic devices, transition temperature, which enhances the movement of poly-
including sensors, electronic skins, solar cells, field-effect transis- mer chains, and abundant sites for dynamic interactions20, which
tors, dielectric actuators and energy devices. In this Review Article, could be based on hydrogen bonding22, metal–ligand interaction23,
we examine the advances in self-healable electronic devices that π–π stacking, hydrophobic interaction24, imine bonding25, disulfide
will deliver the next generation of soft electronics (Fig. 1). We first bonding or boroxine bonding26. The mechanical properties of such
explore the different approaches for creating self-healable electronic a system can be tuned synthetically in various ways to meet require-
materials. We then consider the use of self-healable electronic ments for applications. Some self-healing polymer systems can
materials in the fabrication of functional components (insulators, achieve autonomous healing at room temperature, whereas others
conductors and semiconductors), devices (sensors, transistors and can even heal in water after sustaining mechanical damage.
energy devices) and integrated systems. Finally, we discuss the chal- Despite significant progress in developing self-healing chemis-
lenges that exist in developing practical applications based on self- try, only a limited number of self-healing polymeric systems have
healing soft electronics. been employed in electronic applications. This may be due to the
multitude of requirements of such applications (including combin-
Artificial self-healing systems ing mechanical and electrical properties, electrical and environ-
Inspired by the autonomous wound-healing ability of human skin, mental stability, and scalability) and a lack of understanding of the
artificial self-healing systems were initially designed to mimic these necessary design rules. Nonetheless, several research groups have
properties using clever polymer chemistry17–20. Self-healing poly- recently reported strategies towards engineering mechanically
mers can be broadly classified into two types: extrinsic and intrin- tough elastomers with reliable and repeatable self-healing proper-
sic21. Extrinsic self-healing occurs when dispersed healing agents ties, and some of these elastomers have shown considerable poten-
(or reagents) — typically consisting of reactive precursors and tial for building self-healable soft electronic systems27,28.
catalysts in a polymer matrix — are released after damage. These
healing agents can then repair the wounded areas through auton- Mechanisms of self-healing in electronic materials
omous polymerization reactions and the reconstruction of cross- The self-healing process of electronically active polymeric materials
linked networks (Fig. 2a). Although this approach is highly reliable, is due to the dynamic equilibrium of the cross-linking network and
it unfortunately only allows the material to heal a limited number percolation pathways in the polymeric system. The healing rate is
of times and usually cannot repeat healing at the same locations. In determined by the mobility of the polymer chains, the concentration
Department of Chemical Engineering, Stanford University, Stanford, CA, USA. *e-mail: zbao@stanford.edu
Electrical function
Display Durable Self-healing
process
Energy device
Time
Fig. 1 | Self-healing soft electronics. Schematic of a multifunctional self-healable soft electronic device on human skin. Self-healability of electronic
systems uniquely enables the fabrication of self-repairable electronics and modular and reconfigurable electronics. Self-repairable electronics can
autonomously restore their electrical and mechanical properties when they are mechanically damaged by scratching, poking, rubbing and tearing.
Modular and reconfigurable electronics allow users to customize their own electronic devices with various two- or three-dimensional shapes and multiple
functionalities by a simple mechanical cut and self-healing process.
of the broken dynamic bonds available and the activation ener- stretchable and tough hydrogel materials, as well as tough interfaces
gies for the exchange of dynamic bonds (Fig. 3a,b). In some cases, with diverse surfaces including glass, metals and polymers, were
solvent vapour is also needed to activate polymer chains to undergo previously created by employing self-healing hydrated polymer net-
rearrangements12. Owing to the low conductivity of polymeric mate- works that dissipate energy33,34. We have also recently demonstrated
rials, design strategies for creating self-healing and high-perfor- a tough self-healing elastomer with dual-strength hydrogen-
mance electronic materials have mainly focused on incorporating bonding sites as cross-links27. Such materials can sustain large applied
electronically active fillers into a dynamic polymer matrix. We have, strain, even when a notch is intentionally introduced27,28.
