Article https://doi.org/10.

1038/s41467-023-43574-8

Tough soldering for stretchable electronics

by small-molecule modulated interfacial
assemblies
Received: 5 May 2023 Liqing Ai 1,5, Weikang Lin2,3,5, Chunyan Cao1,5, Pengyu Li2,3, Xuejiao Wang 1
,
Dong Lv1, Xin Li 1, Zhengbao Yang 2,3 & Xi Yao 1,4
Accepted: 13 November 2023

The rapid-developing soft robots and wearable devices require flexible con-
Check for updates ductive materials to maintain electric functions over a large range of defor-
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mations. Considerable efforts are made to develop stretchable conductive

materials; little attention is paid to the frequent failures of integrated circuits
caused by the interface mismatch of soft substrates and rigid silicon-based
microelectronics. Here, we present a stretchable solder with good weldability
that can strongly bond with electronic components, benefiting from the
hierarchical assemblies of liquid metal particles, small-molecule modulators,
and non-covalently crosslinked polymer matrix. Our self-solder shows high
conductivity (>2×105 S m−1), extreme stretchability (~1000%, and >600% with
chip-integrated), and high toughness (~20 MJ m−3). Additionally, the dynamic
interactions within our solder’s surface and interior enable a range of unique
features, including ease of integration, component substitution, and circuit
recyclability. With all these features, we demonstrated an application as
thermoforming technology for three-dimensional (3D) conformable electro-
nics, showing potential in reducing the complexity of microchip interfacing, as
well as scalable fabrication of chip-integrated stretchable circuits and 3D
electronics.

Stretchable electronics with high toughness and reliable electrical components13,14. It is therefore a high demand to develop stretchable
stability are essential in the applications of soft robotics1, wearable solders that can bind with rigid electronic components and maintain
electronics2,3, and on-skin electronics4,5. Substantial progress has been reliable conductivity over a large range of strains.
made in developing stretchable polymers with intrinsic conductivity as Gallium-based liquid metals (LM) with a unique combination of
well as flexible nanocomposites with conductive fillers for stretchable metallic conductivity and fluidity at room temperature stand out as a
sensors6 and integrated circuits7. However, most conductive circuits competitive conductive filler in the development of stretchable con-
often lose their function under strains that are much lower than their ductive materials15,16. Recently, LM-polymer composites with large
stretching capability, due to the incompatibility between conductive stretchability and high electrical conductivity have been developed17,18.
domains and neighboring polymer networks8–10. In particular, the While the weak interactions between the LM and polymer substrates
interface mismatch between soft substrates and rigid usually cause undesired leaking upon repeated stretching, which
microelectronics11,12 results in irreversible changes in electrical resis- deteriorates the mechanical properties and conductive stability of
tance and permanent interface failure between conductors and these conductors19. To mitigate these issues, surface engineering

1
Department of Biomedical Sciences, City University of Hong Kong, Hong Kong 999077, China. 2Department of Mechanical & Aerospace Engineering, Hong
Kong University of Science and Technology, Hong Kong 999077, China. 3Department of Mechanical Engineering, City University of Hong Kong, Hong Kong
999077, China. 4City University of Hong Kong Shenzhen Research Institute, Shenzhen 518000, China. 5These authors contributed equally: Liqing Ai, Weikang
Lin, Chunyan Cao. e-mail: [email protected]; [email protected]

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Article https://doi.org/10.1038/s41467-023-43574-8