for example, recently shown that the nanostructured conductive
networks based on one-dimensional wires, in contact with a cross- Self-healing functionalities in electronic materials
linked self-healing polymer matrix, can be dynamically rearranged The dynamic cross-linking bonds responsible for self-healing prop-
to allow the recovery of its original percolation paths for electrical erties can be optimized to provide additional useful properties to
conduction after mechanical damage29 (Fig. 3c). The size and sur- self-healing materials. In addition, breaking such bonds by mechan-
face properties of the conductive fillers in a polymer matrix may ical loadings is a mechanism for energy dissipation, which can then
affect both the kinetics of self-healing and the electrical responses. improve both the fracture toughness of the corresponding elasto-
It is important to distinguish between mechanically tough self- mer and interface toughness with other layers.
healing materials and flowable viscoelastic materials, as highly A tough, self-healing elastomer is an ideal carrier material for
flowable viscoelastic materials can be used as the polymer matrix soft electronics, especially those subjected to significant wear and
for self-healable electronics as well. In flowable viscoelastic mate- tear over time. A carrier material with high toughness is tolerant
rials, the healing is mainly due to the intermixing of the materi- to damages or small cracks, and can thus significantly delay crack
als at the ‘reconnected interface’, whereas in self-healing materials, propagation. For example, a film with high fracture toughness can
the recovery of broken cross-linking bonds occurs in addition to be efficiently sutured on soft animal skin or tissue without ruptur-
inter-mixing. Flowable viscoelastic materials have the drawback of ing27. In contrast, commonly used soft substrates for biomedical
undergoing essentially permanent plastic deformation, even after a applications, such as covalently cross-linked polydimethylsiloxane,
mechanical force is applied. In particular, even though interfaces can easily tear around the sutured location due to their intrinsic low
can be reconnected by external forces or intrinsic flowability, these fracture toughness.
viscoelastic materials are not able to restore their original proper- Multifunctional electronic systems have numerous interfaces,
ties. In contrast, combining both strong and weak dynamic bonding such as those between the device and the substrate and those
can result in elastic, yet tough self-healing materials. between layers. The differences in surface chemistry and mechani-
The property of elasticity can assist in both efficient and autono- cal properties of each layer can easily result in device failure due to
mous self-healing recovery processes. One prominent effect of elas- delamination under strain. If all of the components are based on
ticity on the self-healing process can be observed in leaves, which similar self-healing polymer networks, they can subsequently be
can close wounds rapidly with the help of stored elastic stress built seamlessly integrated into a single system through the self-bond-
within their underlying structure30. Inspired by leaves, a recent ing (the formation of dynamic bonds at interfaces between layers)
demonstration of a self-healing polymeric system experimentally of the self-healing polymer, making the entire system mechani-
confirmed the importance of elasticity for the self-healing process cally robust29. Thus, this self-bonding property can be important
by controlling its internal microstructures31. In this regard, mechan- for the efficient fabrication of three-dimensional-configured
ically tough self-healing materials will be more suitable for fabricat- electronic devices35.
ing robust electronics than highly flowable viscoelastic materials.
The high toughness of human skin and the high interfacial Insulators. Since most polymers are insulating, an application of
toughness of tendons and cartilage to bone are all due to the self- self-healing polymers in electronics is as protective coatings, sub-
recoverable energy dissipation systems in our body32. Highly strates or encapsulation layers. A self-healing polymer derived from
Mechanical properties
Electrical properties
+
Nanomaterial
Fig. 3 | Self-healing process of electronic materials. a, Self-healing mechanism of a self-healing polymer (electronically active polymer). b, Self-healing
mechanism of a self-healing polymer composite. Self-healing composites are composed of self-healing polymer and electronically active nanomaterials.
c, Schematic of autonomous self-healing process of mechanically damaged electronic devices. d, The expected changes of mechanical and electrical
properties of soft electronic devices during the self-healing process. Mechanical properties are gradually recovered over time. In contrast, electrical
properties are recovered instantaneously on physical contact between two damaged interfaces and then gradually restored together with the self-healing
of mechanical properties. Panels adapted from: a, ref. 27, Wiley; b, ref. 29, Springer Nature Ltd.
Nanostructured semiconducting polymer networks or nanomate- increases at higher temperature, the changes in the ion conductivity of
rials may follow the same mechanism as conductive nanomaterial the composite film can be used for temperature sensing. This concept
networks, for which the reconstruction of the network is facilitated was further expanded to a self-healing near-infrared sensor, which was
by the dynamic nature of a self-healing polymer. fabricated by loading modified carbon nanotubes capable of efficient
photothermal conversion in the ionic liquid. The resultant near-
Self-healing functional electronic devices infrared sensor also exhibited repeatable self-healing properties52.
Self-healing electronic materials can be integrated into functional Humidity and chemical gas sensor devices with self-healing
electronic and electrochemical devices including sensors, FETs and properties have also been made based on the hybridization of
energy storage devices. surface-modified CNTs and hydrophilic self-healing materials53.
When hydrophilic self-healing polymers were used, the compos-
Sensors. Sensors are widely employed in our daily lives to detect phys- ites showed moisture absorption capacity. As a result, the resistance
ical (for example, pressure, strain, light, heat, humidity) or chemical of the polymer composites responded to moisture changes in the
signals47. Self-healing sensors can potentially increase the lifespan of environment. A transparent CNT network coated with polyelec-
such devices for both functional (such as sensing ability) and aesthetic trolyte multilayers was found to specifically respond to only NH3,
purposes. Most reported self-healable electronic sensors rely on the compared with other volatile organic compounds. It also showed
changes of their conductive pathways by external stimuli for their repeatable healability of its sensing performance.
sensing function. Initial demonstrations of self-healable sensors were
made using a piezo-resistive self-healing composite (usually a mix- Transistors. Organic field-effect transistors (OFETs) have been
ture of μNi microparticles and a self-healing polymeric material) as successfully integrated in sensors, memory devices and in the driv-
the active material48. This material is both pressure and flexion sen- ing circuits for displays. Nowadays, multiple organic and polymer
sitive due to the change in μNi microparticle spacing when external semiconductors have exhibited field-effect mobilities exceeding
mechanical forces are applied (which results in a sizeable electrical 1 cm2 V–1 s–1, similar to the performance of amorphous silicon thin-
resistance change). It can therefore detect both a hand shake and arm film transistors. Since OFETs are moving towards printable, flex-
bending when laminated onto the palm and the elbow, respectively. In ible and even stretchable electronics, they are more susceptible to
addition to μNi microparticles, carbon particles and graphene can be mechanical damages such as rubbing and scratching. To realize self-
also used in pressure and flexion sensors49,50. healable OFETs, three self-healable components need to be devel-
A capacitive touch screen was also constructed by laminating two oped concurrently: semiconductors; dielectrics; and source, drain
AgNW-based, self-healable polymer composite layers patterned in and gates. Individual bulk components with self-healing ability have
rows and columns51. An active electrode was then coupled with a already been developed and their electrical performances are suf-
neighbouring ground electrode to form a capacitor. Consequently, ficient to be integrated in OFETs. For example, electrically stable,
capacitance changes occurred when a finger was in contact with the self-healable dielectric layers have been created by incorporating
electrodes. After sustaining mechanical damage, the touch screen metal–ligand bonds as cross-linking sites into a non-polar polymer
was able to recover its touch sensing function by heating to 80 ºC for matrix37. By choosing suitable counter anions, these layers did not
30 s to restore its conductive pathways. exhibit double-layer capacitive effects caused by mobile ions, which
Self-healable temperature sensors can be fabricated by incorporat- resulted in OFETs with hysteresis-free transfer characteristics.
ing ionic liquid into a microfluidic channel embedded in a self-healable OFETs have also been fabricated from healable semiconductors,
polymer matrix52. Because the ionic conductivity of an ionic liquid which were created by incorporating moderate hydrogen-bonding
Ionic e-skin46
Chemresistor59
54 29
Supercapacitor ECG, EMG sensor
Supercapacitor56
Mechanical Electrochemical device57 Strain sensor27 LEC array29
sensor48 Touch sensor51
52
Temperature sensor
Actuator45
Fig. 4 | Self-healing electronic devices. Recently reported self-healing electronic devices based on publication year and complexity of electronic devices.