technologies such as chemical surface modification and interfacial components in integrated circuits through a typical thermal proces-
manipulations have been employed20–22. However, it is still challenging sing method (Fig. 1a–d). During the soldering process, the ULPC
to integrate LM composites with rigid electronic components because deforms to better wrap the mounted resistor after thermal processing
of the fluidity and poor adhesion of LM. There are a couple of pio- (Fig. 1e). The dynamic interactions within the ULPC enable a stable
neering attempts showing potential of solving these interfacial issues, interconnect between both electronic components and TPU substrate,
such as adding additional encapsulation layers23, providing proper to withstand the significant shear stress generated during the ther-
barriers24 for generating interlocking effect between LM and compo- moforming process. Notably, the circuit (Fig. 1f) exhibits exceptional
nents, or adding interface binder to make temporary connections by stability and robustness without requiring encapsulation, which sim-
virtue of physicochemical bonding25,26, but these methods cannot form plifies component substitution and circuit recyclability.
a robust interface between the soft conductive composites and rigid
electronics directly. Results
Supramolecular polymers have been demonstrated as a promis- The design principle and polymer synthesis
ing platform to carry conductive fillers such as silver nanowires and The dispersion status of LMP in polymer matrix and their interfacial
carbon nanotubes to form multifunctional conductive composites for interactions together determine the comprehensive performance of
stretchable electronic and wearable devices27,28. Their advantageous the LM-polymer composites30,31. Although various fabrication methods
mechanical and interfacial properties benefiting from versatile design have been reported in the development of LM-polymer
of non-covalent bonds and the resulted dynamic networks may pro- composites32,33, huge challenges exist in the regulation of interfacial
vide a unique approach to solving the aforementioned challenges29. interactions between LMP and polymer matrix34,35. To overcome the
We here report the fabrication of LM-based supramolecular polymeric limitation, we use a molecular engineering strategy to synthesize a
composites with high mechanical toughness, high conductivity, and typical linear polymer and small-molecule modulators, both of which
robust electrical connections with electronic components. The com- are functionalized with terminal 2-amino-4-hydroxy-6-methylpyr-
posites are prepared by the co-assembly of a molecular engineered imidine (UPy) motifs (Fig. 1b–d). Compared with traditional designs
supramolecular polymer, and small-molecule modulators stabilized which LMP are simply blended and sintered within polymer matrix, the
LM microparticles (LMP). The dynamic interactions within the surface use of small-molecule modulators can bring a couple of unique
and interior of the composite enable the LM-polymer composite as a advantages. Chemical motifs that show high affinity to the oxide layer
self-solder to interconnect with commercial silicon-based electronic of LM can be precisely incorporated in the small-molecule modulator

a b c

Component Component

TPU substrate

TPU substrate

Liquid metal-rich domain Polymer-rich domain UPyMC Polymer

d

e f

Soldering process

Thermoforming

Strain

2D planar assembly

3D electronics

Fig. 1 | Schematic of the soldering and thermoforming process. a Schematic LMP, and UPyMC modulators. d Molecular structure of the synthesized polymer.
illustration of the LM-based composite design and its integration with TPU sub- e Schematic illustration of the soldering and thermoforming processes. f Optical
strate and electronic component. b Schematic illustration of the hierarchical image of a 3D electronic enabled by the ULPC. Inset: The LED remains lit even
assembly within the composite. c Molecular interactions between the polymer, under the action of external force lifting the entire electronics (50 g).

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to facilitate LMP generation. The small-molecule modulator can also ureido at around 1698 cm−1, while the corresponding peak in the
be inserted into polymer coils, regulating the assembly of polymer polymer is around 1703 cm−1 due to the linking with PDMS molecular
chains through hydrogen bonding interactions. The capacity of chain43 (Fig. 2d). The peak broadening at 1698–1703 cm−1 in the ULPC
molecular stacking and aggregation of UPy motifs can assist the for- suggests that the self-assembly between UPyMC-LMP and polymer has
mation of dynamic network within the polymer matrix which in return been successfully constructed35. The semi-crystalline property of the
stabilizes the compartmented LM. All these together result in a hier- synthesized polymer can be confirmed by X-ray diffraction (XRD)
archical assembly for which a heterogeneous LM-polymer interface (Fig. 2e). Compared with the pristine polymer sample, the polymer-
can be stabilized. UPyMC sample shows higher crystallinity due to the higher molar ratio
The mechanical properties particularly the stretchability and of UPy motifs which can contribute to further aggregation and stack-
toughness of the polymer matrix are key for their applications in ings. Similarly, the ULPC sample shows reduced crystallinity because
stretchable electronics. We synthesize the supramolecular polymers the addition of LMP is expected to dilute the overall polymer ratio.
through typical condensation reactions between amino terminated Wide-angle X-ray scattering spectra is used to study the microscale
monomers, UPy precursors, and diisocyanate linkers (Supplementary crystalline properties of the samples. The size of crystalline domains
Fig. 1). An aliphatic extender is included to tune the chain length and changes very little after adding LMP (Supplementary Fig. 7), indicating
adjust the density of hydrogen bonding motifs. Terminal UPy motifs that LMP has negligible effect on the molecular aggregation and
are incorporated into the polymer main chains to help build inter- crystalline structure at microscale, which is expected to enhance the
molecular hydrogen bonding36. A low density of UPy motifs is pre- mechanical properties without scarifying the stretchability of the
ferred as this can avoid their cascade crystallization37,38, and facilitate polymer composite44,45.
the stretchability of the polymer39. Polydimethylsiloxane (PDMS) seg-
ments are incorporated in the main chain, because of the low surface High toughness and high stretchability of ULPC
energy and low glass transition temperature40. The molecular weights The unique hierarchical assembly and crystalline properties of the
(MWs) of UPy-terminated PDMS segments are tuned at ~1000, ~2000, ULPC will affect the mechanical properties substantially. The
and ~3000, and the feeding amounts of UPy monomers are varied from mechanical properties of the pristine polymer film, polymer-LM film,
0.02, 0.04 to 0.08 (equivalent to the molar fraction of the UPy units polymer-UPyMC film, and as-prepared ULPC are studied via tensile tests
relative to total amine groups) for comparison and optimization. With (Fig. 2f). Notably, the direct incorporation of high mass ratio of LMP
the parameters set above, the stretchability (392–1986%) and Young’s (30%) into polymer leads to a sharp deterioration of mechanical
modulus (0.4–34 MPa) of the synthesized polymer samples are highly strength due to the aggregation of LMP as previously reported. While
tunable (Supplementary Figs. 2 and 3, Supplementary Table 1), and the for the ULPC sample, the tested tensile strength and toughness are
toughness varies in a narrow range (between 9.2-11.3 MJ m−3), enhanced remarkably (Supplementary Table 2). Compared with
demonstrating an effective platform for the subsequent fabrication of polymer-LM film, the resulting ULPC film exhibits a 450% and 370%
LM-polymer composites. increase in both the ultimate tensile strength (3.2 MPa) and toughness
(19.8 MJ m−3), respectively. The polymer-UPyMC sample also shows
Small-molecule modulated hierarchical assemblies higher tensile strength, while the elongation at break has a remarkable
The UPy-functionalized small molecule modulators play a key role in decrease due to the high density of hydrogen-bonding crosslinks and
improving the interaction between the LMP and the synthesized the high crystallinity. Addition of 10 wt% of LM can improve the
polymer. They are incorporated with functional groups such as ester stretchability from 480% to 800%. Further increment of the LM con-
and carboxylic acid groups, which are proven to show high affinity to tent from 10 wt% to 40 wt% would further increase the breaking
oxide layer of LMP41,42. As a typical example, ester functionalized UPy elongation, while the tensile stress decreases accordingly (Supple-
modulators are synthesized (termed UPyMC, 1H NMR see Supplemen- mentary Fig. 8).
tary Fig. 4). We then fabricate UPyMC modulated LM-polymer compo- To further understand the role of UPy modulators in the regula-
site (termed ULPC) by a typical sonication-assisted solution processing tion of the interfacial interaction between the polymer and LMP as well
method. UPyMC-wrapped LMP (termed UPyMC-LMP) is prepared by as the mechanical enhancement of the composite, we first test
ultrasonic treatment of UPyMC dispersion and bulk LM. ULPC pre- mechanical properties of ULPC samples with different amounts of
cursor is obtained by mixing the UPyMC-LMP suspension with polymer UPyMC modulators. For those samples, the introduction of ~1 wt%
solution (Fig. 2a). During solvent evaporation, the LMP will precipitate UPyMC can impressively improve the toughness of the polymer-LM
and transform into heterogeneously structured LM-rich layer in the composite from 5.3 to 15.3 MJ m−3 (Fig. 2g, Supplementary Table 2).
final ULPC films (Supplementary Fig. 5). Further increment of the UPyMC fraction from 2 wt% to 6 wt% would
The structure and composition of UPyMC stabilized LMP are cause the reduction of the breaking elongation, although the tensile
evaluated via energy-dispersive X-ray spectroscopy (EDS), transmis- stress can increase accordingly. To further confirm the role of UPy
sion electron microscopy (TEM), and X-ray photoelectron spectro- modulators, another three types of UPy modulators with different
scopy (XPS). As shown in Fig. 2b, the UPyMC can adsorb on the surface chemical structures are synthesized for the preparation of ULPC
of LMP and form a dense wrapping layer as revealed by the TEM samples. Two of them are similar to UPyMC, but the terminal methyl
images. EDS analysis revealed a homogeneous distribution of carbon ester groups are changed to carboxylic acid (UPyGly) and propyl
elements surrounding the LMP surface, providing further evidence of groups (UPyBI). The UPyGly is expected to show similar interactions
the uniform wrapping of UPyMC around the LMP surface (Supple- with LM, while the UPyBI is expected to show limited interactions with
mentary Fig. 6). XPS spectrum revealed that the intensity and position LM. The Glycine (Gly) molecule is selected as the third candidate to
of three representative peaks for -NH (398.7 eV), -N-C (397.9 eV), and clarify the function of UPy motifs (Structures see Supplementary
-N=C (399.4 eV) groups of UPyMC changes substantially in the UPyMC- Fig. 4). Tensile test shows that the strength of the sample prepared by
LMP35, implying strong interactions between the UPyMC and the sur- UPyGly is much higher than that of other samples, indicating the
face of LMP (Fig. 2c). interactions with both LMP and polymer are necessary for the
As addressed previously, small-molecule modulators are expec- mechanical enhancement (Fig. 2h). To further elucidate the role of
ted to co-assemble with the UPy-terminated polymers through polymer matrix in the mechanical enhancement, we change the con-
hydrogen bonding interactions. Therefore, the assembly status of the tent of UPy monomers in the pristine polymer (Supplementary Fig. 9,
ULPC is carefully studied. Fourier-transform infrared spectroscopy Supplementary Table 3). It is observed that the enhancement effect is
(FTIR) shows the typical UPy characteristic peak of C=O stretching in proportional to the UPy content in the polymer, which is also strong