Red, self-healable active layer; blue, standalone self-healable electronic devices; purple, multifunctional self-healable stretchable system. Images
reproduced from: left, ref. 48, Springer Nature Ltd; middle left, ref. 59, Wiley; right, ref. 29, Springer Nature Ltd.
moieties in a semiconducting polymer main chain. Nanosized substrate, electrode and active layer, were self-healing and the
cracks in damaged devices were healed after solvent vapour and device was able to sense pressure and strain, as well as detecting
thermal treatments, leading to the recovery of the transistor mobil- volatile organic compounds59.
ity12. Self-healing electrodes based on CNTs and AgNWs have also Another example of a fully self-healing electronic system is a mul-
been used to make source, drain and gate components29. However, it tifunctional integrated electronic skin using a mechanically tough
is still technically challenging to fabricate fully self-healable OFETs and autonomously self-healable semitransparent electrode29 (Fig. 5a).
due to difficulties in the tedious fabrication process and limited This electronic skin was constructed with an electrocardiogram
self-healing properties of dielectrics and semiconductors in bulk (ECG) sensor for electromyography (EMG), strain sensors and a
or thick films. For OFETs, it is thus more practical to self-heal the light-emitting capacitor (LEC), so that it can effectively monitor phys-
nanosized cracks formed from fatigue. iological signals and display feedback information through closed-
loop communication between the user and electronics. Furthermore,
Energy devices. Energy storage devices are necessary for the opera- every part (including interconnects) was autonomously self-healable
tion of electronic devices. An early example of a self-healable super- and stretchable up to 100%. For example, the standalone LEC can
capacitor was fabricated by simply laminating acid-treated CNTs completely be healed to recover its original mechanical and electrical
films onto a self-healing substrate composed of TiO2 nanoflowers properties, even after suffering a complete cut. After healing, the LEC
and a self-healing polymer54. A polyvinyl pyrrolidone–H2SO4 gel was observed to continue emitting light even at 100% strain.
was used for both self-healable electrolyte and separator compo- Realizing self-healing in electronic devices with multilayer
nents. The as-prepared flexible supercapacitors exhibited good structures is extremely difficult because each layer has different
electrochemical performance with self-healing capability (85.7% mechanical properties, and it is challenging to achieve perfect align-
recovery in specific capacitance), even after cutting it for the fifth ment between different layers in the multilayer stack when they are
time. In another example, a wire-shaped self-healing supercapaci- mechanically cut. However, if each layer has high inherent tough-
tor was built using the same self-healing polymer. The electrode ness, it will be easier to achieve better alignment with high yield. We
was prepared by mixing an aligned graphene sheet, AgNWs and a note that high toughness may also contribute to a much cleaner and
CNT network in fibres55. Performance was observed to be recov- less-deformed surface when a layer is mechanically cut. In particular,
ered by 92% on self-healing at room temperature. Another interest- in materials that are not mechanically tough, mechanical damages
ing approach based on using magnetic force for the reconnection will result in significant permanent plastic deformation (especially
and alignment of the broken wires has also been proposed. Here, a on the surfaces), which will make it difficult to effectively reconnect
yarn-based supercapacitor was produced by covering a self-healable the damaged surfaces through the self-healing process. In addition,
polyurethane shell with magnetic microparticles56. Up to approxi- high toughness will impart a ‘shape memory’ effect to system, hence
mately 72% of the specific capacitance could be recovered after four promoting the autonomous self-healing process31.