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a b

UPyMC LM

LM
Ultrasonication

c d e

f g h

Fig. 2 | Characterization of the UPyMC-LMP and the ULPC solder. a Schematic spectra of polymer, polymer-UPyMC, and ULPC. Comparison of the tensile stress-
illustration of the generation of UPyMC-LMP by ultrasonic treatment of bulk LM and strain curves for the polymer and composites prepared by f different compositions,
UPyMC modulators. b TEM image of the as-prepared UPyMC-LMP, scale bar, 1 μm. g different weight ratios of UPyMC, and h different types of small-molecule mod-
Each experiment was repeated independently 3 times with similar results. c XPS of ulators. (Except where stated otherwise, polymers were prepared from siloxane
the N 1s of UPyMC modulators and UPyMC-LMP. Shifts are observed for -NH/-N-C/- oligomers with ~2000-MW and 0.08 amount of UPy monomers, and ULPC was
N=C motifs in the particles. d FTIR spectra of UPyMC, polymer, and ULPC. e XRD fabricated from the polymer with 30 wt% LM content and 2 wt% UPyMC).

evidence that intermolecular interactions between the UPy- the removal of the oxide layer of LMP through HCl treatment, the LM
functionalized modulators and polymer matrix are responsible for droplet cannot deform with the stretching of the polymer composite.
the enhancement. These results prove the strong and adaptive interactions between the
ULPC and the oxide layer of LMP (Supplementary Fig. 12).
Interface-dependent electromechanical properties of ULPC Micro-computed tomography (Micro-CT) images are conducted
As shown in Fig. 3a, the surface of ULPC shows a heterogeneously to get more insight of interior structure - LMP tend to aggregate and
structured LM-rich layer. The scanning electron microscopy (SEM), its form continuous percolating paths within the composite, which is
corresponding energy dispersive X-ray (EDX) element mapping, and essential for the electrical stability of the conductive materials46
Raman mapping of LM-rich layer confirmed the hybrid surface, and the (Fig. 3b and Supplementary Fig. 13). With the compact assembly of
surrounded polymer compartments tightly retain LM to avoid leaking LMP, peeling films of ULPC can generate sufficient stress to percolate
(Supplementary Figs. 10 and 11). To demonstrate the robust interac- particles for electrical activation47 (Supplementary Fig. 14). Since the
tions between the LM and the ULPC samples, we following evaluate LM content in the hybrid interface contributes to the conductivity and
and compare the shape evolution of LM droplets on the surface of the polymer content contributes to the interfacial adhesion, such
pristine polymer and ULPC films. As the sample film is stretched under unique hybrid interface is beneficial for interfacial contact with high
continuous tensile strain from 200% to 500%, the boundary of LM conductivity and high adhesion9. We further developed a series of
droplet extends from ~165% to ~320% simultaneously when it is composites with different weight ratios of LM in the composite to
deposited on the pristine polymer, while the boundary of LM droplet study the conductivity and the interfacial adhesion. We note that it
extends from ~195% to ~495% on the ULPC samples, respectively. After may be intuitive that an increase in LM concentration would facilitate

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a b

(i) (ii) (iii)

Z
X

Y 3D images of ULPC

c d e
5 400%

Adhesive area
Conductive area

200%

After soldering process

0%

ULPC-TPU

f g h

Fig. 3 | Interface-dependent electromechanical properties of integrated ULPC. with a zero-ohm resistor, scale bar, 1 mm. e Photographs of ULPC-TPU with LED
a SEM image of the surface of ULPC LM-rich layer, scale bar, 10 μm. Each experi- array under strains, scale bar, 10 mm. f Contact resistance measurement for a ULPC
ment was repeated independently 3 times with similar results. b Reconstructed 3D interface using the transmission line method (half of the y intercept: Rc = 0.11 Ω,
Micro-CT images of i) the LM-rich layer, ii) LM only, and iii) polymer only, of a R2 = 0.9961). The inset shows the schematic of the contact resistance measure-
representative ULPC sample, scale bar, 50 μm. c The measured conductivity and ment. g Comparison of relative resistance change of ULPC-TPU over strains with or
maximum stud-pull strength of the ULPC with different weight ratios of LM. All without an embedded zero-ohm resistor. h Resistance stability of ULPC-TPU in
values represent the mean ± SD for n = 3 independent experiments. d Schematic 10000 stretch-release cycles at 50% strain.
illustration and optical images of side view of the soldering process of ULPC-TPU

electrical conductivity (from 10000 to 250000 S m−1); however, the transfer processes (See methods for details). Accordingly, various
maximum stud-pull strength would accordingly decrease from 4.1 to electronic components can be integrated to the resulting ULPC/TPU
1.1 MPa (Fig. 3c). Since the 2.2 MPa adhesion (competitive with com- composite film (termed as ULPC-TPU). ULPC-TPU shows reduced
mercial copper tape) is sufficient to meet the requirements in most stress-strain hysteresis in the cyclic tensile tests at 100% strain region
practical scenarios, the ULPC with LM loading of 30 wt% is investigated compared with bare ULPC films (Supplementary Fig. 19). We further
for the application of stretchable electronics. We also test its adhesion perform in situ peeling tests to reveal the interface stability of the
by 90° peel-off test and shear test to show the robust integration of ULPC sample. It is noteworthy that the ULPC exhibits marginal changes
ULPC with components (Supplementary Figs. 15 and 16). As a com- in resistance when Scotch tape was repeatably peeled off from the
parison, the LM-polymer composite films without adding UPyMC show conductive interface, as illustrated in Supplementary Fig. 20. Specifi-
poor conductivity and limited stretchability before electricity failure cally, small resistance changes (~1%) are observed when the Scotch
(initial resistance >200 Ω, Supplementary Figs. 17 and 18), which again tape was attached on the ULPC sample, but the resistance promptly
illustrates that UPyMC can largely improve the interactions between LM returns to its original value when the tape was peeled off. This
and polymer substrate. demonstrates the excellent electrical stability of the robust interface.
The ULPC is cut into stripes at 1.3 mm width and different lengths In addition to stable electrical resistivity, stable adhesion with
by a cutting machine and then mounted on commercial Thermoplastic electrical components is also a crucial property of stretchable solder.
polyurethane (TPU) film through thermal release tape-assisted thermal The stable adhesion relies on molecular bond exchange and