repeated cutting-and-healing cycles. New conductive inks contain-
ing ferromagnetic particles have also been developed and used to Modular and reconfigurable integrated electronic systems
fabricate magnetically self-healable electrochemical devices57. A Self-healing chemistry is not only useful for building mechanically
self-healing perovskite solar cell was created through the incorpora- robust and durable electronics, but also opens up opportunities for
tion of polyethylene glycol chains in the active layer58. Self-healing constructing soft electronics in unique ways. For example, we recently
electronic active layers and devices are summarized in Fig. 4. demonstrated the concept of stretchable modular and reconfigurable
electronic systems60, in which multiple electronic modules are electri-
Self-healing integrated electronic systems cally interconnected and can digitally communicate with each other
All the devices described above are only partially self-healable, as (Fig. 5b). The conductive interconnects were fabricated on a tough,
only the active material in the device can undergo self-healing. stretchable, self-healable substrate, which allowed the components to
A fully self-healable flexible sensor device with multicomponents be cut, reconfigured and reconnected. Commercial electronic chips
was only recently reported57. All parts in this chemresistor, including were placed on flexible polyimide islands with printed circuits. The
ECG sensor
ECG sensor
Multifunctional self-healable
electronic skin
LEC array
LEC array
Self-healing substrate
Flexible conductive cable
b c
Wearable modular electronics Inter-integrated circuit Building blocks
digital communication Assembly ‘S’ for modular electronics Assembly ‘U’
(four conductive lines)
Connectors
2 cm
Modules
Fig. 5 | Self-healing electronic system. a, Optical image of a multifunctional self-healable electronic skin system consisting of a strain sensor with a
capacitive structure, an ECG sensor and LEC array29. b, Optical image of stretchable modular wearable electronic device composed of five modules and
four connectors on a human arm60. c, Optical images of reconfigurable assembly of electronic devices with modules and connectors60. Panels reproduced
from: a, ref. 29, Springer Nature Ltd; b, ref. 60, Wiley; c, ref. 60, Wiley.
islands were then bonded onto a self-healing substrate with multiple for self-healing electronic polymers or hybridization of self-healing
self-healable conductive lines. Each module had multiple self-healing polymers with high-performance inorganic nanomaterials will be
conductive lines and could readily interconnect with each other via necessary to improve their electronic properties.
the self-healing process. With this approach, two modular electronic
systems based on non-return to zero and inter-integrated circuit digi- Process. It should also be noted that the healing process remains
tal communication protocols were demonstrated. relatively slow and non-autonomous. Specifically, heating, light
Existing soft electronics are not malleable, intuitively pro- exposure or solvents are needed for the rapid healing of some mate-
grammable or adaptable to rapidly changing social and mechani- rials and devices. Therefore, the development of an autonomous
cal norms, due to their inherent mechanical stiffness and lack of self-healing system like a human body would be ideal. In addi-
freedom for user design and construction. In contrast, modular tion, the development of an on-demand self-healing system, which
electronics using self-healing interconnecting technologies with allows the selective triggering of the self-healing process in desig-
inherent flexibility and stretchability could allow flexible position- nated locations, will be useful in integrated electronic systems.
ing of modules on three-dimensional surfaces and structures, thus
offering a variety of skin electronic design possibilities. Large-area. When the size of damages is larger than the thickness
of layers, it is challenging to realize an efficient self-healing pro-
Outlook cess. Therefore, the self-healing process is currently limited to only
Self-healing soft electronics materials and devices have progressed small-area damages.
rapidly in recent years. However, several challenges need to be
addressed before such electronic devices can be seamlessly inte- Thermal stability. As most intrinsic self-healing polymers are based
grated into our daily life. on dynamic non-covalent cross-linked bonds, their mechanical prop-
erties are sensitive to temperature. Therefore, their thermal stability is
Fabrication. In general, the fabrication processes of self-healing potentially poor. Strategies to construct thermodynamically stable
materials are incompatible with existing electronic technologies. In self-healing systems will help to make them more reliable and stable.
particular, patterning self-healing materials with the small feature Self-healing chemistry is a valuable approach to constructing
sizes required for integrated electronics applications remains chal- soft electronics as if offers self-bonding, as well as functionalities
lenging and tedious. Therefore, the development of photo-pattern- such as robustness, modularity and reconfigurability. The resulting
able or self-healing electronics materials will be necessary. self-healing soft electronics are of potential use in wearable elec-
tronics and bioelectronics applications due to their ability to accom-
Properties. Despite the exciting developments in the field, the avail- modate varying external strains caused by dynamic movement. The
ability of functional materials for applications remains limited, espe- materials could also be of use in the development of more stable bat-
cially semiconductors and conductors. Furthermore, the electronic teries, where they could, for example, act as silicon anode binders59
properties of current self-healable devices are not yet comparable and lithium metal coatings61. Self-healing materials will, we believe,
to non-healable functional electronic devices. New design concepts help deliver the next-generation of soft electronics.