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recombination when the ULPC is brought into contact with electrical thermoforming techniques. For example, a 3D electronic circuit with
components27. Welding of the ULPC at temperatures slightly above the fifteen light-emitting diodes (LEDs) on the half sphere and their
glass transition temperature (Tg) is more favorable due to the interconnection via ULPC electrodes is made as presented in Fig. 4b.
enhanced molecular bonding ability48. The Tg of ULPC is measured at The ULPC-based 3D electronic is reliable under stretching, twisting,
113 °C (Supplementary Fig. 21), lower than many commercial flexible and folding deformations without electrical disconnection (Fig. 4c).
polymers, indicating well rheological weldability and good compat- Conversely, the silver paste displayed notable issues including crack-
ibility with thermal processing (See methods for details). ing and inadequate adhesion, ultimately resulting in interface failure
To investigate the electromechanical properties of ULPC-TPU with the LED after thermoforming (Fig. 4d).
with electronic components, we attach a zero-ohm surface-mount In contrast to previous works, no encapsulation layer is needed to
resistor on the ULPC through soldering processing to form a basic but cover the circuit for components fixation, which significantly facil-
representative circuit. Figure 3d shows schematics and optical images itating chips and components replacement. Similar to many thermo-
of a resistor-mounted ULPC-TPU, where the polymer composite plastic elastomers, the maximum stud-pull strength of ULPC-TPU gets
deforms to better wrap the mounted resistor after thermal reduced significantly at sub-zero temperatures due to the rigid char-
processing49. The ULPC leverages dynamic interactions to establish a acteristics of the polymer52 (Supplementary Fig. 25). Therefore, we
stable interconnect between both electronic components and TPU cool the circuit to −10 °C for 20 minutes to peel off the components
substrate. To visualize the stable electromechanical properties of the and substitute with new ones after a new round thermal processing.
ULPC with multiple components, a basic in-series circuit with three The integrated circuit demonstrates robust reusability as evidenced by
LED is stretched to 400% before breaking (Fig. 3e). After soldering minimal changes in resistance and maximum stud-pull strength
process, we used the transmission line method50 to measure the con- throughout repeated peeling-substitution cycles (Supplementary
tact resistance between ULPC-TPU and the zero-ohm resistor, and the Fig. 26). Furthermore, we demonstrate the continuous substitution of
calculated contact resistance is 0.11 Ω (Fig. 3f). Besides, the recorded LED components, which can be verified by the well-lit LED after sub-
breaking strain of the integrated circuit is at ~700% (Supplementary stitution (Fig. 4e). Compared with commercial copper tape, the
Fig. 22), a value 6 times larger than previous study that demonstrated adhesion performance of ULPC remains stable in the repeated peeling-
integrated circuits without encapsulation layers26, and as good as substitution cycles (Supplementary Fig. 27). Since the absence of
encapsulation circuits51. permanent crosslinks in the ULPC, the whole circuit can be easily
As shown in Fig. 3g, the resistance change of the integrated circuit disassembled and recycled into its constituent elements. This recy-
shows a similar trend with ULPC-TPU under 200% strains (R/R0 < 5). cling process can be accomplished with just a few simple steps, pre-
Until the strain up to 600%, a visible increase of resistance change is serving conductivity and quality without significant degradation
observed, due to the mechanical failure on the interconnect between (Fig. 4f, g, Supplementary Fig. 28).
ULPC and electronic components (Supplementary Fig. 23). Moreover, To demonstrate the potential of ULPC-TPU 3D electronics in the
the resistor-mounted ULPC-TPU exhibits excellent durability, main- high resolution and complex 3D circuit, which allows conformal and
taining its functionality for over 10000 repeated cycles at a loading intimate interactions with skins for wearable applications. As shown in
strain of 50% and 2500 repeated cycles at a loading strain of 100% Fig. 5a, we have developed a specially designed intelligent heating
(Fig. 3h and Supplementary Fig. 24). ULPC-TPU has outstanding per- electronic patch that is suitable for the complex surface of the knee
formance in its extreme stretchability (~1000%), small resistance joint, which exhibits non-zero Gaussian curvature. The circuit with
changes over a large range of strains, and strong adhesion, the per- chips and a variety of electronic components enables users to control
formance comparison with state-of-the-art LM-based stretchable thermal stimulation via a capacitive touchpad (Fig. 5b and Supple-
conductive composites are illustrated in Supplementary Table 4. mentary Figs. 29 and 30). The large area ULPC-based heater shows
consistent and low resistance, allowing for rapid temperature
Applications in three-dimensional conformable electronics responses and operation at a low voltage (Fig. 5c). The minimal tem-
Three-dimensional (3D) electronics with customizable features, con- perature fluctuations observed during stretching can be attributed to
formability, and stretchability are in high demand for wearable elec- the negligible resistance changes achieved through the implementa-
tronics. Thermoforming, a cost-effective and scalable manufacturing tion of the serpentine Peano curve design (Fig. 5d). Infrared camera
method, is often used to create 3D-shaped electronics. However, images of the heater exhibit uniform surface temperature distributions
thermoforming requires conductive materials that can maintain con- across various bending angles of the knee joint (Fig. 5e). The conformal
ductivity under high temperatures and stretching. Additionally, the attachment of the electronic patch on the skin not only enhances
strong shear force between flexible conductors and rigid electronic comfort but also ensures reliable heat transfer for thermal therapy.
devices during the thermoforming process can cause electrical com- In addition, we have expanded the application of our solder with
ponents to fracture, leading to electrical failure. other circuits (rigid, flexible, or stretchable) as a stretchable connector.
Here, leveraging the high conductivity and strong adhesion with By soldering ULPC to flat flexible cables and flexible silver conductors,
both electronic components and TPU substrate, we fabricate circuit in we have successfully formed soft-rigid and soft-soft stretchable con-
2D planar using cost-effective commercial technology. Subsequently, nections (See Supplementary Fig. 31 for details). These substrates are
we employ thermoforming techniques to create complex and func- compatible with printed circuit board manufacturing, allowing the full
tional 3D wearable electronics. The ULPC-based 3D electronics are utilization of the performance of chips and electronic components.
produced by following the steps illustrated in Fig. 4a. The circuit fab- This demonstration showcases the potential of our solder in building
rication process typically includes four steps: including mechanical stretchable hybrid devices with different functionality and complexity.
cutting, thermal transfer, pick and place, and thermoforming. To cre-
ate the desired circuit, the ULPC film is patterned using a cutting Discussion
machine. The patterned ULPC circuit is then transferred to a TPU In this study, we design and synthesize linear polymers and small-
substrate by thermal release tape. The thermal release-assisted trans- molecule modulators with UPy motifs, which can co-assemble with
fer process is crucial for maintaining the precise position of the ULPC LMP to produce tough and weldable composites. The hierarchical
stripes which is essential for accurate electronics welding because the assembly facilitated by small-molecule modulators can enhance the
conductive track need to conform to the size of chips and other interaction between the polymer matrix and the LMP, and provide
electronic components. Once the electronic components are fixed in unique interface-dependent electromechanical properties of the
2D planar, they can be molded into various 3D structures using resulting ULPC, which are beneficial for high conductivity and high

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Step1: Mechanical Cutting Step2: Thermal Transfer Step3: Pick and Place Step4: Thermoforming

b c d
Initial state Stretching Ag paste

Detachment

Fracture
e
Twisting Folding

f g

Dissolving Components

TPU substrate

Evaporation
Fabrication
Soft electronics
ULPC ink ULPC film
Recycling

Fig. 4 | Development of the integrated circuit for 3D electronics. a Fabrication LED array, scale bars, 5 mm. f Recycling process: the circuit is first placed into
process for integrated 3D circuit. b Images of the integrated process, scale bar, ethanol, and it can be de-assembled to constituent elements and recycled. g The
5 mm. c Images of the integrated 3D circuit under stretching, twisting, and folding, measured conductivity and yield of the ULPC over repeated recycling operations.
scale bar, 5 mm. d Optical images of commercial Ag paste after thermoforming, Here, yield is defined as mass after recycling divided by initial mass. All values
scale bar, 1 mm. Each experiment was repeated independently 3 times with similar represent the mean ± SD for n = 3 independent experiments.
results. e Optical image of the circuit cooled to −10 °C, peeling off and substituting

adhesion at the interface contact. We show a record-breaking max- microchip interfacing, and thus for scalable fabrication of chip-
imum strain of >600% before electrical failure and relatively small integrated stretchable circuits and 3D electronics. In addition to the
resistance changes over a large range of strains (20 at 1000% strain and synthesized polymers and LM used in this work, our design concept
30 at 600% strain with a resistor) without encapsulation. By combining and fabrication method can be applied to other synthetic or engi-
our solder with thermoforming, 3D conformable electronics have been neered polymers and different liquid metals (Supplementary Fig. 32).
constructed with good electricity stability, easy to process, continuous We also envision that there will be a lot of opportunities in the design
substitution of electronic components, and circuit recyclability. As and application of small-molecule modulators to facilitate the assem-
examples of emerging applications, an integrated 3D circuit with logic bly and mechanical regulation of polymer composites. Additionally,
control functions and a stretchable heater is fabricated to show the the new insight into the intermolecular interactions between the
huge potential of our materials in wearable electronics. supramolecular and the oxide layer of LMP revealed in this research,
Overall, this study provides an alternative method of developing can largely enrich the knowledge and tools for designing high-
LM-based self-solder with high conductivity, high stretchability, performance LMP and multifunctional LM-polymer composites. Even
improved toughness, and excellent weldability that are favorable in the though we highlight the performance of ULPC without an encapsula-
applications of 3D electronics. Despite there are limitations, such as tion layer or chemical modification, these additions can be incorpo-
limited resolution (500 μm) due to the solvent evaporate strategy. We rated for improving the adhesion and electrical stability according to
believe it is an important step toward reducing the complexity of practical applications (Supplementary Fig. 33).

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a b c

50.0

Nonzero Gaussian Curvature

25.0
50% strain

d e
43.9

23.5

Fig. 5 | Applications in 3D conformable electronics. a Overview of the con- profiles of the electro-resistive heater under different applied voltages. d The
formable electronic patch for intelligent heating. b Optical images of the as- temperature change of the heaters under tensile deformations. e Infrared camera
prepared 3D electronic patch, scale bar, 5 mm, the resolution is 500 μm. Each images showing the reliable heating performance of the electronic patch attached
experiment was repeated independently 3 times with similar results. c Temperature to the knee.

Methods was then collected by filtration and dried overnight under a high
Materials vacuum at 60 °C (yield 91%).
EGaIn alloy (75.5 wt% Ga and 24.5 wt% In), isophorone diisocyanate UPyGly, UPyBI were prepared through similar procedures using
(IPDI), poly (propylene glycol) bis (2-aminopropyl ether) (OPG-2NH2) corresponding amino terminated monomers.
were purchased from Sigma-Aldrich. 2-amino-4-hydroxy-6-methyl-
pyrimidine (UPy) was purchased from Aladdin. Poly(dimethylsiloxane) The fabrication of ULPC solder
bis(3-aminopropyl) terminated (MWPDMSm-2NH2) with different mole- Firstly, 1.5 g polymer was dissolved in 5 mL DCM under magnetic stir-
cular weights were purchased from Gelest. All the chemicals used in ring for 30 min. The UPyMC-LMP were made by adding 650 mg of EGaIn
the current work were used without further purification. alloy (75.5% Ga, 24.5% In) and 30 mg UPyMC into 10 mL of DCM and
Preparation of linear supramolecular polymer then sonicating at an amplitude of 36μm (30% setting) for 5 min using a
Polymer with 2000 MWs of UPy-terminated siloxane, 0.08 feed- tip sonicator in an ice-water bath. Then, pour the dissolved polymer
ing amounts of UPy monomers (MWPDMS2000, UPy0.08) was synthe- solution into the UPyMC-LMP and continue to sonicate for 1 min to
sized by the following steps. The prepared UPy-MWPDMS2000-NH2 ensure uniform dispersion. The mixture was then poured into glass
(460 mg, 0.2 mmol), MWPDMS3000-2NH2 (1.73 g, 0.58 mmol), poly molds into films by slowly drying at ambient conditions for 1 h for
(propylene glycol) bis (2-aminopropyl ether) (OPG-2NH2) (230 mg, complete drying to obtain ULPC solder.
0.58 mmol) were dissolved in chloroform (20 mL). In addition, iso-
phorone diisocyanate (IPDI) (277.9 mg, 1.25 mmol) was dissolved in Fabrication of circuit
chloroform (5 mL). After that, the above solutions were mixed and Firstly, the LM-rich surface of ULPC film was attached to the thermal
stirred in a beaker for 6 h. The precipitate was taken out and washed release tape and then patterned by a cutting machine (Sillouette
with acetone three times. Then the product was dried under a vacuum Cameo 4). In step 2, we flipped the circuit pattern ULPC film and
at 70 °C for 24 h. thermal release tape together and attached them to the TPU substrate.
Other polymers were prepared through similar procedures with When the temperature of the TPU substrate was heated up to100 °C
corresponding MWs of UPy-terminated siloxane and feeding amounts and kept for 1 min, the thermal release tape was released and the cir-
of UPy monomers. cuit pattern ULPC film was mounted to the TPU substrate. In step 3,
similar to pick and place technology, we placed surface-mounted
Preparation of small-molecule modulator (UPyMC) devices chips and components on the circuits. In step 4, the circuit was
The prepared UPy-NCO (292.0 mg, 1.00 mmol) was dissolved in placed on a heating table (120 °C) to adhere electronic components to
chloroform (10 mL), then methyl carbamate (90.1 mg, 1.2 mmol) dis- ULPC-TPU.
solved in chloroform solution was added dropwise. After reacting at
60 °C under the protection of nitrogen for 6 h, the solvent chloroform Thermoforming process
was removed, and the solid product was washed 3 times with 30 mL The 3D mold used during the thermoforming process was fabricated
portions of acetone to remove unreacted methyl carbamate. UPyMC by a digital light processing 3D printer with heat resistance resin on a

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stainless-steel half sphere. Next, a 2D planar TPU film with the neces- 7. Huang, Z. et al. Three-dimensional integrated stretchable electro-
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Mechanical characterization electrical interfacing in high-resolution stretchable circuits. Sci.
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(300 ± 2.80 μm). Tensile tests were conducted on AMETEK TCM 100 electronic devices. Adv. Sci. 8, 2004170 (2021).
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Further information on research design is available in the Nature 23. Yamagishi, K., Zhou, W., Ching, T., Huang, S. Y. & Hashimoto, M.
Portfolio Reporting Summary linked to this article. Ultra-deformable and tissue-adhesive liquid metal antennas with
high wireless powering efficiency. Adv. Mater. 33, 2008062
Data availability (2021).
The authors declare that the data supporting the findings of this study 24. Oh, E. et al. Highly reliable liquid metal-solid metal contacts with a
are available within the article and its Supplementary Information files. corrugated single-walled carbon nanotube diffusion barrier for
Extra data or source files are available from the corresponding author. stretchable electronics. Adv. Funct. Mater. 28, 1806014
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